Volumes 1-5, 7, 10, 11, 13. 14. 16, 17, 21, 22. 23-27, 29. 31 are out 01 print.

Pill’ MID

8 9 12 iSa

18a 18b t9a 19b 20 28 30 32 33 34 35 36 37 38 39 40. 41 42 43 44 45 46 47

Fundamentals of Numerical Reservoir Simulation Fundamentals of Reservoir Engineering Compaction and Fluid Migration Fundamentals of Fractured Reservoir Engineering Fundamentals of Well-log Interpretation, 1. The acquisition of logging data Fundamentals of Well-log Interpretation, 2. Tire interpretation of logging data Production and Transport ofOil and Gas, A. Flow mechanics and production Production and Transport of Oil and Gas, 8. Gathering and Transport Surface Operations in Petroleum Production, I Surface Operations in Petroleum Production, II Geo/ogy in Petroleum Production Well Cementing Carbonate Reservoir Characterization: A Geologic-Engineering Analysis, Part I Fluid Mechanics for Petroleum Engineers Petroleum Related Rock Mechanics A Practical Companion to Reservoir Stimulation Hydrocarbon Migration Systems Analysis The Practice of Reservoir Engineering Thermal Properties and Temperalure related Behavior of Rock/fluid Syslems Studies in Abnormal Pressures Microbial Enhancement of Oil Recovery — Re~enl Advances — Proceedings ofthe 1992 lOternational Conference on Microbial Enhanced Oil Recovery Asphaltenes and Asphalts, I Subsidence due to Fluid Withdrawal Casing Design — Theory and Practice Tracers in the Oil Field Carbonate Reservoir Characterization: A Geologic-Engineering Analysis, Part II Thermal Modeling of Petroleum Generation: Theory and Applications Hydrocarbon Exploration and Production PVT and Phase Behaviour ofPetroleum Reservoir Fluids

Department of Petroleum Engineering Heriot Watt University Edinburgh, Scotland



1998 ELSEVIER Amsterdam



New York Oxford




PREFACE NOMENCLA1’URE l:l 1.2 PHASE BEHAVIOUR FUNDAMENTALS RESERVOIR FLUID COMPOSITION PhASE BEhAVIOUR I’urc (‘onipound (‘or rcspondi rig Stales Multiconiponent Mi’xture (‘LASSIFICATION OF RESERVOIR FLUIDS l)ry Gas Wet Gas Gas Condensate Volatile Oil Black Oil REFERENCES EXERCISES 3 4 It) IS

Library of Congress Cataloging in Publication Data A catalog record from the Library of Congress has been applied for.



1.4 1.5

24 25 25 27 28 29 30 33 34 34 36 40 41 42

2.1 2.2

FLUII) SAMPLING Well Preparation Sample Collection PVT ‘l’ESTS 38 2.2.1 DryGas
2.2.2 Wet Gas

ISBN: 0 444 82196 1
© 1998 Elsevier Science By. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior written permission of the publisher, Elsevier Science By., Copyright & Permissions Department, P.O. Box 521, 1000 AM Amsterdam, The Netherlands. Special regulations for readers in the U.S.A. — This publication has been registered with the Copyriglil Clearance Center Inc. (CCC>. 222 Rosewood Drive, Danvers, MA, 01923. Information can be obtained from the CCC about conditions under which photocopies of parts of this publication may be made in the


2.2.3 Black Oil 2.2.4 Gas Conclensate 2.2.5 Volatile Oil EMPIRICAL CORRELATIONS 2.3.1 Black Oil Rubble Point Pressure Gas in Solution Oil Formation Volume Factor Total Farina lion Vo/unre Factor Oil Density Oil Viscosity 2.3.2 Natural Gas Volumetric Data
(;~ Viscosity


67 68 70 70 71 73 77


U.S.A. All other copyright questions, including photocopying outside of the U.S.A., should be referred to the publisher.
No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods,

products, instructions or ideas contained in the material herein.
®The paper used in this publication meets the requirements of ANSI/NISO Z39.48 1992 (Permanence of Paper). Printed in The Netherlands.

2.4 2.5

Formation Water Water Cr,ntent of hydrocarbon Phase ll’ drocarbon soluinlity in Water 5 Waler Formation Volume Factor Compressibility of Water Waler Density Waler Viscosity REFERENCES EXERCISES

80 83 86 87


93 95 99


CRITERIA FOR EQUILIBRIUM Chemical Potential Fugacity Activity EQUILIBRIUM RATIO Raoult’s Law Henry’s Law Empirical Correlations REFERENCES EXERCISES 270


107 108 Ill III 112 114 116 125 127 129 130 131 132 138 140

6.4 6.5


241 247 249 253 254 258 260 260 265 266 270 270 273 277 279 281


MISCIBILITY CONCEPTS Miscibility in Real Reservoir Fluids EXPERIMENTAL STUDIES Slim Tube Rising Bubble Apparatus Contact Experiments PREI)IC1’ION OF MISCIBILITY CONI)ITIONS First Contact Miscibility Vaporising Gas Drive Condensing-Vapor ising Gas Drive REFERENCES EXERCISES



3.3 3.4

4.1 4.2

VIRIAL EOS AND ITS MODIFICATIONS Starling-Benedict-Webb-Rubin EOS CUBIC EQUATIONS OF STATE 4.2.1 Two-Parameter EOS Soave-Redlich-Kwong EOS Peng-Robinson EOS Volume Sh~fl 4.2.2 Three-Parameter EOS Schmidt-Wenzel EOS Patel-Teja EOS 4.2.3 Attraction Term Temperature Dependency MIXING RULES 4.3.1 Random Mixing Rules 4.3.2 Non-Random Mixing Rules REFERENCES EXERCISES


7.4 7.5

141 45 146

8.1 8.2


285 285 288

149 153 154 158 162 165 167 168 175 179 183 189 192 195 197 198 2(X) 201 203 206 209 210 210 215 8.3 8.4 8.5

292 295 297 301 302 302 308 310 314 316 318 319 320 322 323 324 325 325 327 330 330 331 333 334 338 340 345 349 353 385

4.3 4.4 4.5 5. 5.1 5.2 5.3 5.4


GROUPING Group Selection Group Properties Composition Retrieval COMPARiSON OF FOS Phase Composition Saturation I’ressure Density Gas and Liquid Volumes Robustness TUNING OF EOS Fluid Characterisation Selection of EOS Experimental Data Selection of Regression Variables Limits of Tuned Parameters Methodology DYNAMIC VALIDATION OF MODEL Relative Permeability Function Viscosity Prediction Implementation EVALUA’rION OF RESERVOIR FLUID SAMPLES REFERENCES EXERCISES




5.5 5.6

6.1 6.2

EXPERIMENTAL METHODS Distillation Gas Chromatography CRITICAL PROPERTIES Lee-Kesler Correlations Riazi-Dauhert Correlations Perturbation Expansion Correlations DESCRII9’ION OF FLUID IIEAVY END Single Carbon Number Function Continuous Description




221 222 223 227 228 234

9.5 9.6 9.7.



NOMENCLATURE a A b B lI~ It, B C~ C, f G h


Reliable measurement and prediction of phase behaviour and properties of pet rolciini reservoir fluids are essential in designing optimum recovery processes and enhancing hydrocarbon production. This book explains relevant fundamentals and presents practical methods of determining required properties for engineering applications by judicious review of established practices and recent advances. Although the emphasis is on the application of PVT and phase behaviour data to engineering problems, experimental methods are reviewed and their limitations are identified. This should provide the reader with a more thorough understanding of the subject and a realistic evaluation of measured and predicted results. The book is based on the material developed over many years as lecture notes in courses presented to staff in gas and oil industry, and postgraduate students of petroleum engineering. It covers various aspects of the subject, hence can he tailored for different audience. The first two chapters along with selected sections from chapters 3 and 5 can serve as the subject matter of an introductory course, whereas the rest would be of more interest to practising engineers and postgraduate students. Ample examples are included to illustrate the subject, and further exercises are given in each chapter. Graphical methods and simple correlations amenable to hand calculations are still used in the industry, hence they are included in this hook. The emphasis, however, is on the more advanced compositional approaches which are attaining wider application in industry as high computational capabilities are becoming readily available. I would like to thank Professor DII Tehrani for reviewing the manuscript and valuable suggestions stemming from his vast industrial experience - Also, I urn grateful to Professors M. Michelsen and C. Whitson for their helpful comments on sections of the book. Much of the material in this book is based on the author’s experience gained through conducting research sponsored by the petroleum industry, at Heriot-Watt University. I am indebted to the sponsors, my students and colleagues for their contributions that made this book possible. In particular, I would acknowledge valuable contributions of Professor AC Todd, Mr F Goozalpour, Dr DII Xu, Mr K Movaghar Nezhad and Dr D Avolonitis. My son Amir cheerfully helped me in preparing the hook graphics.

H I1~ h 1 k k, k,~ k,, K K~ m M n N N~ P P, P1 P5 0 P~ R R, S ‘l I~ ii
V ~

attractive terni parameter of equation of state dimensionless attractive term parameter of equation of state repulsive tcrm(co-volume) parameter of equation of state clinrensiontcss repulsive term parameter of equation of state gas formation volu mire f~ic tor oil I urinaliiiir volt: lire factor total formation volume factor gas isothermal compressibility coefficient oil isothermal compressibility coefficient fugacity Gibbs energy height molar entha!py total enthalpy Flenry’s constant partial molar ent lIi~l PY peruieahility binary interaction parameter gas relative permeability oil relative permeability equilibrium ratio Watson characterisation factor slope in ~scorrelation with temperature molecular weight (molar mass) mole or carbon number number of components number of pseudo-components presstire bubble point pressure convergence pressure parachor vapour pressure universal gas conslant gas in solution specific gravity, relative density at 288 K (60 “F) temperature irorrirat hoihiig point temperature iriiitar :nlcini.r! enci gy
imiolar votunie velocity

V x, y,

Z Z 55

volume mimic fraction mole fraction in vapour phase mole fraction compressibility factor Rackett compressibility factor

GREEK LETI’ERS a temperature dependency coefficient of attractive term mean value parameter of r distribution function activity fugacity coefficient parameter of r distribution function calculated critical compressibility factor total number of phases chemical potential mass density molar density interfacial tension lowest molecular weight in F distribution functiomi acentric factor EOS parameter coefficient activity coefficient any phase St JPERSCRI Pt’S F h o 5 Cj ~ ~y s~ K V W Iced. imrixliile hydrocarbon phase liquid phase reference state saltmration vapour l)hase water phase j.t p Pu ~ t (i) SUBSCRIP’I’S I) C LI ~ (I It base or bubble point critical point differential liberation process gas e It 0 ACRONYMS hbl r s w hydiocarbirmi oil reduced property salt w.mter = value/valtmc at critical point B IP CCE CGR CVD DL EOS GOR GLR GPA GPM barrel binary interaction parameter constant composition expansion condensate to gas volumetric ratio constant volume depletion differential liberation equation(s) of state gas to oil volumetric ratio (Sc) gas to liquid volumetric ratio (Sc) Gas Processors Association gallon of liquid per thousand cubic feet of gas (sc) IFT interfacial tension MMP minimum miscibility pressure MME minimum miscibility enrichment PNA paraffins-naphthenes-aromatics PR Peng-Robinson EOS PT Patel-Teja EOS Sc standard conditions SCF standard cubic feet SRK Soave-Redlich-Kwong EOS STB stock tank barrel SW Schmidt-Wenzel EOS TBP true boiling point temperature VPT Valderrama-Patel-Teja FOS 7JRK Zudkevitch-Joffe-Redlich-Kwong EOS xi .

Altirotmgh a reservoir litmiut may he composed of many thousands of compounds. whereas oils are predominantly composed of heavier compounds. is generally treated independent of tire water plrase. affecting all aspects of petroleum exploration and production. tire phase behaviour fundamental s can be explained by exami 0 ing the behaviour of pure and simple mrrulticonrponent mriixiurcs. wet gas. but to hicilitate tIre application of tire technology in the industry. Reservoir fluids . volatile oil and black oil. its geological maturity. lateral and vertical compositional variations within a reservoir will he expected dumring the early reservoir life. gas condensate.1 PHASE BEHAVIOUR FUNDAMENTALS Petroletim reservoir fluids are composed mainly of hydrocarbon constituents. therefore. I RESERVOIR FLUII) COMPOSITION ‘lucre are various hypotheses reg~ridiirgthe fornratiorr of petroleum from organic materials. This behaviour is of a prime consideration in tire development arid management of reservoirs. The influence of water on tIre phase hchavioumr and properties of hydrocarbon fluids in most cases is of a minor consideration.s and sonic light non-hydrocarbon compormnd. are formed. The behaviour of a hydrocarbon mixture at reservoir and surface conditions is determined by its chemical composition and the prevailing temperature and pressure. known as hydrates. The behaviour ol all real reservoir fluiuls basically follows the saline principle. Water is atso present in gas and oil reservoirs in an interstitial fonrr. reservoir fluids have heemr classified into various groups such as the (try gas. Reservoir gasses are mainly composed of hydrocarbon molecules of small and mediumni size. thence. The phase behaviour of oil and gas. Ihese views suggest that tIre coisrpositmon of a reservoir fluid depends on the depositionai environment of the formation. unless water-hydrocarbon solid structures.s such as nitrogen and carbon dioxide. Fluids advancing into a trapping reservoir may be of different compositions due to being generated at different times and environments. and the migration path from the source to trap rocks Ii].

However. as iso. The olefin series (~=0)have unsaturated straight chains and are not usually found in reservoir fluids due to their unstable nature. particularly for gas condensate fluids. API6 studied the composition of a single crude oil for 40 years.ine H H H H H—C— C—C —C— C—H I I I I ALKANES (PARAFFINS) I I I I I II II It II It iso-lie ranc II It— C~—H H tt I It I It I II C’ It HH H It— C— C— C— C— C I I II I II I It II— C— C— C— C= C I I I I ALKENES I II I II H Ii It H H I -Itexenc 3-Meltryt. the structural formulas of tire above groups of hydrocarbons with six carbons are shown in Figure 1. Reservoir fluids are commonly idcmrtilmcd by their constituents individually to pentanes. API-60 sttmdied petroleum heavy ends. liquid or solid phases. A . and 0. Light paraffins in reservoir fluids are sometimes identified and reported as those with a single hydrocarbon chain. The niajor classes are paraffins (alkanes). For example. where no changes will occur with time if tIre system is heft at tire prevailing constant pressure and temperature. This can also result in compositional grading with depth. and oils containing bight concentrations of asphaltic material.. tohuene and xylene are often individually identified in the extended analysis of reservoir fluids. The subject of phase behaviotmr. H2S. A phase is defined as a part of a systemli whtcir is physically distinct from other parts by definite boundaries. as normal.I Pentene / H\ . they cannot all be identified and measured. or c02 have also been discovered.~ -~ H /11 c\tt I/It C~ H I1\~ H~ ~ It I H/NC ~C\ 11 Benzcne I /\ It C’yclotrcxanc NAI’IIrIIENLs AROMATICS Figure 1. in different solvents [6]. 6 7 hydrocarbon compounds can be expressed by the general formula of Ci1II2Irf~with some sulphur. N~rphthrenes~mmr(h aromatics form a major part of C6-Ct t groups and some ofthem such itS methyl-cycio-pcntanc.c I. Reservoir Fluid O~nrposit:on 3 are generally considered to have attained equilibrium at maturity due to molecular diffusion and mixing over geological times. The naphthenes are cyclic compounds composed of saturated ring(s) with ~=0.1. These compounds such as carboids. The aromalics (~.2 PIIASE BEHAVIOUR Reservoir hydrocarbons exist as vapour. bcnzene. 1.. C ’s.inrd API-Sti respectively. particularly the rock-fluid behaviotmr.. nitrogen. The compositional analysis of reservoir fluids anh their characterisation will be discussed in Chapter 6. and others with branched chain hydrocarbons. H H— C— H It H II— II H It II I I I I I I C— C— C— C— C— C—li I I I I I I II II U H It II Norinnat Icx. A reservoir oil (liquid phase) may form gas (vapour phrase) during depletion. and aromatics as groups is commonly referred to as the PNA test 141Further information on the structure of reservoir fluid comnpounds and their labelling according to the IUPAC system can he found in [SJ. t’lrase Helun’. The paraffin series are composed of saturated hydrocarbon straight chains with ~=2. oxygen and minor metallic elements mostly present in heavy fractions. oxygen and sulphur are found in light and heavy fractions of reservoir fluids. Hydrocarbon compounds are classified according to their structures. this behaviour is of considerable interest for near critical lluids. API 52 .ou r Fiinukun:e. which determine the value of ~. A number of comprehensive research projects sponsored by the American Petroleuni Institute have investigated crude oil constituents and identified petroleum compounds. S. and aromatics.. naphthenes. The test to measure the concentration of paraffrns. asphaltenes and resins are identified by their solubihity. and heavier compounds are reported as groups consrposed mostly of components with equal number of carbons such as C6’s. Nelson [31 gives a review of petrolcumni chemistry and test methods used in the refining industry. Tire most common method of describing the heavy fraction is to lump all the conipounds heavier titan C and meport it as C +. Structural formula of various groups of hydrocarbons with six carbons. All the 7 possess the same compounds forming each single carbon number group do not necessarily number of carbons as will he discussed in Section 6. As reservoir hydrocarbon liquids may be composed of many thousand components. The formation or disappearance of a phase. I. The compositional grading and its estimiration based on thermodynamic concepts will be discussed in Section 5.. Gas reservoirs containing predominantly N2. The evolved gas initially remaIns dispersed iii the oil phase before forming large mobile clusters. or lack of it. The polar nature of these compounds can affect the properties of reservoir fluids. Nitrogen. oletins (alkenes). there are airrple evidences of reservoirs still maintaining significant compositiomial variations. or variations in properties of a phrase in a multi-phase system are rate phenomena. nitrogen and orgtrmiomricttrlhic compremnds of crude oil strniptcs were investigated in projects API-48. naphthenes.i~i!. However. carbenes. The crude oil composition is of major consideration in petroleum refining. particularly tatcially as tIre dill usi ye rrixing may require many tens of million years to eliminate coiripositmonal hmclcmogeiiuit cs I 2 I Furthermore.3. Polycychic hydrocarbons with fused rings which are more abundant in heavier fractions may contain N. disproportionally higher than tlreir concentrations [7]. however. Cg’s. the concentration of hydrocarbon components belonging to the same structural class are occasionally measured and reported as groups. but the mixture is considered as a two-phrase system in botlr cases.1. For operatiomial puposes. 1.2 1. These heavy compounds may be present in colloidal suspension in the reservoir oil and precipitate out of solution by changes in the ~ tcmrrpcratumre or comnpos!tiomrs occurring durimig production.=-6) are unsaturated cyclic cotripounds. focitses only on the State of equilibrium.. the pressure and the temperature increirse with depth for a tluid column iir a reservoir. ihe sulphur. liighly detailed information on the constituents composing a reservoir fluid is not of very muchr use in exploration and production processes.

Ihey hcconie equal at conuhitions kmiowir as tire Critical point. shtowrr by ® in Frgurrc 1. The term property throughout this hook refers to intensive properties. A phase composed of N components is fully defined by its number of irrolcs plus two thermodynamic functions. Fluids at equihihriumm are also referred to as saturated fluids. where tIre ularker shadmrrg corresponds to a iriglrer density. go me I . the nunrber of independent variables. are not real.2. The assumption of equilibrium between fluid phases in contact in a reservoir. and chenrical potential of each component throughout all phases should be unifornrr at equilrhriunr conditions.. Phase Behan’iour Fu. The intensive properties are those which do not depend oil tire amount of material (contrary to the extensive properties). This plot is known as tire Cox chart. Tire superheated vapour F can he chranged gradumally to tIre compressed liqumid F. The boiling point. It is thre only poirrt where the three phases cart coexist for a pure system. Indeed. is unsaturated single phase as required by the phrase rule.: F = K(N+l)-(N+2)(K-l) = The line AR on Figure 1.All tIre conmporrrrds slrow a sirmnilar tremid.eu’onre t/iC . however. are tire niaxilriuni terriperature arid me at which ii proe conrpororil cirur fomnmr coexisting ilrascs. The scale. can be determined by identifying either its pressure or its tcnrperalume. At equilibrium. therefore.2. of some compotrnds foundt in reservoir fluids are given in Table A. The fluid above and to tire left of the line is referred to as a compressed or under saturated liquid. the temperature. temperature arid prcssurre are specified. I in Appendix A. Tire discontirruity across the vapour-pressure curve becomes less significant as tire temperatui’e increases arid vanishes above tIre cmitical poirrl.Sa?tiC uiiid iF. tIre vapour and liquid rlemrsiries bccorrre equal at tIre cnrtrcat point. necessary to (lefirre a multiphase system is given by. x is the mole fraction of component i. The state of a phase is fully defined when its conrposrtion.arid tIre critical pressure. Tire lure AD is the solid-vapour equnihihriunr line or the suhlitrratmon curve. P. wlrereas that heiow and to the right of tIre line is called a superhreated vapourr or gas. The line AC is commonly known as the vapour pressure curve. that is. presstrr’e. Figure 1. All the conditions at winch tire vapour and umquid phases can coexist at cqtrrlmtamrrrir are shown by the line AC. which is an adjusted reciprocal of the absolute temperature. which is also krtown as tire mrrclting point curve. as will be described in Chapter 3. that is. However. The state of the equihibriurm of a vapour-liquiuh mixture of a pure lluid. I) A triple Ponni Vapour tennperatnnrc > Figure I . but simply extrapolated values. commonly tenrperatumre anul pressure. a pure corripound at a temperature above its critical value canirot be called eitlrer liqumid or vapour. lire variation of saturated fluid ulensity with teirrperature for a pure compound is shown in Figure 1.2 is the solid-liquid equilibrium line.6. OtIrer properties also show tire same tiend. The temperature corresponding to the atmospheric pressure is calleut tire normal boiling point or simply tire boiling point of the compound. F. the degrees of freedom is equal to three nrinus thc number of phases.4 1. This inrpuses (N÷2)(icI) constraints.rdamelrta/. Tb.3 shows tIre logarithm of vapour pressure plotted against an arbitrary temperature scale for some compouinuls. Any fluid at any otlrer pressure-tenrperatui’e conditions. I lence tIre vapour pressure values at temperatures above the critical temperatures.5. Thums. The densities of vapour and liquid phases approach each other as tire temperature i iru-reases. wimlr all tIre fluid constituents present in all the equilibrated phases.ce liehaeu~ur S system reaches equilibrium when it attains its minimum energy level. !‘ha. for a systersi with K phrases. is valid in engineering applications. lire continuity of vapour and liquid is scherrraticahhy strown in Figure 1.l 1.3. in most cases.. The intensive properties are. or so-called the degrees of freedom. has been selected so that the vapour pressures of water and most hydrocarbons can be exhibited by straight lines. Pure Compound The phase behaviour of a pure compound is strowir by tire prcssurc-teiriperutrrre di:rgrurnrr it Figure 1.(IiStiprh’i415/i(1ble at tire (‘ritical point. Critical Poini 8 A Solid ii. Wi tirout any abrupt phrase cirange. as it shows tire pressure exerted by the vapour coexisting with its liquid at any temperature. where. Pressure-temperature dragrrrmrr of pure suibstairce. lterrce. but constrained by. A pure substance cannot exist as liquid at a temperaturre above its . The number of independent variables to define such a system is determined by the Gibbs p/rose rule descrihet as follows. All tIre differences between tire phrases are re(Iuced as the system approacires the critical point.4 shows I Ire variation of saturated Ii uid chensr Iy with temperature for a nurmrrbcr of prime Irydroearbomrs . determined by only N+I variables a~ tire concentration of components are not all independent.2. All the intensive properties for such a phase at tire prevailing conditions are tmxed and identifiable.2) For a single-component (pure) system. 1 The ternrs vapour and liquid are ret’erred to the less and the more dense phases of a fluid at equilihriunr. thiough an arbitrary patlr EG F. I leirce. N - K+2 (1. (II) critical temperature. a system may form of a nunrber of co-exiting phases. the p/maces i. such as the density and tIre specific heat. tire total 1 number of variables are equal to rc(N-f I). l’hre intersection of the vapour_liqummd and liquid-solid lines ts the triple point. TIre density at e~rclrpoint is sirown by the shauhing intensity. ‘Ilre en mciii tenrrperatrire. I~. The solid carbon uhioxiule (dry ice) vaporising into its gaseous form is a common example of this region of the phrase behaviour diagram. by N÷2variables. as will be disctmssed in Chapter 3.

’ 700 ~ ~00 000 Temperature.67)/l. Vapour pressure of normal paraffins..r Fwrda. U.2. ‘-~—-~ ~ ~ LE~L 7Z L 2 7 . :i~_~:. homer 181 wiih permission. - 2 ~ ~ ~ ~ ~ 0 ~ ~4 200 ~ 00 iso 250 300 350 400 450 500 350 600 no. °F K=(°F+459. °F K=(°F-f459. Figure 1. 0~ IL. Figtmre 1. Phase Behaviour 7 t-i--~ ~ j~.re.-~J - L- 1000 -IL ~ no 2 !L~i~ H~ ~ -~ moo mOO no V “I U.006895 psia Rcpnnxiuccd Temperature.s 1.3 (Coin).m. McGraw-tlitt Companies Cnnpyrigtrn. Phase Belrannon.8 MPa=Q.8 MPa=O. Vapour pressure of normal paraffins.6 1.67)/ 1.006895 psia McGraw. Rcprnstuced fioi~n I~! s~iitrpermnnicsionn .3.‘O U.url.Hitt Companies Copyright.

McCraw-ttilt Coninpanies Copynigtnn Reproduced from 81 wiih permission. Saturated fluid density of pure compoumnds (curves iderrtilred by letters are related to binary and multicomponent fluids described in Reference 8). at Point 13 where tire first bubble evolves.2. As tine liquniul is relatively incomrrpressiblc tine finn uI expansiomn is small until tire vapour prcssnrre is reaclred.oF Figure 1. ~h’lnis point.K 200 250 I.rtat.me Rehannonrr Fnondamnre.r 1.5. . For a pure substance Ilie pressure remlrai us constant mmd equnal to tIre vmrpourr pressure.6. at a tercrperature below tire critical temperature. . (‘onsider tire corrrpresseul hiquniul. lbe reductiomn of fluid pm’cssure at constant teirnperature increases its volume.8 I.. ~ 10-44151 41401 ‘!•iUIU ________ H II fttiWH-ft1t-tt fH+HIfH P-H-I-/ ftt±1-i’H±H+~f+H1-I-H+H-fl rLIFHU —100 0 tOO 200 A ~tiIi~iJllhI!~ Ill~ftI~FI~IIt1 ~1f~-~’IU U~I-~-tf~f~UIt II~ ~B ~ ~t Ii~A LflI ~Yt-14 ~kY U •1 700 a C. 300 350 400 450 S00 550 600 650 A San urmued I _rquiul C I) C il Hifli It I U Saunnr~niedVapour ‘tennnpr’rarure f I I ~‘&I I I 1f~ITU uigure 1.7. Temperature.. Point A. until the last drop of tire liquid virponises.. Phase Behaviour 9 Temperature. where tIre vapour is in equnilihrnumrr with an imnfinitesimnral anrnount of hiqtnid is called tIre utew poinn. Point I). 1enrnpermninrre > Cnipyrngtii Reprnstnncent trim - 30C 400 500 600 ll~llt~ll~ ii Irginr’e I . Vamiatiomrs of saturated tluid density with tennperature. Further exparrsioin of tire systeirn results un chi~rmiginigtire liquid iran tire vapour phn:ise. TIne pressure—volunre diagram of a pure substance is shown in Figure 1. a consequmence of tire phase rurle.4. Pha.. Mc(Ir~nw-Ititt(‘onnipannies IS! with pernnnnssionn. (‘ontinltrity oh’ vapour anul hmquid.

The system bubble points at various temperatures form the bubble point curyc.( 1.’ !‘nondan. Poimni N. Tr. Z. The occupieul volume of one mole of gas at various standard conditions. ‘l’he cham’rge of plnase from liquid to vapour is accortmpan. the reduced pressure. Application of tlne correspondirmg states principle to the vapour pressure of pure compounds. Two Phase Regrnnin (1.95 rim ‘ItcgumIInt U 0. As omre minnIe of a hydrocarbon gas amnd one mole of air occupy the same volume at the standard comrditions.414 mnr /kgmot 23. or vice versa. Ii can he expressed. follows a similar trend.2. tire reduced temperature.3 in Appendix A). Molar volume of ideal gas at various stammdard conditions. In emrgimneering applications. An isothnermal expansion of a fluid at a temperature above the critical temperature does not result in any phase change. without arty change in tire mixture volume at the critical point. have been produced to improve the accuracy of predicted values (101. lime real vunlue of critical coirnpressibihity factor. S. particularly at elevated pressures.ne.96 kg/kgmol. Pressure-volume diagram of pure lluid.( 1.10 I. hence. calculated by Eq. Z~. Indeed the system changes front all liquid into all vapour. Pv=ZR~l’ Volume -> (1. P is (absoltmte) pressure. provides reliable estimates particularly for simpercritical gases and at low pressure conditions.ed by a large inncrcmrse in volrime mit low temperatures (Figure 1.5) Figure 1. The expansion reduces ax the temnnpcrature approaclnes the critical point.8. Note tinat tIre compressibility factor depends only unn the ratio of temperature to critical tcmnrperature (ahsolurte). Muir is the mrmolectmlar weight (mnrolar nnass) of air.1. and the ratio of pressure to critical pressure. th’te speciFic gravity of gas relative to air (relative density). known as the corresponding sta:e. Unit ~perarurc - ‘~ure. Any fluid within the phase envelope.V_olnrnne Frctd Mennic St 60(1 “F 271.nials 1. is given in Table 1.. ethane.8. t S K 2)18 K 14. as Pv=RT (1. I) Sg=MglMair whmere. trowever.3.nn.2. similar to Figure I . l’hne conmprcssihility chart.. Fine comnnpressihility factor can be deteurnined from various theoretical-empirical equations of state (Chapter 4). The pressure vokrnne relation for an ideal gas is. The bubble point and dew point curves appear as a single vapour pressure curve on a pressure-temperature plot for a pure compound. T >Tc Single Ptiunse - T<Tc A Table 1. shouhul Inave equal critical compressibility factor. hut specific to compounds such as rinetlrane. as.3) is extemnulcd to remit systemrrs by including a compressibility factor. is not thne same for all compounds crumble A. is simply determined by. which states that suhstamnces helrave similarly when tlney are at the same relative proxirinity to their criticmrl poimnts. This inrphies tlnat all substances behave similarly at their critical points. Phase Behaviour Ii N T=Tc where v is tire molar voltrmnie. The logarithm of vapour pressure of pure compounds approximately varies linearly with tire reciprocal of Iemsnperature as shown in Figure 1. whereas the dew points form the dew point curve.c principle. The two curves meet at the critical point and together identify the phase envelope. propane.7). equal to 28. Charts relating the compressibility factor to tIne reuluced pressure and temperature. forms two equilibrated phases with the vapour/liquid molar ratio equal to BM/MD. This fluid is called a supercritical fluid. Point M.6) Corresponding States All gases behave ideally when the pressure approaches zero. gases at tire standard conditions can be treated as ideal. Fq. 15 r- TIne above approach is based on a very inrportant concept. ‘F is (absolute) temperature. Hence one mole of any ideal gas occupies the same volume at a given pressure mmd temperature.4) l)ue to imrtermolecrilar forces remit gases din mint behave iulcahly.3) . and R is the umnivcrsal gas constant (Table A.7. or determnnined from a generalised chart for gases as shown in Figure I . I in Appendix A). Figure 1. therefore.69 psia I ann Its) kI’mn 380 tm~IIhriIot 1 22.3). P/ia Cf Behan’. Pv (1.1. however.

At the critical point P’IPC=TIF.:‘ a .: . falling oil the saline line. tins (hoes not occur. — - ~.28862 ln(T.: . ~ -~ - )‘1. Calcnniate the vapour pressure of normal hexane at 355. as the third pmrrannreter of tIne correspondimng states principle. plotted inn tIre redunceul form. 0 a ~_ 4 ~ - Tire acentric finctom Imas been widely accepted as the ttmird parameter in generating generahised correlations.f.: .13.ie l/e/nannonnr 13 ~ :. I at tIne reduced temrrperature of 0.t .7) winere P~ is tire vapour pressure amrd ~t annul ~2 are constamnts for eurch substance. U~ ~ ~ -.~)=~ (l~_L) 1 If tIre cor’respomnhing states principle were exact.l. ~ .444. -~‘/t.- .:Ii~ .92714 — 6. lIne imnchusiorm oh a tlnirul parmmrmlcter.) ~~ — ( I .. .0 1 (1. I in Appendix A. F=nnmnc/cznn.‘~‘.~.s to thee rnnolecinlmur structnnic shrould imnrprove tIne reliability of the coriespomrding states primrciphe. Pit~. amrd irntroduced the acentric factor.u:~. resulting nit (litleremit imnicrmnroleu-unlumr Iorues.. The values of acentnc factor for sonne connpoimnds are given in Table A. 4~ ~ — ‘5 T .. particularly tlrose related to fluid plnmse cqnmilibiia.~ ~ ?~T ~. as.09648 /(T.1 6934(T~ )5 )6 15. anul ph) are furcctiomns of the reduced temnrperature.9) I -~ i -:~ U~J~ 4~t 41H ~ t ~ tJ ~7 . :~ ~: 1:: ~ .1 .t’ t1=~. ~. tire vapour pressure curves of all line commipounds.4721 ln(T.~ ~ ~ t~’ I -... iriulccd lie on tine samnne curve wmtln a reduced vapour pressure of I). snicln as argon. .n’ !te/nnnlioin. ~ /2..= I . ‘. should have tIme sammne slope.~--- ..7. For examnnple. lIt)).12 - 1. (h) tire Lee-Kester equationn.) + 0. .~ ~ - ~ ‘ ~r~.j--’ 1 .--P ~ —~±~-—i~z t~ 4t~f ~I.-.0.f..~ ~i ~ ~ . t~Pir~ I:: ‘.* - I 4~ log(P. !‘/na. ..nqn0n/. for otlrer substances he selected the deviation of 7 tire reduced vapour pressure curve frommn tlnat of spherical molecules at Tr=O. based omr tIre corresponndinng states principle. . ~ 1~~U~ifi=~j ~. I. hence ~ t = c2 anul. using: (a) hire Cox drum. 1. lmr practice. ~.- = log(P’ I P.nrj’Ie 1.~s-‘TT . aduhtiomnal to tire rcduceul tcmmnperalnmre mmml pressure.j fl.~ -.~ I mi. 1. ~ . lIme vapour pressure of pure comcepounds can be reliably estimirated using the Lee and Kesher 1121 correlation whniclr is based on the three parameter corresponding stales.1S K. tIm 1- L o i_. (fl=—log(P’/P~)(. kryptomn and xemnon. Hence. ~1 he nhevrat mm of mrnoulels haseuh omi fire two parunmincler correspon(lr mrg states pm nc Iplc rs due tic uhi Iferemnccs in nmroleculunr strinctunres oh various commrpoummnuls. P’ /P = ~1 ~ I ~ I exp(f”” + ( fW) 0 (I. (1.r :~ ~tm 2 .er LIIJ noticed thrat tIne redunced vapour pressure curves of sinnple spherical rnrolecules.6875/(i~) .~ 2 ~~T~W: ~ 0 The ahuwe definition gives arc acerniric factor of zero for simple spherical molecules. svhnichr corncnmr.43577(T. It)) wlnerc... E~T~b~ o 0 ii L~n. z ‘-~°n°~i cli mqlscaldwo3 1 . I 8.2518— l5. ~ .~ / AI/~ ~ a 0 0 0 1t~t~~ = = 5. ~ —1.:t =:u —— . ) -I.) — 1..8) 0. ~t~t t. !-‘/no.~:~f t~t-L_. . . The acentric factor generally imrcreases with imncreasing size of iromologuc irydrocarhons. and positive values for otiner corurpourids except hydrogen and helium.~ . tlrat is equal ~ n . .

(X)83 144 MPa. TIre plrase diagranr of a mixture is determimned by its comtrposition.92444 v’.2 160 MPa.n(/(’.08775u (1. is: V=mnifp=I/425.ne. to he Z=0.69966 1” -2. 0.The greater the difference between the critical The values of ZRA for some substances [l5j are given jim Table A. am T=355. The donurpressihility factor. II . ummnd used in Eq.(I.796=0.1)009902 tim’ Multicomponent Mixture Fire phrase helmaviotmr of a mrrultr-comrnponnent system is more elaborate than that of a pure cninmpound.-m. ‘flme two curves meet at the critical point (C).30t3 1. Tineir phase beiraviour..0023 1 m’ . kg/kgmol 58.15 K (179. particularly in Chapter 4 dealing with equations of stale.5838 and T. K P~. as long as the mixture remains two ptna. Figure 1.15 MPa (21 psia). is very much similar to a curt imruilti-comnnponent reservoir fluid.l2).nlra.10.nt/me. 2. both the temperature and the pressure are imrulepeindemnl variables.3. The vapour density am the above conditions can be calculated from Eq.. p’ = M/v’ The volume of cylinder. tlnercfore.95 Lnuinn nd butane vol mm.K 425. Wlrat is mIne volume of liquid butane remaining in tine cylinder after comnsunninmg 0.306192 C” -2.12) V’ =0.(l. TIre phase helnavioumr of a hinany system. which results in: P’=2. at 393 K. kg/inn’ 4253 where the density. llme highest trressnirc (13) annul the higlmesl tenmrpcratumre (D) on the phrase envelope are emil lent tIre (rnu(n.13) The application of acentric factor and critical compressibility factor in developing generahiseul correlations will be described further. Tire locus of critical points is slrosvmn by tire daslned litre in Figures 1 . (b) The critical properties of normal hexane are read from Table At in Appendix A.ce 1?elntn. p’. conntrunn-y to Ilumnt for a punme conrrpounnul.=0.12 PC’ MPa 3. Fixaunple 1. it can he estimated from the Yamada-Gtrnn correlation 1161= ZRA=O.9. respectively.3 iii Appenmutix A.3 -440.( 1. rcspcclively. The vapour pressure can be calculated from the Lee-Kester equation.iou n /nnnndnn. 123/I .6 The umse of critical compressibility factor as the third parurnnetcr for (levellmpinmg genemumlisi. MI’un 0.4°’ (1.00235 I-V )< 57. /‘/na.m’/(K. although relatively simple. 507.i(je. line pinunse nile inruircuntes that inn a hmmrary vapour—liquid system. where mill dnfferences between lIme two plnunses vanislr and the phases beconne nmnnlistmngtnishiatnlc. Note tlnat tIre systemnn pressure decreases during ant isothermal expansion between its bubble and dew points. In 393 K.7). equal to time irormal butane vapoumr pressure.306921 P’. where the critical compressibility functor hrmms hecim replaced by the parameter ZRA. rs bouiimulcd by tIme buibble poimrt mmmmul chew point curves.2. Z~UT. the vapour pressure is remid eqniuml to 0.796 7~ 0.3=0.67.5 kg of botanic? Solution: Reading the critical properties of normal butane from Table A. A more reliable estimation ofthe liquid molar volume is expecteul front the modification of the Rackett equation by Spencer and Danner [141.9244. to be 0. inside which the two phases coexist.00. I Icncc.8. from Table A.mmmd tIre cri(o. I in Appennutix A ammul substituting them in Eq. exceeds the values of boOm commipomnents as pure.123 T~.11 shows the phumse diagram of etlmane-Imeptanie sysnenn. no read fronmr Figure 1. Ann exmmnrpie is tIne Racketl equation [131 for the saturated mnrolar volume of pure comnnpounds. therefore.216/3. TIme pressure-temniperattmre diagram of a binary mixture is sclnennatmcatiy slrowim inn Figumre 1. Z. 5 nrr=Vn ~4 v p~ 1 t).1=57. the phrase envelope. Calculate the density of saturated normal butane liqumid at 393 K. Reservoir fluids are mainly composed of Inydrocarhons with smnmrlar structures. sinrihar to that in Example 1.1. v~ = (RT / P~ (1.lO) to calculate the vapour pressure as follows: MPa 3. 0. using mice Ruickeit equation. ‘l’lce critical temperature of different islixtures lies hetwcenm tIne critical tenrmperatures of tIre two pure comrrpounds. known as the Rackett compressibility factor. has been calculated as. however.2730 r. nrn’/mnnt 0. The universal gas constant is read.14 Solution: 1. I in Appenulrx A.and v~are the saturated liquid and critical molar volunnes. an appropriate substitute for explaining tine qunalituntive betmaviounr of reservoir lrydnx_’arhon mixtures.ces at 393 K. The critical pressure. v = T.’d correlations to predict volumetric data has also proved successful.=P/I’~=2.6 ‘F). 5containing 1kg of the satunrated liquid butane.13665 Don siny. we ohtaimr: M.1504 Tlre cylinder pressunre remnnains curnrstmnnn. It is. l’/na.I~I/ Jm = I IX)) mmn’/kgmrnot. ummrnt tIm’ vap~nnnruhemisity is 5 5 p =M/v =58..11) where v~. v’ / v = ‘/.kgnrol). ‘l’lmc comnmplexity gemnerunlly conrmpounds as components with widely differemrt structures mmd mrnolecular sizes corriprise tIme system. is not generally highly cnirmplex. A cylinder contains I kg of satunrated liquid humane at 393 K. Eq. in most cases. For oIlier compounds.95 kg/inn’ lIne minass balance resumlts inn.025 m 0. None tlmat tIre two plrases can coexist mmt some c(inditions above tire critical pnnnmrt .(I It)).29O56-O. at prevailing reduced values of: P.nan/s /.ce !?e/rannonnr 15 (a) From Figure 1. rlre piessure-voluimme diagram of a binary mixturre is schematically shown in Figure 1.5=V x425.

Mcflraw. A rrumber of mnlixing nrles have been proposed. 16) to Figure 1.. Imowever. Pseudo critical properties of a mixturre are calculated by applying a mixing rule to the critical propertmes of its constituents.nne. instead of true critical properties in applying fluid niouhels develuiped for ptrre strbstances.nt.. the higher the mixture critical pressurrc earn rise as sinnnwn nm Figure 1.0~~ (1.nni f81 winin l~enmnissonn . mmmcui volimmmre.71 4 77t)9 5 58. pseudo reduced tennrpenatuire: n-i. K Figure 1.10. B C A I) wlrere /. such as those in Figure 1.nn’nmr Fnnpnnla. such as. is also used for mniuhitcomurponenrt systetnrs. IS) ~ (I . Phrase diagram of etlrane — normal hreptane. P/nose Re/mnn.9. amnd Eq.ipyrig)ni Reproclunceut frn. Figure I . Pseudo cmiiical values mire used. Schematic pressure—tenniperature di~ngrammmof mm birnary mmrmxlunre. Pressure-volume diagram of binary mmxtures. . is lice cnnticmul properry of comnponemmt i.(l. 9 8 ‘1’ I T2 C Criiicat Poini 0~ C) 7 6 m. Properties scaled relumnive to tine pseudo crnnical vunlumes are referred to IIS pseurdo reduced properties. such as tetnrperature. ns tIne mrroic inuncninnn. and.}tnhl Companies C’.11 . described for pumre stibstances.8.12.zI. ‘lime cnnrrespomnding slates prmrrciplc.te% citnanne I i()0.71 6 2654 7 790 8 1012 9 4.s I 2 I’/nase Aelmavionnr 17 points of the two components. No binary nrixture can exist as a two-phrase systenn outside tire region boummdeul by the locus of critical points. pseudo reuluced pressuire: ~ Temperature > = = l/~T~ (I .16 I. mnnnd 0. but molar averaging. is the most common rule. ~0 a 0 pressure.3 2 ‘i/tnt it 250 300 350 400 450 500 550 600 Voiunne > Temperature.05 it) 000 a 5 A 0~ 4 1:1 Vapniur 0 U .00 2 9685 3 88.Il).14) is unmry pseudo critical property. also known as Kay’s nnixinng rule.

Thmem are.18 I. as evidenced in Figure 1.13 slrows that there are two dew point pressures at any termmperatunre for retrograde gases. P/nose 8e/nnr. Figure I .cutw. Figure 1. is of little interest in reservoir operations. Tire upper dew point is sometinres called the retrograde dew point. 0~ (a 0~ 4 2 () Tennperature.mdo value. forms the first drop of liquid at tine dew poinit.15. however. Tine lower ulcw point is of little practical significance for most gas condensate fluids. This behaviour. which earn mnlso he cunllcd rerograde cuindeirsation. TIre vapour-liquid phase diagrannm of In typical mnulti-connponent system. however. An isothermal reduction of pressure for a vapour-like fluid. Further reduction of pressure will result in further condensation. Note mlnunt tIme mrhove behaviniuir occurs only if the gas temperature lies between the critical temperature mind Ihe cric(imrdentlnemnmr. Tlre cuindensation will cease at some point. simown in Figure 1. describes lIne helmaviour of reservoir fluids inn nnnost cmtses.°F Figure 1.12. at 160°F. wlmcrc pressure reduciiomr resumlts jim comndensation is referred to as tIme retrograde region.c 1. e. McGraw-Hill Conrnpunnies Copyrngirn 181 n~imtnperunissiorm. 13. Time relative posilion of tIre critical poimin to the cricotrdentherm and the cricondenbar on the phmmse emnvehope can lead to other retrograde plnenomena. K 100 ISO 200 250 A typical phase diagram of multi-coisrponent system at constant composition is shown in Figure I. Critical loci for binary mixtures.3. and the condensed phase will revumporisc by fuirtlmer reduction of pressnire. Weinaug and Bradly [171 observed an unusual belmaviour for a naturally occurring hydrocarbon ninixture as shown in Figure 1. are different from the pseundo values calcumlaled by averaging. 12. however.n. Vapour and liquid phases coexist at any pressure-temperature conditions within the phase envelope. 14 shows that an isobaric iircrease of tenipcratune from poinrt I to point 2 results inn condensation. exceptional cases.13. as indicated by tIre qumality lines. Reproduced fronn . Smmrmmll pressure or Iennperature changes at a region near the critical point cause mrlajor phase chamngcs. P/muse Belman’ionnr 19 Tire true critical properties. limat rmmisirmg tIne tcnmrpcralumre of a high pressure rich gas may not be a proper iirocedimre to avoid conulensation inn fluid haimdling. This plretromenon is known as the retrograde conden. Point D. Tlre vaporisation of liquid by isobaric tennnperature decrease. The prediction of true critical properties will be ulescmiheul inn Section 5. Note that an isothermal reduction of pressure. Point A.2. or by isotimermal pressure increase is known as retrograde vaporismution. 300 350 400 451) Crinical Poinmi 12 A Ii) U 0~ 8 ~1 in tcnnnperamure > 0~ as a is a) a is Figure 1. Note ttrat tIne distamice hetweemr iso-volume or quality lines decreases as the critical point is mmpproached.g.16. It indicates. 13. Plnmtse dimmgramn of a mnulticomponent mixture. Tire liquid/mixture volumnietric ratios are sirown by the constant quality lines. Temperature. Point B. Figure I . The true critical pressure often shows the irighest deviation froirn tIme psen.u’nnn Fnundunnnrenikn!. TIme shaded region of the phase diagram.

A simrrilunm behaviour has also been reported [18] for a multieorrrponenrt Irydrocarhon oil. prior to belraving normally again.nie. pp Temperature > A single plnunse Iryuhrocarbonr reservoir flumnd may fornn rrnore (Iran two phases uhumimrg depletion. fl t4 Figure 1.2 0~ -. Liquid % 0 U 0. l’I.14. or senini—solnd pbrunses.n. rich in lrychrocarbotm connpounnds of different lnonrologous series.15.- But.5 Fngunne I . mnray corndense two imninriscible liquid pirumses. hyulrocunrhomi ricin coundensate phase. is nIne cIrzmmnge un molar volumes of the two phases. such as aspiraliemies can formrn at sonume conulinions.. ‘a 0 K=(’Fm-459.. 270 pa 27. Retrograde condensation at constant pressure.mC. 21 results in an increase of the liquid volume after an imiitial norrnnuml helraviounr. The calculated gas to liquid ratio mn mrnoiar nermir is showtm also inn Figure I. The reason for the apparent disagreemennt between tlnc two plots. as expected. Retrograde vaporisation at constant pressure. 5% Curve SI C I I) — A tni.ifa/c /2 /‘/iace !/eIn. I 6.use fle/nani. . I /1 ‘ Sm.ou.20 I.Ic R. 17. The ratio increases very gradually over line winnie tested pressunme rairge. l’lnasc uhnmngmmmmmi of a hnynlm ocmnn horm nnixtumre SPF Copyriglnn.17. eaclr rich with one structural type of molecules. Volnnnmnc Ranio 1.nnn (81 wnltn pcnnnnissll/nn. (‘PyngIni Varnuni ions of gins In liquid rmmtio by reduicimrg pressure below humhhlc poinnt Rn’pr~~duccd tn. 1/ 0% t)ew t’onnnl (n/rye 207. Reprnxiuccd rrncnn Ii 71 wnllm a~. ci . Gas mixtures rich inn C02 or ii2S at low terirpermniures earn formrn a rich liquid phase imnniccihle svifin tine Figure 1.hie Poinn 85 % 2. wiilrourt airy peculiarity. Sohnd..8 2(’0 Crnuical Poinn ~ ~ -o 0 265 t’rcssure 0..67)/l 8 Mt’a=0..~ri. The trend reverses over a lmmnited pressunre range.. 70% -5 ‘S. Note that the gas/liquid volumetric ratio increases initially below tIre bubble point. as showmr iii Figure 1.006895 psia Figure I .Ja. I 7.nr Iim. A bnighn pressunre gums.

20.09 0..in reservoir fluid correlates reasonably well with 5~ GOR. C . Figure I . and these fluiuls bebnave liqumid-Inke. Gas and liquid phases are produced at a ratio differemrt to thmnt in the original combined state. tIre initial producing gas to liquid volumetric ratio is considcrc(l mrs lIre nm(nsl iunpiinlant innuhicator of Itme class of a reservoir fluid. to water at 60°F(288 K). A reservoir cminnnuminrs gins if its temperature is higher tlran the fluid critical tennperatnmre. I 3.200 SCF/S’I’B) and 12. Cuniponeni. 1-lence. which can be appropriately applied to each class of fluid for reservoir studies. °AI’l = ( 14 ISIS.91 36.5 nmole% (‘~ are valid boundaries for gas and oil systems [19].85 1.03 nCS C6 Cli’ 3.25 0. cummm be used convenieirtly to describe various types of reservoir fluids.22 /. or relative density. mumy vumporise half the oil volume. Critical temperatures of heavy lnydrocminboirs ate higher than those of light compounds. otherwise it comrtains (nil lIne depletion of reservoir will result in retrograde condensation inn tire reservoir if the reservoir temmnpermmturc lies between the critical temperature and the cricondentherm. It is evident.47 9. as sitowmr sclnenimntically in Figure 1.41 0. As tire stock tmmmmk oil is minosnly connrprised of tIns fraction.93 (. i. is often used.saieVotaintcOiI N2 Critical Poinl ‘a 0. . the inverse of the above ulcfimnitiomi..80 1.35 0.n. In a hydrocarbon reservoir consisting of a gas cap and Inn oil coiunnn two separate phase diagrams. ((. .67 1. when a saturated gas reservoir is discovered.33 16.5 (1.’.29 Receuv. wlrere tIre pnodrnced fluid is predomnninantly gas. Wlnercas tIne teirnperatuimu’ of a reservoir mainly corniposed of urethane. in a reservoir with a temperature just below the fluid critical tennperatumrc.)R. Similarly a saturated oil reservoir may strongly indicate tine presence of a gas cap. known as material balance equations. hence it cmiii also he used as air inrdicmrtor.uuifin-a iron of Re.51 1.67 C3 iC4 nC4 iC5 2. 0 Thre concentration of lremmvy fractionn. as simuwn un Figure 1. will be higher than the mixture critical temperature. As the material balance equations relate tire tnro(luicc(I liuuiuls to those inn the neservoir.uerroir Fluids 23 1. one for each phase can he connsidered.22 0. l’lie gravitational segregation of the two phases with different densities will also inimihit the contact between the phases.36 0.2. resulting in changes of the overall comnrposition. therefore. ‘l’lne stock tank oil gravity generally varies significantly for different classes of fluids.95 144 3. Althroumgh identifying a fluid as gas or oil is adequate in most phase behaviour studies. it is more comrnron to classify the fluid in accordance to its volumetric behaviour at the reservoir and surface comnditions. Gas Gas C02 Ct C2 625 234 81. whereas no hiqumid will forrmm if it is above the cricondenthcrm.17) where S is tire stock tank oil specific gravity.44 1. ‘lIne gravity is expressed as API degrees in field units.e. Figuire I .59 5.ace Refnrn. The two phases are both suntunratcul. the critical tetrnperatunre of Irydrocarbonn mixtures predominantly composed of heavy connpoumids is higher tinmnn ttrc nnunnnmmmml mmnmrgc (if reservoir temperatures. Moie% D~yGrsGasConden. Typical comnnposmtmomns of variotms classes of reservoir hydrocarbon fluids are given in Table 1.22 0. witlr a critical lemunperaturre of I 91)6 K.nir t)iI When the reservoir pressure falls below the saturation point.35 0.18. The phrase behaviotir of mm reservoir fluid is deten’nined by its composition.nwla I.12 6.64 33. an oil coiunnn below it is generally expected. I’Inasc dimugrutmos of segregumted oil and gas phases in (lie vicinity of gas/oil contact.2. Table 1.22 4. Therefore. Petroleum reservoir fluids can be classified according to various criteria. Typical compositions of various reservoir fluids. the phase diagramrm of tIne origimimtl rcscrvomr fluid is no longer valid.50 69.’. CGR.48 012 1.19.31 i)kmck OnI 0 n6 0.24 029 1.13 7. that the location of reservoir temripem’ature (in tIne phase diagram can be used to classify reservoir fluids.14 7. hence preventing the achievement of equilibrium throughourt tIne reservoir.29 0. Sclnenniatic diagranur of slabilising produced oil as stock tank oil and gas at standard conditions.) — 131. lIne reservoir fluid is prouluceul annul nnieastnred at tine surface as tire stock tank oil and gas at stmmnndunrd conditions.20 shows that an initial producing GOR of 570 v/v (3. with tIne saturation pressures ideally equal to the reservoir pressure at tIre guts-oil contact as slnowim in Figure 1. Time temperature of a reservoir is determined by its depth. is rnrost corrmtmn(nnrly nlcinimed as tIre nnurrmber of cubic feet of the associated gas produrced at stamndand comrditionms lien barrel of stock tmnnk (nil in tire Field umnits. Iemnnperaiurc > Figuire I . This approach yields a few set of formulations.72 79. A smmiall redinction (if pressure hehow tine bubble point.1 (Ia.. kmnown as line courdensate to gas ratio. For gas— c(nnndemrsatc Iluids. oil.r F. it can also he used as an inrdicmmtor of tIme reservoir fluid type. The gas to oil rmmtio..3 CLASSIFICATION OF RESERVOIR FLUIDS A 1’he typical phase diagram of a reservoir hydrocarbon systenni.61 4.19.18. The oil in a reservoir witln a tempermulunre close to its critical point is more volatile than that at a lower temperature.76 0.55 4. /‘/.. shown inn Figunme I.nthnnn.

///~~ Separator 0.nni U A iypnu’unl guns cn. ‘[‘Inc hillase enrveiope is relatively tight and mostly located below the anthienrt temperature.. lenruperanunre Dry Gas Dry gases are predominantly composed of ninetiraune an(l nonn-hyulrocumrhions such uns mnitnogenr and carbon dioxide.01)0 v/v (50. therefore.. voluntile oil aund black oil. when fire pressunre falls below ttne dew point. Su’punruutor tests urru’ gcmneral ly comnuluncled to detennnnnre time unnniounnnt unnd properties of tine condensed pirase at tine sumrf~ncecomnulntions..21.000 SCF/STB).n. as shown in Figmrre I . nnnaneuial b~nlumnrce equninlionns for a dry guns are equullly sunnt~nlnlei~nr un wu’i guns ‘[Inc ninly l’Vi’ test ncquninu’d unl line reservoir comndmniuinns is the gins connrpressibilnty nnneumsurcrnrennn . n Inc reservunm tcnnrpem unitmue lies inctwcu’nn (lie crinical poini and tine crieonndemntlnernrr.22. Gas to Iiqumid ratios range helween 570 to 30. simnnilunr no a dry guns. temnnperiiture. dl.1 (/ar.21 sirows tire phase (Iiuugrunnnr of mr ulry guns..nitç C + nnroie % 7 Figure 1.24 L Phace fie/. Reservu.23.000 v/v (3. A wet guns reservoir is connnnnnounly produmeeci by siminpie halow-dowur.5 iO0 A wet gins is mnnunrmiby eonnihnoseul of nnuctimumnc amrcl other light conipoinents witir its phrase emnvelopc lou’unled entirely over um tenrnpcrmn(uire rminngc below ihumt (nf lIme reservoir. however..23.000 SUI:/Sh’13) mid rcnrrunini constunni dunring the entire life of tIne reservoir. will riot drop-out condens~tc inn line reservoir during depleti<nnn. time condensation in reservoir .ndenitlnernmn ntear the reservoir leniperature will behave very mmntnclr like a wet gas. Reproduced from 1191. A wel gas. mmnuny conndennsc at the surface conditions dine to the gas cooling.sa(e U Ojt a U 0 700 500 em 30(t 7. C — GOR relation for typical oil amid gas connulerrs~mte fluiuis. Water. ‘FIre presence ot lrn’znvy I my dune ~nn hu.. Figure 1.’i. l’he producing GOR initially remnnunimrs conrstamri unntii tire reservoir pressumme falls below tire utesv poinl and increases thereafter. Gas iicld.nt I’. Phase diagram of dry gas.i’o. FIre conrulenrs~ntecolour is tnsnrumhly w.22 The sep~nruntor conditions lie. hence. > ‘[lie uuinmoimnt of siternlinlly coniuiennsahle imydrocmnrhorrs irr the reservoir increases with lime 1 as Ineavy connpounrds shifi the critical temperature towards the reservoir ricinnress of tlne guns.001) v/v (100. Note that the gas remrrainns single phase froni the reservoir to time separator conditions.m.20. (‘~nIrrcsyu’l tOni 7~ Pnnbticanion Inc. WIncn’c~nsu gas wiihn a cricu. ~ li ( . ice I’.a.21)0 In 150. prodtmcimrg sonmne connulensate at tine surface.mrs exlnunni uls lIre pl rinse envelope re lint sc to a wet gmus. Irunwever. gas condensate (retrogrmnde guns). 25 Wet Gas too Gas (‘o. wet gas.c.nr Figunre 1. The gas will (In 1i~ourn I iu uiid 1 by in2lmogiaule eunnndenisationn inn (inc reservoir. Further connulemrsation fronni tire produced guts also occurs at sepumrumnor comiulmtiomrs ulnie to coolming.vi(hin tIre phase envelope. fmomnn 1)10 (2) inn Figunre 1. F. (1)10 (2).000 SCF/S’FhS) earn he treated as a wet gas. I’roducinmg gins to conrdensate ratios are typicunlly above 10.nndu’nnsuntu’ phunse drungmuntni is slmniwni inn Fngunrc .ntrnI. For guises willr G()R of unhove 20....<v/a. Phase diungramnn of wei gas.nler-wlnite with a low specific gravity which rennrainrs ninebmuingeul (itmri ing lint’ reservoir pruidurci iorn life Gums (~ondeimsalt’ A ( rni.i (‘urve ci A m2 5 50 75 20(1 225 (7ntinil/ i’u..ie..i r ~ Sepsu.anr..000 v/v (50. For practical punrposes In gins condensate reservoir with a GOR of mnhove 1(1. .n/ka/rorn of Ren .III 5 2 Rc’st’rv. Temperaimnre Figure 1. / .01)1) SCF/STB)l l9J. Fyi’ tests in tine laboratory are iinnnitc(i to tine guns compressibility measurement. As inn connulenrsunle is mmmcd inn tine rcsenvomr. 9 V~’t~.s nnn line Southern Noriii Seun mire gounui exanmnples of this type of res&’rvomrs.nnon The most common method of identifying petroleurnsn reservoir fluniuls is to elassily Ilnerin mms dry gas. ins rio cnnndcurs~nteis fornmtu’ci mm lime neservoir.

.n. The anrount of liquid recovered from tIne gas constituhes a sigmnif’mcant portion of the total oil recovery.82 (60 to 40 °AP[). A snrmmnli reductionn of pressure below tIre bubble point vaporises a significant fraction of the oil.no. volatile oils are referred to as near-criticuni oils.rrr. Recent results [22].. ‘l’he comrcentration of heptanes plus is generally less tinan 12. A very seldom cmrrrieut out beemunse of shortage of gas. time liquid loss by depletion will he lower mufter recychnng. A composilionnal material balance method should be used below the dew point.mti. Dark condensates usually irunve relatively high specific gravity and are associated with higlr dew point gases. However.snfln.s. Volatile Oil Volmmtile oils hmmve mnnlnury c(innnnsnon femniures with gas conrdensates. as a significant iiqsnid production is due to condensation of the rich associated gases. TIne liquid drop-out reaches a maximum and then decreases by vaporisation during pressure depletion.74 and 0. Saturation pressunres of volatile oils are high. The GOR increases when the reservoir pressure falls below tire bubble point durinng the reservoir life. Figutre 1. not only reduces tire prcssunre decline rate. Ilowever. Phase diagram of gas condensate. Gases produced below the bubble point. The rennroval of a sufficient amount of heavy hydrocarbons from a gas condensate reservoir may iulcmnhly shift the entire phrase uhiagramni fartiner away fromni the reservoir temperature to form a wet guns reservoir.25. hut it can noticeably reduce the gas recovery rate.n. lIn practice.24.200 S(’FISTiI) (51. In recycling opcrmitionns inn(ennneuliumle mnnnd heavy connipounds of the produced fluid are separated and the reirraitmimig leaur gas is imr~cctcd hack inrio tIne reservoir. mire quite riclm mind heirmmve as retrograde gases. where it is economical to do so. Compositional material balance nretlmods shroumld he applied generally to study volatile oil reservoirs. Comndeinsale specific gravity ranges between 0.although values as high mms 0.u/. Liquid (Imp-out behaviour of gas condensate. Initial producing guts to Iiquiul ratios (GOR) of volatile oils typically range between about 310 mmmd 570 v/v (1.5 mnioie% inn gas conndemmsate fluids as fluids containing tniore than tlrat alnuost always behave hiqunid like in thne reservoir. U a: A ‘a Temperauunre > Dew Point :9 Figure 1. .5 mrnole% and oils witir as low as 10 tnmole% of heptanes plus have also been reported 1201. It is commonly assumed that the condensate fornned inn reservoir remains immobile due to its low saturation. The specific gravity decreases (luring produmctioun below time hunhble point. Note tlrat iso-volume lines are tighter and closer near the bubble poiurt currve.23. The phase envelope of a volatile oil is relmrtivcly winIer nlnamn llnmit of mm gas contlennsate.. witir a higher critical temperature due to its larger conccntrationn of heavy commnpotmnrcts.r 1. Condensation and loss of valuable compounds in reservoirs could be avoided by maintaining the reservoir pressure above the fluid dew point by gas recycling. A typical volatile oil phase diagram is shown in Figure 1. The condensate colour can be water-whrte or dark.u.82 (higbner than 40 °API). however.I. Exceptional cases with condensates as high as 15. hennce the name “volatile oil”.. Separator conditions typically lie on how quality (iso-volunne) lines... 27 has negligible effect on the properties of produced gas..88 (as how as 29 °AP1)have been reported 1211.ir f (nod. Material balance equations develuped for dry gases can be used for a gas condensate reservoir as long as its pressure remains above the dew point. Inowever.26 I I’hone J(.p. Ihe condensate will be recovered by revaporisation. hunt also makes the system leaner. have indicated that the condensate can flow even at very low saturations. by the time the pressure falls below the dew point. This behaviour may imply that when the reservoir pressure decreases sufficiently./n.n of Reuem. Tine reservoir teninperaUtre is near the critical temperature. Partial pressure maintenance is more cninnimon to minimnnise the losses of condensate. lInt tIne lack of conmiplete uiisplmmcemmnent mind mixing of the recycled gas with tIre inn-situ fluid limnnits tine stnccess of tlne ~nhuveoperatiomr. and is mostly non-recoverable.u 13 (‘l. this is ‘a’ ‘-I N —V Pressure > Figunre 1. hence. PVT tests simulating reservoir conditions wilt he described in Cbmmpner 2. the original phase diagram is no longer valid as tire system composition changes during the production period. ‘[Inc reservoir cann tlren he produced by blow down without much loss of vuultm~mhlcliquid. Tire stock tank liquid is coloured with a specific gravity umsununhly lower than 0.750-3. tlmerefouc.24 shows a common characteristic of gas condensate fluids. particularly at high producing GOR. The recycled gas which is predominantly rnrellnmnnre. but as they contain more heavy connrponnnnds Itrey hehurve liquid-like unt reservoir conditions.

ervn. The GOR may ulecreumse mmritn~mhlywiienr (tie reservoir pressure fmmlis below tire bubble point. II.751) SCF/STB).n. The GOR. ‘I’ rc.. n. llumgginms (‘.4.e . Enigiunnid. “Gennchenmnistry nif Petrolcunmi Reservoirs’. of the Anrierieunn (‘lmenrricuui Society. ci ~ni: ‘‘ I luunulhook nil Natuirunl GaS Ennginicerinrg (1959). winicir is typically of two nnmuiers ot inniugirnurde. KaIz. t). nineneiniru. cii: ‘‘St Fmngiince’r inng I )unlun ltunuik’’. mnrc the Inmost connnmnromn type of oil reserves. R. McGraw—Il ill. WA. Cmii. Ilrenm increases slnamply as tine gIns to oil nnmohn In ty rat no wit Inn nn lire reservoir varies inversely witlm tire viscosity ratio. annul Ennt i nipy iii V~npumris~nnionr.nr Terniperunnunre > 1. in comparison with that of volatile oils. McCuminm. oil annul guns.‘ ~ 20 60 40 . AN ‘‘‘[Ire (‘Iicmmnncunl (‘omislmiunenits of l’etrnuleunnni’’. Sine. 3 . as the evolved gas renmtumnnrs mmnmnrnn hrle at very low s~nIunmuninouns. (‘onmipnessilnihity Fuiu’tors..e. 4th Ed. R . mrnuny lie soiincienii for sonrne reservoir siunnlies.. mns mug as lIre pressure keeps dcclinnimng annul no gins corrinng imnkes place. New York 4. lIre qinumhity limes are broadly spaced at reservoir condmtrons witlr seputruntor connlmliuins lyinmg (inn relatively lnigbn qurinhity lines. 20 0~ ( .. Sn ‘a I.s. Pit. .26. 29 (‘rinncal t’nimnt tPumnnrcurvt A 99. hunt to uhisimngunnsln nt fmorrn line vunlunt he on I. REFEREN(’ES I ltnmnt l. Figure 1. line GOR uicu’i inres tlrrouglrount the produncinng life of tine field. Preennnutn umnrd (‘ui. wInch trea( the reservoir fluid uts a twin conmnponent systcnnn.. 34333441). The above characteristics lead to a low shrinkage of oml wlnen produrceul. KS.. the uncceponbi hity of resur its uihtmuinu’d by tire volunrmclmnc nnrefirout is’~ip acincunl cm nieriomr for uhistnnguislninng between tIne two types. 8..( ‘: ‘‘ Rcservonr ( cou’licnmnisiry : Men Irods. its pimunse emnvu’lnnpe. A. NGA of Antreric~n..’’ J..n / I (‘(o’uirfin(mtnnn of Resernoir b/nod. W . (1945)..S: Gcologiscire Runrnulschnuntn..” U . A typical black cml phuuse dimrgrmnnnn is shrowir mn Figure I . In frunctinred rcservonrs. Appiic:nt mmmv umnid ()ppomtunniniics’ Inn’ l:nngiunnrd. 2. 2rrd Ed. WA. 958). Figure I .nd. l. The stunt-k tuunnk Inqunnd ns dark witlm In specn Inc gravity lmmginer Ihtmnmn 0. 214-237(1989).a~ l’rou-essors Suppliers Assnicmuitmuinn. ~nstincne is nun de In in inc hounnrdunry betweein hi unck unnnd volunti he oils. J.1 . New York (I 984). or ordinmnry oils. Johmnn Wiley unnrut Sonns..C:”Na(mnrai Gasohimne and (lne Vumh~mliie I lydmocarhoirs”. 1955). Plrmnse (Iiuigrannn of mu hI mit k oil. ‘lIne vumm iuntionr of tIne specific grurvniy is relmniivcly snmnahi. Vunpumm hiressunnu.M mmmd l’eterscnn... Scpar~nmnnr 0 .28 1 P/nnn. Reinihoid Pub. Nd snurn. Black Oil Black oils..11.uumnn.. ‘‘. A.80 ( lower ihrmtmr 45 niAPI ) 12(11. W . dunring tIne reservoir proutumctionn life. l’unhhicuilnoin ( 1994). I’ . witlm ins critical iennnpermnturme well mnbnnve tire reservunir temperature. is the widest of all types of reservoir fluids. Tire iii I is gemncn ~nl iv u’uninuposeul of more tharn about 20 nnole% heptanes amnd lreumvmer comnipounrds. ‘lIne s~nlur~ntnumnr li~CS5OiCinf black oils is n’eluntively knw. unird Cunhilt. inowever. Critical point A C’ (( 7 I urn Icr.25. t).n..‘l’ulsa. 2(n. 9. (Jnniy 5.A.. Commlrihunfluin ~if inemrvy conrrponnmnnis present inn evolved gunses inn reservonr to tIne total hiquunl recover) is miot signnificairt t lennec vnihnnnnicnmnc nnma(eriai halunnicc eqnmintrunrrs.’ Reluin’. Penmnwell h3ooks. WI): “line l’roperlies of Petrolennnrn Fluiuls’. / ~40 McGrurw—l Ii II Book Coin npanny ‘I nil~ui. M ‘Pet nolu’tninr Geunclru’nrristry mnnd Geology’’. S.’nnnnl.on.’riiture > hO. 6 Suit-Inunnrenr. 5. (1948). 78.en.u. Phrase diagram of a volatile oil. Browmr (1G. Oberfell (1G. )klunironmiun (1980). Kum(.L.E: ‘“l’hne Vohuunnieni it’ unnnull’hemimnun&lyniumnnrie Prnipcrtics of Fluids.F. . II. and Alderm R. ‘Flit’ niunnnne dunes riot reflect the colour. Jr. uund ApI inn.nnmd ‘I’esiinng “. Imnuiceul. I)...’l’umls~n (1990). Separator S .. Sunnn Fr~nnrci.‘‘‘ lnntnunl prurducmng GURu mire less tlnumnn about 310 v/v (1. svhere Ihe fractunres provide a gounul comnltnii for (lie gins Inn risc by grinvi ty..scni (1979). (‘o.“~ (it) / T reservoir feinipm. (cdv) ‘“lire ( euncireimtistry nil Resemvonrs’’ euil . 77.uppnmrannmn 1)7. Inistniumie nil l’etnnulcnnmu: Methinids for Amraiysis’. unnid M~nckcnniic.Tine lnnstinntc nil Petnok.. “Pcin unleunnmn Re finery Fnigrnreerinrg” .

and Gunn. unsung: (a) tIre Cox chart. tcnnpcrattmre for thre following eonnpounn(Is mm lire redunced scales of (P~P~) and (l’IF~): nietirane.D. Trans. A cylinder contains I kg of saturated liqunid butane at 385 K..2t No.in illmini nut vumpoum pressure and inverse of temperatunre eonncctnnng tire nomnniuml hoihinmg point mind lIne critical point. Lee. . Esttnmrmrte tIne eritmemnl tennnpcrature aird pressure of a mnnixture conmnposed of 55 rnole% ethane amrd 45 nmmolc% nornmnmii Ireptaune.M: “Experimental lnvestigatinitn of Criticunl Condensate Saturation and its Dependence on Connate Water Saturation”. No. 1975).t.1005 (Aug. SPE Res.G:”Equation of State for Saturated Liquids”. What will lie tine cylinder 1.2. Kilgren. 514-517. Pumper Prcsemrted at the Scvetrthm Synrposiumnr onr Eurhrmmnceul Oil Recovery. Journal. J. Estinniate its prcssumre. R:”Smmturatcul Liqumnd Molar Volunmnnes: tire Rumckenl l/quiuu( mum”. 18 No. Data. 1. B. April 22— 25 (1990). J. 82-89(1978). CF. C.. Enig.L: “Engineering Applications of Plrase Bebraviour of Crunde Oil ammd C’onmdensate Systenrs”. 1991). hcnzene.nn’.F. I. J. Chem.5 EXERCISES 1. 19.. h-lenderson. Flow mrmumcln propane will be left in the cylinder when the pressure falls by half. . 16. 35—36 ( Junmi. No.T. and Bridges B: “Volatile Oils and Retn’ogrurule Gases-Wlmuit’s tlnc Difference’?”.. A 5 litre cylinder contains 1. MG:”A Generahised Thermodynairnics Correluntiomm Bursed on Three-Parameter Corresponding States”. and Peden. Eng. 18.1.5 kg of propane at 393 K. as the third parameter in a three-parameter corresponding state model for lIne vapour pressurre 1. 11.Data. 336-342 ( Aug. 7 15-723 (July. (c) a Ii nrear re hat urn bet wcemi IImu’ iiig. Moses.P: “Prediction of Bubble Poimit Pressure nil Mixtures”. nnorniumml decunne. Yamada. Plot tIre vapour pressure vs. C..31 12. (1973).5. 15 Spencer. Danesh . A.4. mmmd cicosmnnme. or critical cornrpressihiliny fmmctor. Suggest a physical property. 20. AIChE J. Ctrennn. D. S. 17. IS No.2.. P. and Kesler. such as the acenlrie factor.nnn ( . Data. Data.1 Chem. mind [odd AC: “ An Evumlunationi of Cunhie Equnmutiumni of Stunle Our Phase Behaviour Calculations Near Miscibilmty Comrdnlions “. Weinaug. (1973). (0) tIne Lee—Kesler cquatiomr. JPT.. Eng. 234-236 (1973).2.nn. 230-234. J. A. 1001.nnn/. AIME. 1. and Danner.B:”A Critical Reviesv of Equmationns for Predieimnng S~ntrmr~nted Liquid Density”. Vol. anti Adler. 192.4.ntnnln I ~ (‘ n (Prune. W. Calculate the vapour pressure nil normal ulecane at 355 K. Xum.30 / /‘/na. 21. 13. and Bradley. 22. GD. Eng. 233 (1951). K. .Oklunlnoinuun..4. normal tmexmnne. H. Spencer. 23. TumIs~n. 510-527 (Mmmy. 1. Eng. 1966). pressure after consuming 950 g of butane. 1986). Rackett. Chem. 18.. MeCain Jr.H: “Phase Behaviour of a 1-ligh-Pressurre Condensate Reservoir Flunid”.ce Itehnnn’n.B: “Phrase Behaviorir of um Natunral I lydroeunrbomr Systennr”.F.. R. SPE/DOF 20267. Daneslm.3. JPT. 14. Petroleurmn Engimrcer Imiternuutiourmnl. 1994).

(Ire nescnvnuim pressunne. iimu’nei’mnrc. unnc iulemrtilied my flunstuimmg lIne rcservonr llummtl at lire stanrulumrd comrdnl ruins. Imenree time nanmre (pressumrc—volumnne—tennnper~mlmrrc)PVT datmn.2 PVT TESTS AND CORRELATIONS Aecnnraie mind n’eiiunble phrase helrunviuutmr mnnrd voltnmnuetric data are essential ehennemrts for proper nnramnagemrnemmt of petroleunnn reservoirs. ‘tine nnmainr variable Ihumt ule(cn’nuiinnes line huu’Iravnonrr nil t hunids. Onnly in special cases such as gas iniection or miscible ulmsplacennent Ore conrposrtionral approaclr is unseti for black oil reservoirs. gmns mmml tiil. These pseumulo conniponents. Hems-c.. and chnar~mcternsmmng tine sepan’mmteul gmns annul mu phn~nscs by tlneir specific grunvity and mmnuulectmI~ur wengirt valunes. Most reservuuirs mire produrced by depleton in wlmtch tine reservoir pressunre uleelnrmes Its fouls mire rceovem’euh.e. and the ~npproach is referred to as line black onl nnnethrod. . uure oftern conulueted ftnr gas comndensmn(e mind volatile oml reservoirs. uinnnimug du’pleninnnu is. rcla(nvt’Iy snnnmplc tests whit-in sinmnunlate mt’u’mnveny himuin’esses mine cnummdmmc(cnl by vuuryinmg tIme flnnnd pmcsstirc. i. ‘lIre inforuriation is required to evalumate reserves. to develop line optinmnmmnir recovery p1mm. where uletailed innformaniomn on tIre fluiuh eonstitucnnls mire used to cslinnrmnte flumiti properties. ‘lIne mmcmiii enmmpl mmivis is omr tIne vunlum mmmetrme ulmnlmm ~nttIre reservonr mnnnul vu riace 1cm n pcraturres. ummider reservour u’nnmnulitimnmns. (‘onmrposiiiomruul d~ntmm on tIne procluncetl t’Iumids are nnaimrly determnnineul for timeir mnpplncationns in Irydrocarhorn processinng. ‘lIne prune innfonnumntionm fronrr PV’l’ les(s mire tine ratio of pirase volunnnue at reservuimr condihonns Inn that urt surface coniuhitionns. 1mm tIre simnnplcs( appi’oincln of predietinng tire PVT (Immua. lire reservoir temnnperatumrc stays practically cotmstanr( inn nmrosl recovery nnnetlnods . l’he informationi is generally smnflicicnt inn stnrulies nil hlumck oil reservoirs. anul to determnimre the qumurlity mnncl qunaiity of produmced hiumiuls. tIre reservoir oil is cnunsidt’reul tim he connrpnuseui of two pseunulnu cnnmmrponremnts. Ctnnrnpositional stumdies. mind the solumbihity of guns in oil.

When tine reservoir pressure falls below the inntimul smmturmmtion tiressumre tIre hydrocarbon phase forms two phases ol gas and hiqumul. Samsipling proceulures Inave becnr discuissemi in details [I-SI. if the well bottom hole pressure has fallen below tIne oil bubble point. tIne energy transferred to the liquid by the llowimrg gIns mmnumy nmnt be stifficient to carry the liquid. ‘hIre mmumthnors cnnnmrparcd tIne nnrimniisnunnnn gmms velocity required to lift time entrained liquid svithr tlnumt for trumunsfemn inng tire Imhnnn un uward. t)istmnurce Figure 2. and partly as a Imlnr on the wmnll by tire gmns slnemrrimng effect (annular-mist flow) . in principle. Figure 2. witlr nnimnimal clnanges over a short period.!. the advancement of the two-phase region is slow. the condensation wmms limited ounly within a small zone around the wellhore. A comnvem’sionr table is giveun inn ‘I’ahle A. Ilence. by properly conditioning the well before sampling. In this chapter phase behaviour considerations related to the smmmnnplnnng of reservoir fluids unnc described. to estimate PVT properties fronr himnnited Inelul data. Tine gravity force is determined by the size of the drop and the liquid-gas demisity dilfereunce. pamnicumlarly ann unuiersaturated orre. however. to unrmmintmmin the rmmte pmnor to samnnpling. and in mommy cases air impossible task.1.1. At such conditions. The most con’mmonly conducted PVT tests mire detailed next . nrainhy renniniscenee of dumys wlneur inmmnul calculations were the norm to predict PVT data. It is imperative. svhenn mIne pressure is still above the saturation value. tine chance of collectnmng a represenrtative sample is high.3. possibly above its original bubble point. 71 ulcvclopeul a mmmeehimnunistic two-plnmmse flow mmdcl amid mupplied it to the removal of liquid in a gmms well.~rTressur~ Intinuw Gas 7~nc Reservoir fluids should be sampled as early as possible durimig time produnctnuor Infe nil mm reservoir. it should be ensured tlrat representative fumitls are flnwimrg ount of tIre formnaniomn. however. Ore overall composition of the gas-comndensate mixture flowing into the wellbore is the same as tlmat flowing into the two-plnase regionn. umnd recombined urn tIne prodrncimng ratio. Inn tIns honik tIre rrmmitlmennrmml ncmnl expnessnmnuns nil line correlations are presented in preference o tlneir originral graplmical brims. Flnmid Sampling 35 A compositional phase behaviour model. it is reasonable to assume a quasi-steady-state condition around tire producer. Sumniden cimanges of suite will disttrrh tIre steady state conditions and the outflow composition. 2. Producing fluids. Tine mrrajor forces whiicln detenniine tire velocity of a liquid drop are the downward gravity. The pressuire build-up may vaporise tire condensed liquid in the reservoir into tine gas plrmnse In) form a gmrs condensate even richer than the original fluid. The mmii iii mnnunnnm flnmw rmute 0mm u’nnmrti nnnmml menumovmnl of I iquids (eomidensmite or water) by tIre flowing gas cunnr be dctermniiired by minunlysing tIns’ fihmnn 11mw mnmrd time emrtrmmirncd drop movement.5. ‘l’hey wene nnnnustly developed nriginally in grmupinicmui forums. the well is generally conditioned by a period of reduced flow. Surface sampling is conducted (in producing wells eitbner at the well head. well I wni’t’tm~nsc~ ~—— Rcgmnnrn I . the direction of liquid flow in the Inlmrn is reverseul amid tIme cmmtrmmincul ulrops frill hmuck. The models. is relmmtively a mmmcli simpler tuisk tlnmnmr tlnumt from a gas condensate reservoir. is capable of predicting mmli tIne PVT dunta. An inncmease in the gas velocity increases the ratio of tine drag force to tIne gravity force. are generally at two-phase conditions. as a sample representing the producing mixture stream.1 FLUID SAMPLING bulk as the pressure declines during produmction.c and C’orreinmnm. which can provide reliable information rapidly using advanced conipumlers. Empirical correlations annd charts. using only tire composition of the original reservoir fluid. The sample can be collected either as a single phase at tIre bottonnr hole. allowing the disposal of (Ire ricirer gas over a reasonable period of conditioning. insinig labonuntomy dmmtun. ilnerefore. as will be described in Section 9. the collected saun’iple will not be representative. tire collection of a representative sample becomes a inighly dennianuhiung. and tIne umpward gmns drmrg. as no condensate mnccumuia(ion occurs in that region. mnmnh councluulcd thrat tIne former svas tire controlling 1 hinurit. Ihemnce. Producing tire gas al mm low rate to unrmmintmmin the bottotin hole pressure above the dew point can ensure tine flow of single phase gas inrto tIne welibore. The formation of condensate initiates arotmnd the wellbore. As the depletion rate is low. hour resultinrg in well flooding.34 2 PV7’ l’esn.. can be evalunated by numerical simulation of the flow umemnr the wehlhorc unslung a comumposi(ionmtl model (6].5 nun Appendix A. and are reported as such in this chapter. —pr) 4 /4 1’ “Pg - (2. that the well flow rate remains above a nninimunn value for tIne continumal up-lifting of the condensate formed witbnin the wellbore. lIne eoinelatmunms unsc field units. Tire validity of the above assumnmrption. Time bottonmr Irole sanmiplcs are usunmnlly collected during formation testing. where the pressure is al its lowest value in the reservoir. The method is not . are reqmimel to be evaluated and tuned against the measured PVT data prior to bemng used in reservoir studies with confidence. Schetnmatic dimngram of two-phrase flow around wellbore. ms heennnnninng mmmore popular. or at tine surface.1) .nn. Unless.sumitable for a gas condensate reservoir.67 &‘ (p. as will be discussed in Section 9. or as separated gas and liquid samples out of the separator(s). however. ‘h’lresc correlations have bccn genermmtcb over years. It is advismuble. TIre mnrole ratno of time two plnases flowing into the well is not generally equal to that formed in tIne reservoir. Tunmer Ct al. First. however. TIre transfer of liquid between time luhin mmmruh ulroplets is a countinumous process along the liquid path up the well. The two-pirase region gradummilly grows into the reservoir 2. should represent the original single phase reservoir fluid. if collected properly. When the gmts flow ruute is reuluiced below a mnnimminrnumm value.c 2. This lowers the pressure draw-down and raises the oil pressure. Ileurce the reservoir outflow. prior to production. followed by a shut-in period of about 1-3 days. are also givemr. As long as the reservoir pressure has never been below its saturatiomn pressure. wlneremus tIne drmmg force is domiurated by the gas velocity and the physical properties of tire two phrases. ‘lire liquid plnase is trmmnrslcrred rip tire well partly as entrained drops in the gas core. Then. l’umner et al. fluid sunmnnpies slnounld Inc collected from all co—existing phases. Next. tIre sanvnplmng procedure should aim at collecting both phases at such conditions where tine suhsequnennt reconrhination provides the original reservoir fluid. The compositionmnl method. liennee.Selected ctrrpiriemml correlations. balanced the two forces and derived the following relation for the nniniuinmmrrn gas velocity to tnnload ttre well. Sunnnrplnmng fronun an oil reservoir. “gnn = Well Preparation In oil sampling. are still used. and mm snnnglc phase sample flows into the sampling bottle.

along with the producing gas/liqumid volunmetric rmtflnu mnrc reported to the PVT laboratory. primarily by mmneasuring tine opening pressure and comparing it withn the reported sampling conditiomns. ‘lIne samnrple flowing is collected winO a fluid velocity in the tube equal to tine average fluid velocity in tine turhimng.2) where P is the welihead pressure in MPa.1. Note the nnrmmrked difference between lIre condensate drop—out belrmmviomrr of different fluids. flummni properties arc unsed to mnemtstnn’e thre produnction rates. For mm recombined oil sanmnple. tm 721 kg/inn (45 lb/flu) Condensate density Gas-condensate interfacial tension: 20 nnnN/nni Gas specific gravity: 0. As tine collecied samples are saturated fluids. they often form two phases in the smmnnrphinng bottle (lime to cooling. Separator samples are recombined in the laboratory according to tIre reported gmts/hiqumid ratio recorded in the field during sampling. as it cnuld be dune to tine tlmenmnumi contrmiction.m 0 LL 8 a ‘0 a ci- 1(1 20 30 Pressurre. but the effect on the gas . relies on the assumption that the comndensate is homnnogeneoumsly distributed inn lire tubing flow. The effect of adsorbed material on tIne mrnunlti-pinase flow belravioumr of oil-water in pores is probably moore significant than on tIne PVT properties in mnmosi cases. mis (Inc hmmhble P~imntus semmsit ye to tIre gmns/hiqumid ratio ann increases nvitlr it. Vg~=i.5. lire recomnuhimred sumnnrple is expected Inn reasonably represent the reservoir oil.36 2. Fluid Sannpling 37 where V~. Sigmnilncamnt differi’mnees inn eonmnpnisiiionm bctwcenn produiced ilui(ls’. wlnielm mnnmuke tlncnmn iimnnnnobilc shining convemntional smmnmpling. instead uif relying omn the reported gas/hiqumid ratio. dependinng (in tine smnrumple. Variations of c(undensm(ie (lrop—oumt witlr undjumsting rccounrhination rmutio. The effect can be serioums for lemmn gmus comndensmmte systemmns. Further information on the use of phase behaviour models to evaluate and improve collected samples are given in Section 9. consisting of llne gmns mmnnd enlrmmnned drniplcts. This may he examined by heating the bottle to tine sampling temperature. A small amnrounnt of utnrecovered mndsorbed material is not expected to sngnnif’ncantly change the saturation pressunre amid tIne guns-liquid vohunnmrctric fractiorn nil aim oil sanrple. Turner et al. cn is the gmus-condensate inmterfmncial lension. lIre pnesstmre-tennperatunre at the gas oil contact identifies tire smmtumrmmtnon point. The pressure of collected liquid samples are often lowered puirposely below lire saturation pressure to form two phases for safety reasons. N —‘— . n. rn/i.. tine reported ratio shoumid be adjuisted usmng tIre vmmlues mnncmmsured in time laboratory. it is advisable to adjumst tine reconmnhirrmmtiun rmuiio to achnieve it. Section 2. however. may trot he suritable for special phrase behaviour studies such as asplraltene deposition. respectively. A narrow tuibe. instead of tine approximate data unsed un tine field. hunt shies not necessunrily inrdicale a represemntalive gas samnnphe.111. I’VT Tn’. Ann alternative surface sampling method is the collection of blowuing plnmnses in tIne tnrhinng mit tIme well head. A two phase sample. l ignnme 2. Tlrc samples collecteul from a flowing stream. Cone extm’mncts ofnemn imndicate a richer fluid in lneavy fractions particuularly sunrfacc active mrmmmneniais. l’lmis is to uuvoid preferential collection of gas or condensate becmmuse of their duffcrenrt (lenrsities mmmmui mnmomnncnntumium changes due to changes in the fluid velocity.3. gas/hiq vnii/vnml — — ‘ 245 1401 1509 C 0 0 12 . known mrs the iso-kimnetie smnmnmpling [8).. and Po and Pg are the oil and gas density. is inrserteui tn tIme cemnnrc nil tire tubing. l’Ire oil (condcnnsame) mmnnul gmis samples must be collected as single phase fluids.‘ “. Any leakage fromni mm sainnphumng bottle containing a gas-liquid mixture will change the sample conmmposition. with the inlet facinng tIre blosv uiiree(iomr. TIns cmnn he mnrostly due to the mmdsorption of polar compounds onto the core surface. (l0~P)t/ 4 .mn(l core extracts irave been reported 110. is eohleeieul tlrmuuumgin the narrow tubing into the saniphing bottle. a mimalcir betweemr tine Iwo values indicates a representmmtivc sanurple. and to adjust the flunid conrposilion if a fluid loss wmms indicated [9). Wlnemn time reservoir flumid is satunrated and the compositional grading within tine reservoir is nnminimal. The condensate carry over by gas in In separator cmmn sigrniiicumntly distort nIne nmremnsurru’d condensate to gas ratio.2.5.ctn anmd (‘orrelatinn. tire nmnemmsurred saturration pressunre of time recommrhined fluid slnoumld be comurpmnre(l wmtin tire imelul dmnta. 2.i. Samples received in the laboratory are evaluated for Ilneir integrity. mN/rn. ‘flre sepmnrator temperature and pressure. Ii is qumie evident tinmn( nmratchming line dew poimnt is mrot a reliable tmnclinod for reconnnhitning a gmms eorndemnsmnte samnmple. to avoi(i excessive inressumre dunning transportation in case they are exposed to high tennperature. and to use in the recomnmhitmation process. whilst tlmeir dew points are ainrost tine sattne.2 Sample Collection Surface samples are commonly collected from lest separmilors. knowing the tubing inside dimutnicter mmmnul estinnnmitmmng line gums cnmuiuinnessibnlity factor. ‘J’he method.is the minimum gas velocity. see section 5. l’hme dew poimnt 1 mmnmny irnerease mr (ieercmnsc by innenemnsinrg tine comndensurnc/gmms ratio. The production rate of eacln plnase shoumld be monitored over an extended period to ensure a steady mtnd stmth.4. to estimate (he expected opening pressure. 49 (2. A nmrmitt’hm betwecmn tIre mm memmsmmred slew pnni trt in tine Immhommmtory amnd the field reported vuultie is desmratie. A phmmse helmavinunr model can also be used afterwards. when the fluid compositiomn mnnd PVT dmmtmm are known. The homogeneity can be improved by insertiung a nmiximrg sectionr mmlremmd of tIne summnnplinmg tube. amid mmrc not neecssmnrily tine smmmmme mis tlrose present witinin pores nnf a reservoir. TIme mininrrtmnr gmns veloenty can be cnnnrverte(l Inn tIne gas production rate.le flow.2 slum inn’s Ilit’ I iqun ii drump—ounI lid nmmvinnumr of mm NontIn Scun gmns conrulcnsmmte at I Ire resu’rvoi lenmnpcimnttire prepared mml diffenennt recomnnhiinaiiomm rmm(ios. Time uric of ptrase hehmtviour models to evmrlurate and imnrprove tine fluid recommnhiiurmmtionn ratio is tlescrilicd irn Sec(ioir 9. MPa 40 Figumre 2. Smnnnuphes tested imn PV1’ lmnhormmtories arc blinds collected mit the bottonnr mole or at lire sumrlmnce. When flow meters with coefficients depending on tIne ml) — Recoin.6 0 Gas temperature: 322 K (l20 F) and proposed the following equation...(7] used the following average values in tire above eqummmtion. all unt lime well mcmi conditions. The information is umsed to evaluate the integrity of collected samrmples received in the laboratory. Ilenice. Whren the oil hunhhle point is known with confidence. kg/mtm. A kiwer opening pressure does not necessarily indicutte a fluid loss.

The effect would he of significance in pores typically less thmmmn 8 l0 m. Surface forces can be significant in tight pores. winicir inclunles a nmumher of issilating valves. Hence. ‘lIme mulca of lumhh stremmnrn (dim-eoi) snumnipliung is quite innlerestinmg. l’Ins’ valve itself is generally heated up to help elutimrg Iremuvy conistitunenls. withn tight cmrvities filled with water. where gas condenses in pores due to fluid-solid inicrmnetion. wlnere the removal of a large quantity of a phase will distunrh tire overall connnpnnsitioum. as the sampling valve Iras to be assembled to a high pressure cell kept in a constant temperature environment. a large amrmoumnt of the fluid is required to fill up time smmmnrphtumg loop system. kmnmwmm as tIre “blomn’-d. tIne cnnnecnntra0on of these cnnnstituents could be highly under-estimated. Therefore. as the injection volume is very smrnuull. have prevented its wide apphicationn. is inn nnnetastahlc eomnuiitionns. respectively. which vaporises the sample unto mu gums clrromnnmitmngrapln eonlummnnn for amnumlysis. as further ulescribed in Section 5.wlncrc a snnnmill anrronunnnt of inigin pressure fluid is directly injected into a guns cimrmnnnnmntmngm unpIn. The compositional grading can be very severe. The trapped high pressure lltmiol is tbncmm cxpnnscd tin hunt flnrw nnf mm cmmnicr guns. !‘VT lenin 39 condensate dew point may be very marked as its phase behaviour is dominated by lhe concentration and properties of the heavy end. Inmms mccci ved 5mm ire altennt ion mis ruin mmitcmirrutive to the blow donvn method inn tIre punst deemmnlc. is a remmsonable engimncerinng approach. as condumctesl by tIre above nrethod. hligln suipersaturahion has been observed no tests where tIne pressure hmts been lowered rmnpidly. such as bubble nucleation in water invaded reservoirs dunring dcpleliomn 118. PVT Testn mind Cmnrrelasimi. Should non-equilnhrmunmrn ioforunnation hecnnimnc innrportmmnrn tmi field operation. mmdi mis in ruupiul pressure build-up near Ore weilbore or in higbn pressure gradient flow. A olirect samnmplmmng tcelmnnnqume inn whniclm a smmuhi samnipie of a hniglr pressure fluid in a narrow tube is pminclned by mnmr aumxmiimnry fluiol (snnlvennb) at the test pressure has been proposed [24] to avoid tIne above problems.1. especial tests could be designed to generate the required data.2. will be furtlncr discussed in Section 2. ‘Tests inn a cell packed with 30-40 mesh head have resulted in tine samrre dew point as tinmut msreasured conventionally in arm equilibrium cell (171. l’he nrajority of tests arc depletiomn expeninncmrts. In conventionnal PVT tests.r” nnicllmod. The reduction of pressure results in formation of a second phase. An important test on all reservoir fund samples is tIre sletcmmnninmntiomr mnf tine fluniol comnmpnnsiniunnn.16). ‘lIre Imirge lonss oil line lest fluiti slurring tIre sampling ansi the problems associated with the tnmunnsfer limes mmmd isonlatinng valves Inumve becmn avoided by designing special vapour-liquid cells in wlmmclr tIne sannnphinng vmmlve cmnmn I-me imrstaihed directly onto) the equilibrium cell 123]. hence. the capillary condensation effect may be ignored. as tIne expostnrc nil a Imiglm pressure fluid to an empty cavity is generally mmcconmpamnned by mmmc phase ehmmnge. The introdumctiomn of a Inighr pressure fluid into an evacuated hinrc gemrcraliy rcsumlts in plrmnse clnmmmrges. TIne eonmnpositininnunl grmmditng is described in Section 5. using the rmniio of tIne separated phases. PVT TESTS PVT tests are designed to study and quantify the phase behaviour amnd properties of mm reservoir fluid at sinmulated recovery conditions. ‘l’Iuc test fluid does not flow througir the mnbnunve valves and. The above review suggests that the assumption of equmihihriunn betweemr nIne phases inn reservoirs.’. This has greatly simplified experimenr(al amnd theoretical stundics of the phrase behaviour of reservoir fluids.rs 2. ‘flre ireavy constituents of the samniple in all the ah.21]. ‘l’Ine flow 0)1 tIme solvemnt directs the slim slug of the sample into a high pressume valve wlnicim has replaced (Inc injector of a gas chromatograph. whncic tIne prcssunrc ml tIre siungle phrase lest fluid is lowered in successive steps either by imncremnsing tine flunitl volsunne nir reunnoiving pmurt of it. rcntrovai of a representative sample cannot be ensured. of tIre order s)f nnicrnnlitres.sslunl inn nIne analysis of gases tinan liquids that have very hiemmvy counslitunents. The effect of interstitial water oni tIne phrase belrmuvioumr of hydrocmmrhon fluids are ignored in most tests. to the conventional blow-down technique. lIne nnncthnod. tIne sannnples mnre generally expected to be similar. The most common method of counposilio. ammd the valve is detached from the cell for tine fluniol to be tramnsfcnresl to a guts chnrounnalogrmmpbn.2. brave rcsunltcol in some degree of supersaturation. the samples collected fromrr eaclm 7.191. however. wlrere tIne error involved in measurement of the two plnmmse ratio is relatively small. affecting the pinmmse bchnaviounr of fluids. to mrpproacln equilibrium. Details on connpo)sitional analysis and various techniques applied to characterise reservoir fluids are described in Section 6.ral wralvsi. l’he formation of a new phase is generally acconnipanied by sonic degree of snipcnsmmtumrmmtionn.4. line dcviumtininn fromnnn equilibrium may become significant.2 numnierically rcconrhined. a large volunre of the fluid has to be passed 1 through the oop to ensunre mu represenntative sanmple for injection. The two phases are innclividuahly analysed and then . The gas and liquid phases are commonrly atmalysed by gas chromrnatography and distillation. Phase behaviour models can be ursed to evalunate tIne extent (if comnnpositio)nnal changes due to grading in order to evaluate tine sannples. Such a fluid.’nnn’. and time PVT tests mmrc cormdmmcteui iii tIme absence nil water. l’hc pressure of an oil sample can be lowered below its hunbhhe ponimit grmnulmnmnhly winilsi main(aimning it as a single phuuse fluid. and neglecting the surface effect on fluid equnilihnia. tine technique is unnrehiable.sannpIium~. tine flunids mire given amrnplc tune mnnrui agitation in equilibrium cells.one arc expected to) he reunsonrmntnly in equnihiinniunmmn witlm each other at the reservoir pressure and temperature. Capillary condensation. Certain (nperationmal probleurms. resunltunng in mm column of fluid changing from a gas at the top to oil at the bottom. Altinotigln lIre smmmnnple vohunne actually injected into the gas chromatograph is very smmnuitI. Repemrted smumirplimng is mint an eunsy onr a safe operation in the above arrangement.131. or just isolmntenl from bite colunihihmitmmmm ccli. it is then exposed to flow of a hot carrier gas whichn mnn~eetstine samnnple mnmto tue gas eimromrnatnngraplr. ‘l’Ire hmmsic primneiple is to flow tine Iniglr pressure test fluid throungbn a special vunl ye tin trump mm sununli qunmmuntity nil (Ire smmmnmple imr tIne valve for injection. 2. and most ofit is lost wlren tIme smmmmrphimng valve is memnroved onr Ircmrted. Gas condensate reservoirs are generally assunnncd to be wInter wet. excepn urn dry mmnrul wet gas mixtures. All tIne limes irave to be cleaned and evacuated after emnclr injection to repeal the analysis. ‘lIre samnnphing valve with the flumid trapped inside may be physically rcmnnoved fronn time sampling port mmmrd transferred to a gas chromatograph (20. For small sannples or high pressure gases. locked in. Compositional grmrding dune to gravity mmmn(l temperature gradient may however exist in a reservoir.. signilicmnnnt sunpersatnnration is trot expected 1141. l’he vmuponised sample is directed to a gums elm onmnmttngrmtplr IInronuigln a incateul trrunnsfer litre (221. can give reliable results for large sanniples of highr pressure liquids.4. particumlarly for the comnrpositional amrmnlysis of eqtmilihrunted plnunscs in PVT tests. without any phrase boundary. where the condensate volume fornncd by blow down is low. Tests conducted in laboratories on liquid samples contained in a pornnus mediutnni. wmthr values as high as 5 MPa (12. with samples collecteti from different depths being vastly different.2. mumnol Ilnenn heatcoh up.s hate been unwire suicee. ‘lime umhinive unnmurlysis mmppmuimmchm. hnr a reservoir where the pressure decline is slow. When the onnncomnmuunnninate(l smmnnnpte reunehnes line valve. At certain coniditionms.s til Inigin pressure fluuids is to i’laslu mu relatively large volume of the fluid sample at the atmospheric pressure to fomn gennerally two stahihised phases of gas and liquid.38 2. line preference of the direct compositional amnahysis. When different samples are properly collected from the same reservoir. Inn saturatcul reservoirs contmuinnmmg Inn nnml conhmmmmmn muun(l mm gums cap. A small vnnlummnne oil line test flumid enters tIme vmulve. however. is a well known phenomenon (15. Fun!! stream .ove methods may be partially retained between tire smmmnmpiing valve and tbne guns clnroinnatograph colummn and.

we obtain. 0 ~C.. Tine value of R for different units are given in Table A. ‘llre specific gravity of the gas. Cg. P: psia) Br=Vs/V.005396 The measured pressure-volumnrre data are employed to calcmnimmte tine compressibility factor.2. (Bg0.65Ox2tt. calculated by dividumng tire tontunl nnmmuss. 5~ respectively. trunve been adnnpncd ‘flue are 60 “F. 8 Ba =. 0 The volume of gas at reservoir conditions required to produce mimic mint volummrns’ of guns mnt tIne standard conditions is defined as the gas formation volumnme fmmctor.(/288.65t).~1(-=Z(~-)(3) (2.85(it) Pv nRT ‘lint’ guns mnmmilecnitunm rn’t’mgbni (2.=. respectively.tt2)/(O.nninle 2. Z= PM(V/m)/(RT) (2. In the Fuelol ummnnts. ~I’~‘l ~.4). Inowever. B .3 in Appendix A.531 ennn . mIs connposition remnrmnins unmnehuminged duiniung production.5) ns c~mtcniIunts’mtfrnimmr Fut. as.3)= 146 kg/rn tm (V/m) is the specific volume.4-2. The formation volunne factor of a wet gas.. (1. Sg.> Figuire 2..(2..c 2.(2. A volume of the gas is loaded into a cell maintaimned at the reservoir lenrnperuutnmi’e. ‘I’lne gums volume is measured at the reservoir pressure and a numnnrber of prcssumrc intcrvmmhs Iiehonw it. Bwg~ is defined as the volunmnc of tIne gums mit reservoir comnditions requmireul to produce onre untnit volume u-mI tIne stock-tank liqumid. where VR is the gas volunre at reservoir conditionrs of pressure P unnnoi tennrpcrmmnunne T wilim tIne gas conmpressihility fact(nr of 7.79x I 8. . 7X 10’~ Z (T/P) (2. as gases almost obey the ideal gas law at the atmospheric pressure.3. Mg.40 2.r where T and Pare in K and MPa. needed to) uletemmrnimne tIne muminonumnt ansi properties of prouluced fluids at tbme surfunce conditions. 4 Bgrr3. IS “C and 21(8 K. Scpunrmnne tests are.2 I’V1’ lenin 41 t’ Z ~. The gas specific gravity. As no phase change occurs for a dry gas.=( tOO/I 8533)=Z(380. ‘1. mmmd V.6) M~=S M. nIne olemnsity is cumlcnnlated.2 Wet Gas common values PV1’ tests fonr mu wet gas mt reservoir conditiomns are simirilar to throse for a dry gas.i. Selrcnmrmmi mc vmmmnuniromns of guts fommnrmnl imimn vonlnnnnre factor willr pressure. p. 7.4) a a. including 60 “F. umsing Eo~s.8500x0. ‘[‘ire pmoiuiccui guns specific gravity is 0. Solnuin’n.=t). nnmisn linnmnk wlnerc time uimnvcrsunl guns connstmmmnm is tmmkemm from ‘T’ahle Al un Appennulix A.7 psimm. kuti.( 1. I 5)x(O.. 2.4) liii) turn’ of a gums mi mime rt’semnnnin u’ommnli(ionrs of . mmmd the gums density at (Ire reservoir connnl itionrs. The only PVT test required for a dry gas is tine pressurc-volummmne melmttion at tire reservoir temperature.3 K (225 nm : mmmd 2(1. where n is the total nunniber of moles.(2.t5n)(n7+t’iO) “it.(2.3. and is equal to the inverse of the density. in SI absolute scale. Sg = ~ V k ~l’ )‘~ (av~ (a7~ (27) A typical guts fonmnrnainin volnmunne fmuctnr plot is showmn in Figunre 2.O 28 Writing Eq. mummnl 288 K or (. 3 Z (T/P) T : °R.(n) z=— Z=O. wlincln arc uccum inn mInus interchangeably.3) a 0 t’ressmnre --------------.79)=O..3). i . 1. h/20. The isothermal compressibility coefficient of the gas. A o Sn.2. Various siandards for nennperature.1 MPun (I hmnr) or 14.79 Ml’ui (300(1 11 hnsi~)was bnrourglnn tui I Inc St mmniulurn d u’nmmrnl it ions. in Field Units.96=i 882 5 tisinmg Eq. p=(PM )/(ZRT)=(20. are related by lire followimrg relation. or by using the guns nmoleculurr weiglnt kmrowimrg its composition. can be calculated also umsing tIre variation of Z with pressure.6).3). loaded in time cell by the gas molecular weight.0083 I 44x380. (‘alcmmlale Bg. and the molecular weiglnt. arid 288 K.c mud (‘nrrehmmio.0 Mg/Mair Mg/ 28 96 . and the gas formation volume factnnr Bg.1 Dry Gas 2 !‘Vl’ ‘ic c. wtncrc tIre guns ocs’nn pied a volnmmmre of I 8. tIne guns voilummnre is ursumunily expresse(l un termnns of barrel in the above defimmitionnr.~ is tIme gums voltmmnne uul Ilie stururulunmnI s’ommntmt nnnnns ol lcssmum’e ~ and temperature T equal to 0. relative to air at 60 nup (288 K)t is deteninined by mmremnsurrimrg tIne weight of a known volume of the gas.. inn. Substituting the values at the above slaundard conditionns inn Eq.180..

rc ii—t’n. TIne liqumid density.16 36. The molecular weight and specific gravity of produced condensate are nn’reasuured in tine laboratory. Typicuni PV’t’ lest (lumla mum reporieol by a lmrhoralowy is given in Table 2. ~‘mn= - ~ (~~)T (2.1 B. and. This is analogous to oil formation volume factor. In the flash vaporisation test a sanrple of oil is placed in an equilibrium cell at a pressure equal or greater than time initial reservoir pressure. Section 2. and the differential vaporisation test. the evoilved gas flnnws towards the producer. is determined by a pycmnotineler or mmmi oscnilmutitrg tutne mlenmsitn’mnnmeter. In tIme wellhore. ‘FIre pressure umt whmiclr tIne slope of pressure-vohumnie line changes is (Inc humhhle-point pressure. currently uised in reservoir simulators.67 696 I 4.1 A. 2.nh compressihiimly ofoil.1. Figure 2.4).41 ticmnsnry-~85l5 kg/nmm’ (34.1 A.nni.nancs plus — —— — tepu:nnncc pills t~rn~nwn i cv mum cc. tine oil expands as a single phase liquid. A plot of Y function versus pressuire sinould yield a lime eillner s(n’unighrt or very sliglmtly cunrved. for zone C. 33. and extrapolated by a dimensionless function \‘.97 Sc paran n nr • 0 rn—ltnni:nnne t’n’nnn:Innc’ Oil (..> Itt 4.7 bar. The presstmre-volumme olumluu mnf tine black nnil.42 2. ‘lire slope of tIne cumrvc above tine bubble point. described in Section 2..89 2.. Tire pressure is reduced incrementally by expanding tine fluid volunsie.1.>.. ‘~‘ =f(P~P)/P]/[(V. A series of flash tests mit selected temperatures are also conducted to simulate the surface conditions. Table 2. and B. m’hnii. (4100 psig) Eunmpiricai correlations. olo’linreml mrs tIne runt inn nil lIme total vodumnre to the immit imul bubble p~mmnIvoiiunrme. In zone C. (Inc nrrixlunre nnmonleermlmmm weight can be detemminesl by material balance cumlcunlmmtions. unsinng Eq. Tire data is mmlsnn plontled un Figunre 2.8) winere C. The test 1 is also known as fluush liberation.2.enre and measuring the depression of its freezing point.09 3. Humid : Good Oil _______ Reservoir l’cumnpcrutlumrc: 378 K (220 “F) Originral Reservoir Pressure: 283.2.5. for zones A. it is assumed that the phuuses are at the equilibrium throughout as time pressumre depleliuin runie is lumile low. . The apparent specific gravity (or relative deursity to air) of time reservoir gmus is de(ermmminneul by calculating the reservoir gas moiccumlar weight.95 I. are also available 10 estimate the reservoir guns specific gravity from production data when some of the scpuurators data.nrnc I’tnnnnane liurtmnne 0.3 Black Oil The phase transition of an undersaturated oil during depletion is depicted in Figumrc 2.10) svlncre tIne sunbscripi h. All tIne reservoir tests are conducted at time reservoir temperature.orc 43 A more practical definition of the gas formation volunrme factor. zone A. ‘Fumb-de 2.05 6. but segregates from the oil dume to gravity and suurface forces.43 flimixide Nimnnngen Mum ionic ntn. constant composition expansion.3. is shown in Table 2. I’V’! Te inn nnnd (~m’.2.’nnmmnnc I ts’XnnncS I. -.10 3. Away from time weilbore. The above reservoir processes are simulated in line laboratory by (he equmilibrium flmmsh vaporisation test. ‘lunble 2.-_-. partmcumlmmrly in mnnuilti-stunge separation. 1 laviurg nnrcmmsunrcd tIns’ mass mmd molecular weight of proxluccd gas ansi onil (corrulensmnle) plrumses. is a nnreasunrc oil tire is(ntirermrr. per cunhic foot of the dry gas produiced fmnnmmn it mit stanrdunrd conditions. . wilin comnrpnnsitionmn mis in ‘[‘able 2. snunoonhed. meters to (Inc bubble point conditions. The molecular weight is commonly deteninined by drssolving the liqumini in bcn7.51 W~tnt% Ilydrmngcn SulFide Cunrhmnn Nil 0. The system voluinne is commonly n’eiimirtcol my t Inc relatime so/maine.24 3.m 2 2 PV1’ Te. flash expamrsion.iC.~j~. Phase transition in an unnder saturated oil reservoir. is mrmeasured at each pressure stage.M~L7~_ . the two phases are considered to flow togellner due to tine dominunmnu mnnixinng.3.27 ((. . report witlr permmnission.9) Mnr =(mg+mo)/(~L+~2~] (2. and pressunre volume relation. hence. The total vohuime. are missing._-_-NnI (tOt 0. Selected luthnles froumn a typmcmml PV’i’ report on black oil.4. ins specific gravity relative to water.1 5.29 77. V .44 I It . Reproduced from Core Laboratories June. is the number of barrels of reservoir gas (inclumding time liquids dissolveoi inn it) mut reservoir pressure and temperature. ~Vb)/VbI (2. (“onrnpositionn snf rcsemvnnrr oml. Mrlecutar Wcight=2t8 Reservoir A ‘lIne lmuboirumtory slatum is of (em evurluated. (nnirnpnnncnt —— . where tire pressure is still above the bumhhle point.47 9. is tIne minI rsnntlnu’mmnnuml eninmmpressnlnmhmty coefficient.( 1. defined as.4.5 ‘AI’I). The pressure in zone B is just below the huibble point ansI tire voilunine of the evolved gas is too small to allow its mohilisatiomn.

mit tIne ensi of tIre test is converted tni One v(ilunmmmc mit 6O’~F(288 K). Pressure Relative Volume Y Function Densiiy psi~ bar (1) ~ 5000 345. Time compressibility fuictor of produced gas is determined from.3 0.67 16 0. I’Vi’ l’e. B m&i.2415 1.9845 0.6808 4500 311.122 2. defimned as the rnttio of mmii volumnne/resisiumal volununne.96 x 10 4) Prminm 4001) psig (276.9946 mr.5 Relummive Vum(nmmmme wincre V is (Inc expellesi gas voluinie mit tine test pressure P.6585 F (288K) (‘omnrnpressmhiimry nil snnturmnlcd nnil t? reservoir iennperanurc: (Voi/Vol)/psi ((Vol/Vmnl)/bunr): Froirn 500(t psng (345.6 .6609 3000 2900 2800 27(8) 2620 2605 200.5000 .2 kg/mimi) ‘thermal expansion nil rcscrvoin nnil 4000 3500 276.6763 4100 283.7 0~9639 0.5 166.7 burr) = V @ 220fF (378K) = 1(18795 ((.7 58.72 x I0”~) V (ii’ (no @ 5000 psng (345.418 2.pniinnt tircss. I. mmd tenmnperatunre T.4 1.8 har)= 13.497 2090 1897 1698 1477 1292 1040 830 640 472 145.I(n27 1.6 174.11) 10 0 0.9 x tO~ (2. 40 no tlurhhte I’nninl 20 / 0 Figuire 2.3).0648 2.5 156.2 18 1. .8 har)= 15.5.9 i.~ is barrels al i ndicamed pressure per barrel am saiurmnminnn pressurns’.6 0.3 1. at lire mnt mniospineric pressunre.325 2.s ‘l’ahle 2.911 1.0 5.0353 1.nmhble point pressure. 4.6572 1)6562 2591 2516 2401 2253 179. The ga~formnration volunurre factor is calculated fronr Fu .6665 0. hunt onftemn diviuled by 5.99.nr.9984 1 .1 131.64 (m.9 194.lC Volunrretric data of oil.e ii n 2 ii 1. A eumclr stage tire nemnmainimmg oil volunnne.8 0.6.8 bar) inn 3(X)0 psig (2(17. conrnnrnunnrly ursing ann unvcrimge I hermmnal comntraet nmnnm cuici incicmnt oil 0(88)46 (v/v )/“F.6 bar ? 378 K) 40.(2.(nI coirvertiung ml to huirrel per stuumndard cubic foot (hbl/SCF) 1 unsung time Field unmnits uus time gums volumnire mnt reservoir commslitiomrs is to be added to the oil wlmemn vnnlummnme inn barrel to (le(erilninC the total hyulrocmurhon volunune.tiaI m’nmp(mI’r. hontlr mr ahsoIurte scmnles.7839 2.3611 1.30 x 0~) Frniirn 30(X) ~i~g.7 hmmr) Inn 4000 lisig (276.637 (I) Relative Volume: V(V.1709 2.1041 I. 0 Figure 2. Sclneunuutic diungrmmm of ditferential vaporisation (liberatiomn) test.1 33.6 180. 1.1B Pressure volume relation at reservoir temperatunre. and lIme gums specific gras’rty mire nnieasunrs’d.1 72.(2078~ (181. All the evolved gas is then expelleol mit cnnnstumnnt tircssunrc by rcslumcmnmg (Ire Cnhuiulihriummin cell volunmnme. Saturatinnn pressure (hniintitc.m’ imnmd C’orrm’lmntimi.0157 1.satuni or Iiliermitio’mn test.0042 0. Time rennnmninninmg (nit vmnlummrre.n’n.5 x ttt~ (1.033 Iin tine e/iff~’.6 har)= 18.nm’ 2..5 1.8 90.9702 0.7 0.9928 0. Pressure-volume plot of Good Oil at 220 °F (378 K) to uietcm’mmnimne its t.1 102.8 242. 220 “F (378 K). ‘line vnnlnmrnrc oil oil at cureIn sluuge is reported by tire relmntive onil voltunire. mmmd n c erred Ion mrs time mcsisiunmml oil.1(1(1 1.OtX)0 1(1(121 1. 45 Table 2. I’V7’ l’o’. Z=(VPT c)/(VscPscT) 5 (2.9770 0.22m) 2. It). Figure 2.2 45.3 207.9756 0. the expelled gas volunmnre at tIme cell uunnd stanrdard conditions. ‘T’mntile 2.718 1.2.7 x i0~ (2.8 118.44 2.6961 2.7603 3.st.6597 0. Density at saiur:niion pressnnre: 3.1 187.97 lb/fr’ (656. ‘I’Inis pronce(lunme is repemnted iii 1(1-IS pressunre slunges olowmn 10 tire atmnrospireric pressure. tire mnil pressnmrc is reoluiced below its bubble lnmninmt ull I lie reservmmnr lennnpcrmntmnre by rxpummroiinng line systenmr vnilumme.6726 262(1 psig @ 220’F (181.mre): 2.

divided by the residuuul oil volunnne. ‘lime effect of scpurrmntor arrmingemnmcnt beconmes mnnore significant for volatile oils. Bi. Tine test is usunally conrducleul at mm nunrber oil separator pressures to determine tire optinnmuunn field sepmuration cotnslitinnns. The crude oil gravity. ‘lire tots] volume is 8reported by the relative (otal vtnlumnnne. Time ratio of reservoir oil vmnlunmrrc to stock tank oil vonlumrre is givenn by the oil fnnrmatiomr volume factor. The nuunnbcr of reservoir oil hmurrcls ton proolumce one stock tank barrel of oil in Field evolved guns is reponrtcd by tIre solumtmnnmn guns to oil ratio.1 E.7 - 1.007 (rums/oil Ours (. mit tine standard conditions (se).n Vmilunrnne Jmacnnnr is barrels ml saturraled oil 50 2620 psig and 220’F per barrel of stock tank oil 50 60’t~. .600 1.s iii tIre oil plnase with mu separator pressure of about 100 psig.ID Differential vaporisation (liberation) test results. Retanive Oil Relative Solu0nnn (las/Oil Pressure Ram run (I) Vnntunsne (2) Tonal Votunne(3~ p~ 1 1 n.215 2.9(13 1)922 (1.445 I 412 1.t’API @ 60’F 97 85 74 63 52 40 28 1) 1. Separanmnn Oil Vnnlunmne Facnnnr is humrrcts nil onil 50 indicarcul pressureand memperamure per barrel of stnrck tunnik mini 51’ 6I(’t~.601) .! C’orre!aninn.65 psia per barrel of stmnck tank oil @ 60’F.479 . The stock tank pressure is always atmospheric.5 1.3311 0.797 0.016 2.18(771 000882 0. OAPI.1 245 246 1.ceparalor test.51. Inowever.rniianim.7182 1)7892 (1941 1)965 0.as Rumilmu nn cnnlnrc leer mnf guns 51’ (n ’ and 14.007 1.474 1.1 1611 59.748 1. (2) Volume of oil an indicaned pressure and nemperamure per voiunnic of reonslual oil an line snanndmmrd cnnnmlnmim’ns.~~iuy of Flashed Gas l”’5 5(1 Ii Inam 4.8 1) 21.6508 06889 (1. unsimng tire prevailing B .665 1)846 0. Schematic diagram of separator test. ‘rahlc 2.1 12.rmnvmmy ‘ At’t Vmulunnnc Finctuir Vmiluiunne Sped tic ( . All the vniltmnumetric results mnie reported relative Inn tIme stock tank oil voiuunme.6 III 3 94. 1. The concentration of (7~ in the gas phrase is very small in most cases. delmnned uns tire u’mmtinn of totmul volumelresidural volunre. (4) Volume mif gas at indicalest pressure and temperature per volume am nIne slanidand connulimions. defined as the difference between the total gas evolved at tIre atmnnosplreric pressumrc (tIre iinnuul stage). The differential relative volume data cuin be evunlurmilcd umn(i smnnoontined by plmnttitmg lmug( I -I versus iog(Ph-P). In the . Rcb defined as the volumetric ratio of lIne tn.254 6975 14.~~s ~nclnsr (4) (hasiny -- 2620 2350 SCF/bblvnnl/vo 18 I .483 1. Sepmnmator test results Sn’pniinnur l’rcscnnne Oil Dcnsniy g/crnn’ 1)6562 0.0 763 136 -~ I . PVT Incus (nun.786 010851 1)988 . defined as the 0 units. and each pressum’e stage in SCF.039 411. ‘[‘he oipinnsmuirnr scpmurmntor pnessumre is amboumt 1(8) psig winere tine fornration volume factor (FVF) is nnninrmnnumunn umursl tIre nnrunxinnnumnru slock tmmmrk nil is produnced. a known volume of the reservoir oil at its bubble point is flaslncd generally in two stages. more tinaur one iniennnedma(e separator is often used.693 (1.859 2.4 1.7. Gas/Ott Ratio nun cubic feel of gas (~1’60’F and 14.704 1.818 0.851 1) 859 0. regunrdlcss of the separation conditions.0 684 612 S’t4 479 416 354 292 223 57 0 122 109 Gravity of rcsr~ual oil = (I) Volumnie nif gas at nbc smandard comndinions per volume of residual unit.rs 2. Figure 2.6 854 152 bar 63.02042 o.S t).363 0.075 35. Rsnt.65 psia per barrel of oil @ indicated pressure and 0 1~ icnnnpcrature.1) 0 1.c 47 The total volume of gas evolved at each pressunre and all previnnuns pressunre stunges.8 28.954 (((12951 ()0S1%. The stock tmnnk mnil generally contaiums only a trace of metirane and an nnnsmgmnilmcunnt amnoumnt of ellnamne.831 (1881 itt 75 “F (297 0 .01051 11(11 2. inn bunmrels.495 1. mns shown in Table 2.840 1. All tlrese indicators point to a Inigirer accumulation of intermediate connnponncnrt.46 2.554 I . Operational lnrmnitumlmomrs mruuuy.45 (1 7. mmiroI (Inc ~ uninml tcmnipcrurtturc of scpmura(oms.872 1)887 ((. For oils with high gas in solution. ‘[‘he relation is expectesi to be limmeuur. where the last stage represennts the stock tank as shown in Figure 2. B .1 F.732 1. lIre nlnsiritiunt nun nil cmnnmrpninnemmls lnetweemr lIne proolumccoh guns airol stock tmmnk oil depends on the nmum mmrtns’ r ol sepmmnumt nun sIurges.7.00685 1825 21(51 11150 16(5) 1150 tOO 1150 6(8) 350 159 145.481 11(0 ins 1) 2(8) Inn t) 31)0) (1 (I) (2) (3) (4) 92 6(12 178 549 — 40. lIme results of sepmuruunor mests fmir the oil given inn Tumble 2.148 40. also motauns mIs mrnaxinnmunnor vmmlume at line oipnnnmnuro pressure wimercas the gas to oil volumetric ratio (GOR) rs umt its nnmninnrummim. PVT l’e.n~/( )nI Rumu no (I) .~S (101552 ((.t.9 I) 14.515 1.6 42. The volume ummnsl tIme specific gruivily of the stock tmunk (nil at 60°F(288 K) are also delennined.182 I 351 1.286 542 177 478 40. is calculated amid commvcried Inn tine volummmue un tIne lest pnessumm’e.2.7’~t 07)4 0811’) ((. It is time relative distribution of (he intermnnedimnle frunctiouns bctwccun line plrumses thrat detennmimnes tire optimuumr’r separation conditions.SCI/tntnt 715 41 637 91 Ours I )nl Rmnm Inn (2) . Table 2.8 [25).4 25.283 1. A field avs’rimgc lempermntuirc is selected for the separator tests. The (nplimumm unrrunmigemmnemnt is tIme omne wlmicln pinuluues unmore of Ore stock lank oil.1 F are shown in Figure 2.007 1. (3) Vniluinne oil oil plus liheramed gas at indicared pressure and remperarure per vnnlunmie of rcsnduat nil an Ihe siandard conditions. Table 2. dictmute otlrcr pressure conditions in the field. Fmulnle 2.11 2 1.6’t69 (1.329 0. Pn.1 F.244 1.031 1(1117 1.6655 C ormupres.6731 0.214 2 593 3 I (i9 4. Gas FmnrimiumI lmncrenmneninat (macunit Votunnnnc ( .062 0 .7 t) 1)7198 1)7291 0.1/S Ut 737 41 676 Snuck Inmnk 50 (nuT Fnirnenatimimm (3) vnnl/vot Sepunrunmmir Factnnr (4) vol/vol 1. The evolved gas is reporleul by tIme solunlionmn guts to unil rumlmon. and is added to tIne oil volumunc to ohtaiir tine tsnlmml Uwo-Inimurse) voilumumre.32(1 1.nl/l nxttn) Tire cnnmposmtmonr mutnd spccnfic grmmvity of flumslnesl gases aie urneasured.(uml gums evolved (sc) to the stock tmunmk oil (SCF/STB in Field units). considering also otircr cconomnic criteria.7044 1) 7121 (1.1 D.uf.

0164 2)).W.6 42.6 I 63.2.123 58(23 72.0149 (1.29 11. dctenrninred 5 by ulmflcrcnrlial hiberatinimn.15.1G.8 59.Pentane n.0134 0.0) 125 (1.653 1)742 (1. ‘FIne differetntial liberation test data are based on the residual oil un the reservoir.c 2.097 58. mit pmessunres below tIne inilial huibNc point are available in PV’i’ repnnrts.3558 .6850) .624 I . Eiemnce.2.013 35111) 3(1181 2818) 2620 235(1 2100 .0 (1418 11. lb/It . E ~ — : ~.6 48 6 0. althonigh pant of lIme liquid plnuuse is recovered wlnilst the gas is immobile.7 32.33 0)26 t). The amount of these compounds is expressed in ternnns of galionrs per tlnousand standard cubic feet of gas ot’ GPM in field units.n ntis! (‘u. As ~ and R d.6305 .are the mole fraction and lime molecular weiglnt of time comnmlnnummennt m inn line 3 produced gas phase.104 Propane i-Butane n-Butane i.67 44. and the specific gravity of the component i.32 71. Ilnese vmilunes are often nmnistmnken as time fornration volume factor and time solutiorr gas in mnrumterial halammce calculations.36 0.5840~0. 15(1 84 Heptanes plus Calculamed gas gravity (air 0.621 .m: The specific gravity and Molecular weight of normal butane are read frommn Table A.3. Pi’ and S~ are tire density. the prnnpci(ies oil humid prmnduiccd at tine surface are relalesi to lirose at reservoir conditions by tIme mesunlls mnf scpmmrummnnr Icsts. delemmnnirned by tIne separator test represent tIre original reservoir fluid 51 belrunvioumr mit lime initiuml hunbhle poini. So! ofio.. Example 2. plig 5)11)0 451%) 41)1)11 345. I’VT Tent.1G.l2/Q. ‘Fine produmced gums viscosity is 011cm calcunlated umsing a prediction nretlmod.0111) 28. 5(1 72.s 49 & 4 0 W U ~ C ~ n • 1.379 1)373 (I 394 1(4(6 11.9 bar mind 1 297 K).017 . The flaslr sepmirmnniomr siunntnlmmtes tire llnnw nil guns ummnsl (nil in tIme well lnnnre and tlneir suibsequment separation in lire scliumn uilmmr.5623 .5 28. Hydrogen SulFide 0.Pentane Hexanes 16. decrease as tIre pressunre fmulls below the bubble p(nint. Sectimiar 2.0l98X58. Nitrogen Methane Ethane 0.i.01 42 36.s 212 3 21(7 8 94 I 11(1.481/p ) 1 1 1 = 0.~Dcs~/cinn Component Mol % (1PM MoI. time oil formation volume factor.2997 .5840 and .7 311. however. cmimnumesy ml PennwWell Publishing Cnnmpany.92 1.0) 1. mmmd mnol Ihmnnse of differcmrtimnl hilneralinun. !‘V7’ 7e.502 1)542 ((.1(70 44.128 103 . The GPM of a component is cumleulated from: (GPM) 1 = (l0001380)y M (7. mind its helnaviour is simuilated by Ihe sirrnple isotlrerminal expannsion inn Ihe pnessure-volumnre lest. time pressnrre—voiuinrne test (Iluishm vaporismntion) almmnost describes tIre process.450 (1.786 Processing of separator gases to liquefy intermediumlc lnydrocarhoms unnay be economrnicunlly feasible. Compositional analysis of senarator gas at 100 psig and 75’F (7.5834 . Yi’ and M~. mmmd (Ire solumtiomnn gums Isi oil runtion. Repriinncnl frnimun 1251.12.590 0. Viscosity of (nil at reservoir tenmnperature.00 Carbon Dioside 1. I 76.1 73. I equal to 0. l3nnthr variables.2. ‘I’lre vurlucs of nntn uumnsl R .01 i6 59. Tire process tinemr becomnmcs mrnore smtnnilar to the dilferetrtimnl vmnporisumtion. Table 2.98 0.3l5y M 1 1 /S1 (2.440 (1.01 73 0. Calculate the Iiqumid n-bulan’ne content of the gums prmdiiced fromnm tIme separuuimnr nil tIne (Imnund Oil at 100 psig amrd 75 °F.IF.0(96 (I.51)65 .08 15. variations of oil properties witim separator pressuirc. A part of the gas.12) where. ‘tIne reservoir oil rennains single phmmmse as burg as tIme pressuire is unhove its buhhle poinmt. tlnurt is. The pressure below tIre hunbhle point is achievesi by depleting lIme visconnmeter fluid clnamber and expelling the gas.7370 1851) 16(8) I 350 111%) 85(1 600 351) ISO 0 I cennnmpoisc= I rrnPa.ct. 1mm materimml halazrce calculations.62l gallon of liquid per thousansi ft’(sc) of gas .413 • l’hc oil viscosity is conomonly mntemnstnred by a rollirrg ball viscometer at tire reservoir temnperatuire amnsl a nummrnher of pressunre steps above amrd below the bubble point.29 = .469 t).2 0)0156 0.4 41. Lior.9 ‘FIne belmmrviour of mm reservoir suil slumrinng slepletiour is siinmurlated by a combinatiomm of all tinree types nil tests discussesl above.043 30. I 22.128 2. The corresponrding values by the differentimtl test are alnrnosi unlways higirer unnd earn lead to errors of 10 to 20% in the calcunlated oil in place and t3 1.1 12. TIne guns evolved jun51 belsnw tIme bubble point initially remmrains inrnmmrohile in pores.854 1.8 128.6 111.8172 . whereums tire volume factor and solution gas slata based on the stock tank oil nrust be used in immutterial halammce calculations.0 . 121) .000) = 0. rcmmnuniuns inn comntact wntIn lIne oil connlraiy to tIne sliiferemrtial vaporisation test. I in Appendix A).3l5X0.41)1 0 385 ((.t) 183 0. ‘lIre results for tIne Good Oil umrc simnmwn inn ‘Fable 2. respectively.58.3 94.rrr’knI/mu.27 4. GPM=0.8. 0 ‘8 ‘1475 it 0 (‘atcutaned Gas Viscuisily 1691 ccntipoise ()nt/Cas Viscnnsrnv Ralio o psig lb Separamor pue~aur.7 25. The evolvesl gas hegimms to unmove away froimm the oil as the gas saturun(iolm exceeds a critics] value.52 7. at standard conditions (Table A.094 . Tumble 2. as liquid.434 on ‘ ~ I s’~ C . respectively.4 25.48 mill 2. Prcssmnre Oil Viscmisiny liar cenlipnnise 0. Hence.8086 .299 . The differcunliurl libcramiomm lest is cnnursideresl Inn simumiate lire evorlution of gas and the associated slrrmmmkurge nil muil in line reservnnir below tine hurhble poimnl.3 276 II Figure 2.

10.)-~55 (2. The evolved gas per S’I’B is (lmemn enjunuml tmn.16) 1 II tire solution gas in Field umnits is ulescribed by ft lbbl. below line btmhble ponmmn) Figuire 2.14) I lemrce. mus tlncre is very billIe emngineerinng application for the near residual data.9. The gas in solution below tine bubble point by flasir test can also he cmmlcurlated by comrmbnnmiung tIne differential liberation data and flash test results of time original oil. B . ton deternmniune tine required data for reservoir studies [27J. tue nnretlnnnd is used widely for Inlack oil systemins slune to its simplicity and acceptable accuracy. by one unnit volume of tIme stock tunnk oil B Figure 2. Hence. where the sunbscripts h. The reported data by conventional PVT tests can be combined.ns I 2 2.ns —‘ R.. it may be cleimned as the reservoir volume occupied 1 and its associated gas. These confusions could have been avoided mostly if tine residumal oil irasl heeun reported at the reservoir lenrperatunre.13) lime cmmlculmitcul R lnnm I lie mint inn l’unblc 2.s 51 recoverable oil 1261. . 1 — (R. Adjustumrent of oil relative volinme factor. I Ire gums in sol umtnonn R is equrunl to. respectnvely. I’VT Te. aunsl tine olrflercnmtimnl test conditions. TIme gas evolved below tine (2. ‘line s’umlcuilun(cd duntum mime unmmcccptahlc near lire residual oil cnnnrolilionun~.ni. I . MI’a IS 20 Figure 2. ‘lIne unnit of Ihis gas is inn SCF per hunrrel of (Inc residunal nil. In S It) IS 2)) Pressure. PVJ Te. however. . however. tire gas volume must be divided by 5. MPa lIre ratio of molal guns mmnid oil volunme unt tIre reservoir conditions to the stock tank oil volume is expressed by (lie lontmrl volumme functor.qn mind Cm nelnlio. - R. and separator tests haul heenr comndumcted on liberated (nil samples as well as line original reservoir oil.50 2. I Is slnmuwnn in Figunre 2.. . Tine adjusted formatnon factor for tine oil in Table 2.n) ~ (2. (2) The relation between tine FVF of flashed aund differeurnially litneruited smmnnmples mcmnummmmns constant over the entire operating pressure. and d refer to (he initial bubble pount. hunhble poimmt is equmal to the origiunmnl gas Rcdh tininnuis tIre remaining gas R d by the differential 5 prnsccss. l’lre oil fonrnratidnn volunrnme factor B by.9. is slnowur nun > 0 0 0 C > 5 I)) l’rcssure.61.15) 11 at any pressure below lIre hurbblc pnnmmnt is llnemr s’urlcuniumlcd B = B~ 0 (2. l’he above two assummnptions inn cumInvu’ iii mng (Inc5ml 1 Is’rcmnt imml I ibenuit in inn olumtum Inn I Ire selnumm mutmir slatum tiecommme less rcliumhle as more gums is Iiberumned lo nnnn line unit. Tine main assuuumnptmons are: (I) Tine gas in solution at reservoir conditions below the bubble poimit llnmlt will be Iihermmlcsl mit the surface by flash vaporisation is equal to time difference between tire original guns inn solumlmon ansi the liberated gas by slilferential liberation at the reservoir pressuire. = R.10 Adjustuunent of gas inn solutisin.

CCE. l’Vj’ i’m’.b—R.4 Gas Condensate The compositional analysis of gas condensate fluists is conducted gencrmnlly inn nnrore details thamn that of oil. or the pressure-vumluimne test.simlc Mcllrunnnc 0. Coinnpninenis MniI ‘Ye b~t~ = B. Cyu’Iumnes C.127 (1063 t/. we can write. = 2.298 I . 45 0. mis described inn the blow down method.2.11.’aincs 0)1154 1)084 (1. 1 Fllnanc l’inmpannc 7 4113 3.b BOd.2. is slrowmn in Figure 2. The fluid heavy fraction is analysed to islentify nnajor componnenrts.ptmis 0.1 kg/inn’ TIre two mnnost connmmrnon tests at tIne reservoir temperature are tIme constant composition expuumnsio)ur.! I’m.553 Munlecurtar Weiglrn 27. nil tt’pn inc 1 )u’ruinmcs ‘t’mitumr’nnc Cyclumncs C. Gums anol conndcnrsmute vnnlumnmres unre recorsled unt cumcin pressumre step mrs well as time onhscrvcd ulew poimut. unre sinmuwmn in Figumn’e 2.icnnsmnnes. nn~l)cu’unne Unnnlccaiies Dmxtccanes ‘l’nintecunncs ‘Icirunnlccunnics l’cuniunmlc. A Iypicuul pressuire—volumume curve.. The compositional data are used oftenn in plnase behmnvinurr nroolels.282 (1. the dew point camnnot he measunmed accuralcly by nnooitoring pressure- . Armmurmaiics C’. re’In.176 0 10 20 Pressure. 144 ti 126 I lcxumdu’n.2A.~___+B~(Rsdb_Rcd)j__ (2. a knnown mumoumnml of gas coundennsmn(e is loaded into a visumal cell above lime initial rescrvnnir pressumne.c 2.5(5 1. pumr(icunlunrly in reservoir simulation.!. In CCE. 0 n-I lu’pnznnes l(emn.u 53 B 0 + B 8 (R. o Occinnu’ i Nm. l’Vi’ l’e. Ilennce.mnnc (‘yctunnes C’.61 (2. Mu)cculunr Weiglni = 353 l)ensiiy ai 21(8 K= 852.nnummncc C 0 I).Fluid A Nsnrmln Sea Gas Condensane Reservoir l’enmnpcrunlunre: 394 K (250 ‘F) Using the differential liberation data. + Bg ~~imtu~ (2. ‘l’mmhle 2. in Nmnnanne n~t)cu’unnnu’s (115% 1)143 1) 061 ((. . Selected tables fronr a typical PVT report on gas condensate. mmmi. CVD. l)etails on testimng lire listnniol frumctiomn to characterise the fluid are given in Section 6. I 5)) 1)253 1)1 (i8 ‘a 0 Arnmiiizmtics 1.721) 71) I 39 The variation of B with pressure and its coinnpumrisomr witlr 13. and also to characterise it by extended carbon grounps. Tire properties of single carlnonmm nnumrrnher grnnuups mmreuusuiicoi inn lIne iinlmnid lulninse are considered lobe Ihe same as those in tIne well stm’eummnm. 1711 0.2C. 2. B.. 1)etmnr led__comrnpcnsmt monnun I ummnmnlysrs nil Ilne web I slreamrm.iim. Arm abrupt clramnge of slope at time dew poimnl ulnncs noit gemrermnlby occuir.2.11.12.innics I ln’piundu’canes (klunnlccuuncs Nnnrnuiutcu’unnics (1.2. whereas Table 2.111 1)271 II 31(9 1)2)5 n-tlcxumnie 0 LI.1. lIne systcunn pressumme is lowered stepwise -by incrementally expansiing the cell vnnluinnre.’.64 MPa (7 911 psia) and in Field units.3 ‘‘t0cnmsunnesplmms’’ clnuiracierisinn’s. l7um) Nilnungen ‘an bonn ulim.)15. The fluid is comnrmonrly alrmulyseol by flumslnmmng ml mnl tIme umnnmrosplieric pressure and measuring the composition of tIre stabilised gas and liqumisl plmase.17) Rcseivmiir Prcssure:49. Selected tables fronnn a PV’T laboratory report on a North Sea gas condensate sample arc presented ins Tables 2. witim lIne data reported in Tumble 2.359 1)551 0.16mm) Table 2..2A shows typical measured connpositiomrmul data. MPa 30 4)1 Figure 2. as the results of phase helnaviour mmrodels are very sensitive to the heavy end description of gas condensate systems. unmnd time constmnnl votunne depletion.mm.2C.ti.Pcnnmunncs n-I’cnmiune it Icsunnies ((.318 0273 0) 253 0. Bm momBOb .113 (1.334 11.293 i—Bu(unnic n’Bumianc i. ‘i’umble 2.225 (I. l’ahle 2.. Variatiomrs of oil amrd total forrrrumtinnmn vonbummmmc fums’knns wulin lessnums’.52 B.255 0..s.213 describes tIre distribution and properties of lneavy conlpnincnnts uns simmglc cmmrbmnnn nnmimnnber gnnnunps deternnnimncul by distillation.

88 203 23. Densily an 288 K=834.nm’ n nO rcirm grumnk _Iunc or.9620 2. Tlnese fluids may also slrow mm grmmdumunl reversible eolnrumr change.e.Ini.0 318.)) 749.15 ~ 1’- Spec. ________~YLY~1~). is shownn in Figunre 2.s.0)2 12.9181 2.0 332.7229 5..9395 0.6 kg/nnn3 > 11 6 S • S Pressure-volume relatisnn of tine reservoir fluid at 394 K. Mt’a 40 50 Iugumre 2. 7.0 421.grade liquid am indicated pressunre)/(Iolat volunmnne an saluralionn pressure)xtOO (no ncnnpcrumnuire. = PV/nRI’ (n imniuml mnninmihcr ..m 55 volume changes.0 51)1.0 181. in rich gas condensate samples.1)550 1.0 481...41) 11. 7)).0 4’tOS 39(5 3335 2610 0. panic Itun)anncs Pennunnec 0 00 1)1)0) 0.k’unnlunr wn.igIni — 50 40 30 I texancs Ilcpnunnes Os.1039 1. as shown in Figure 2.56 7.ulunrmc ni liuki nI Salultaiinnmn pru’ssnnrc and indicaicd nerunperalure. I’Vi’ Tm’.12 I’iessuie—vmdumnne cunn ye br gums cotndcmnsumtc umt 394 K.70 8.79 7 18 9. The expelled gas at each pucssumre stage is collecled mmnd Os composition.5 271.0 332. I nmnm nI rcscrvmnmr pressnmne.4 1. 89 0(5 21) Nnunanes Decanes Undecmmnnes l)nxlccanes Tndeca~s Telrantecanes Pcnnadccanes Itesaslecanes Hepradecanes Ocnadecanes Nmnnundccanes Ficosanes’plus 7. II is cminnnunnnumnly umssnmmnncsl timunt (Ire uunnrdemnsumle dropped ount in pnnres remains inrmnnobite.2.5 254. which nrakes the measured dew point qunile subjective.7 838.2 835.00 0.5 466.1876 11718 I I (~60 1.04 5.8953 It) 20 30 I’ressusc. tlnerefunme..9815 3. Pressure ~ RelaIn cc v.89 5.uiule Meihamne t’nlnunne Fr. Tire dc )lclionnm process is.3)) (1112 (.2710 3.3959 1.9113 2.5 271 5 288. tIne dew point is manifested by fornnation of a large amount of conslensuste.0 175. ‘lIre lest comrsists of a series omf expansion 1 bollniwed by cxpcllimmg line excess guns mit conmstanrt prcssumrc in suclr a way that tire cell volume renimuniums co’snnstaot mut nine end oleumclm stage.88 3.0 7975 7540 7250 7183 7105 6960 6822 6743 6598 6380 6)190) 5655 5075 ~ 311.2C.si.2.0 -.8012 2. vobunuc and compressibility (deviation) factor .0(333 3.50 3.05 (I) (2) (3) (4) (5) Salinrunniunnn pressure am nnmticamcsl nennpcrannnrc.1) 100.11 2.5 8295 832.0 175.0 796.93 127.0 3111.9094 ((.0 456.1302 1.0 (2) 496. Table 2.0 — — — — — — — — — — — 152. hr nnnosl curses tine innitiunl Iioinniol hmmildum n 1 is gradual.e - ‘a C. V. ‘FIre volummnre of csnnndcmnsu’uI liquid in Ihe above test for the Nortlm Sea gas.29 4.0(74 1.73 2 92 4.(5J I 2866 I 2429 1.4844 1.153)) 1.44 3.9935 I 0000 1.tnnnn.9765 0. getting darker.Inc _____________________.0 351.0 219. sinnnmnl~nls’dmy CVI). i.1 776. mis tlne dew point is uupproimclmed.0 ((81)1 127.5 2880) 303. Il 363) 70.40) 13.0 (I) 471.5 197.(u’s) (Vumlunne mnl reiru.7 121 138 sI 10 0.9401 ((. Tine nnneasurcd slew point is..9599 0.0312 1.2B. 13.0 231..)) 711 5 79). 22)1 234 2’t9 263 353 5” 2 10 “Undecancs’plus”clmaracmerisrics: Molecular Weigh(=23t Table 2.2632 1.0) 2365 254.0) 271.’thncs ((.1687 1. Table 2.0 236.1.5 81. ~ Inqunl.13 Liqunid bumilul_urp clmrve for gas condensate at 394 K.~)__ volume 551.0 521.5 1970 2(9.9297 2.0 303.4 81.9 810. Coniponent Weighm Range nil ulismillununonn ‘Ye Carhnmn Dio.00 0)00 ((.0)11611 1. Distillation results of the liquid fraction.5841 1.0 441.4 822.7664 4.8894 00)) 0)0)1 1)1)0) 1)1)0 0.6 1.i mmim.48 5.0747 3.54 2..2 1.9787 0. nninprcssnhnlnIy Vm.8620 2. = s.1619 4.6 71(5.2158 1.0 391.0971 1.1456 3.2074 1.1991 1.0 ‘ 764. close to tlneir critical tennnpcrmnluli’e.r 2.0)661. Note tlnunt the condensate fraction is defined relative to line total volume.1 164 178 192 206 Relamive Volume Figurre 2. therefore.31 5.1 852.9773 2.8 II) 1.0 152. I 0195 ((‘1764 0. qumile accunrate.0)1)17 3. PVT Tens mnum! Correhijimnn.9826 0.4 I I 0) 2.60 3.14.4 491. ‘C Dcnnsiiy mn 288 K kg/inn’ Mm.(.51 5.

0 c:i 0 U 0• •0 s 0 S CVD 0) 1) • 10 20 3)) 40 .(2. Note that the accutmumlated condensate volumes are very much the same during tire condensing region.17 9.111) 521. TIre results of CVD test oim a Nortlm Sea gins condensate are given in Table 2. Table 2.l’ remrungradi’ liqunid an indicaled pressure/luntal vnnlunnmne an samurannmnn pressure)x I (Xl 3915 31)45 2031) 4. The liquid volume produced in CCE lest is also shown in Figure 2. Time volumurme unt tIre dew point is comnsiulercet mis tIne reference (constant) volume in this procedure.0 (2) 496. Cumnmnmlalcd I’ressmnre 551. Lislumid drop-out bclnaviour of the North Sea gas ccnndensate at 394 K in CCF.66 0.15. Schematic diagram of constant volume depletion.2866 1.15.31 7 53 ID 111 11.943 0.2429 1.845 1.2D.1718 1. S. The tailing behaviour in the liquid build-up curve inums been tire sumbjeet of conrsisleruuhle imnterest with diverse views on its cause. which is taken as the reference volume. lnuuve been repsirtesl. Irnilial reservoir pressnnre. incre. the test can be simplified by jumst expandiung the cell volume without removing any fluid from it (pressure-voiunme test). production and sampling.67 17. Table 2. The dropped out liquid vaporises back into the gas phase at lower pressure conditions. the presence of in’imobile interstitial water and marked differences between the solubilities of different compounds in it.2158 0.1876 1. using Eq. 12 0 0 0 S Figure 2. The initial gradual and small build-up of tIre condensate plnuuse has been attributed to the contamination of collected samples with hydraulic fluids from various sources during drilling.00 0.737 0. The liquid drop-out 1mm both tests has been defined as the ratio of the liquid volume to the volume at the dew point.1) 211.56 2.943 0.00 1(00 Speeil’nc gravity (relalive to air) of produced gas 0. . PVT Teds 57 are determined. Constant volume depletion test results at 394 K.114) 1. Z retrograde liquid.0) 1160) 76.14. as sbmown in Figure 2. PVT test data often show a liquid build-up tunil.4 491.211 11.728 0. A 2 MPa tail was successfully eliminated when the dew point was approached over weeks instead of the conmmon practice of over hours or minutes[291.15 for comparison.32 10.943 0. The condensate volume is also measured.2F.2.0) 141.0) 4111.1) (1)471. and it is the overall result which exhibits itself by the condensing and vaporising regions. The liquid volume.2074 1.943 Comnnpressihilimy faclcir Volunme of of produced gas.29 0.943 0. wlmerc time condensate build-up below the dew point is insignificant over a considerable pressure ramrge. Table 2.89 0. (Mmnies nil wet gas prnxlniccd/mnnmilcs cit fluid am initial reservm.797 09479 42. however.s 2.9171 81.1991 (1. It should be remembered that the transfer of components between the phases always occurs in both directions.51 2. 50 Pressure. 0 0.49 ‘nindemisane 1 ~> ’dew “dew ~onnoIemnsaie nnnmlensame t 1’<< otew a 16 S S Figure 2.9176 60.889 ((. Exceptional cases. Po at the jUn depletion stage is calculated by.941 (1.5 401. and analysing the collected fluid phases.: GAS’’ (I) (2) (3) (4) ‘m.0 ‘‘GAS:’: •:GAS~ Hd~~sH GAS. There is no firm evidence. Indeed.1)0 0.nmlemnsuniu 29.2E.9476 Sumnuratinnn pressure uni inslicated temperature.i. MPmm Figure 2.5). (4) 1. are commonly nreasured by flashing the gas at the laboratory conditions.90 0. TIre compressibility factor is then calculated.760 0.00 0.1) 7183 7105 6960 61(22 5804) 4930 0. As the gas connposition remains unchanged above the dew point during depletion.943 (1.2D. The condensate properties at other pressure stages are calculated by time material balance [30J. PVT Tesi. and the adsorption of surface active and heavy conmpounds on reservoir rock surface may contribute to the above behaviour.17 0.rr pressure)xt00 (Vmnlumnne m.0 7975 7540) 7250 Prnxtuciion. The test procedure can also affect the observed dew point and the liquid build-up beimaviour. TIme produced gas deumsity and csrmposition. (3) (1.0) 51)1. except in the last pressure stage wlnemm tire eonrslensate is also expelled fronr the cell.00 0.tscs witlr tire pressure rcolnmelionmr below tIne dew point at a significant rate. tirat the tailing cairnot be tIre true characteristic of a real reservoir fluid.40 1.s and Corre!aiio.0 341. The condensate density. and CVD tests.0767 1(1056 271.15 shows the liquid drop-out volume in CVD test. with a liquid build-up tail extending over 10 MPa 1281. Properties of time condensate accumulated inn tine equilibrium cell during depletion are not measured. as the fraction ofcell voiunre at tire dew point.00 0 00 (1.00 0.

29 28.19) ‘Fumble 2.41 3. T. Drohnn et al. Xjj = [ninYlin —~n~yjj _(V_Vn.0(0) 1) 32 I’ll 82.77 7.nluun.32 (1 20 085 23.21 (1.Bunianne n-Bumane i-PennIunnes n-t’enniane ttcxancs Ilepmanes CX’ianes N.07 0..85 I .5)) 0. bar Pressure 49303915 Ilydrusgen Sulfide Ninrnngen Cuurhmnnt)ro.77 82 58 7.71 79.06 4.0 34 I . Pt’l’ Te.22 11. and compomnent groups containinrg unusually high fractions of aromatics or naphllmencs is expected.nn Remaining oil (moi..1)0 0.80 = = = = = = initial number of moles number of moles of gas removed nnolecumlar weiglmt of gas at equilihriuumm with comislemmsun(e mole frumction of connponent i in condennsate nnuole fn’actmonr of comnnpomrcnt i in gums url equnilibriunurn willm conuk’mns:nle initial trumnber of unmoles of comnnponent i ‘ l’he eqrmilibriunu’nn ratios at eumch pressunre step caun then be delerumninmed smsimmg tIne calcunlumled condensate connpositmon and tIme niemmsured gas compositiomn. suncln mns nitrogen. Compositional analysis of produced gas in constant volume depletion test uut 394 K.71 0.~ 0.46 0. a punrunurncler which indicates lire volatility of tire components.90 0)68 ((.~)p / M~] 61 (2. Faclr data point refers to un counnponenl identified by a function which depends on its crilicuml pressunre.75 (02 71 7. Table 2. Mmntedud hunlumnce cmilcumlations can be uses! then to evaluate tIre meliunhility of sIuituu innstcumsl nil cumlcnilmmlinng lIne pmnnpemlics of time c(nndcnsalc plrumse and tire :mssnncnumtcol eo uuilnbu nmnnnu runt mis.31 7 5..46 ((64 0.ns Rennnanmnnng gas ~mm4.42 2.)’) 0.845 202 ((.47 0. (1.87 25. The equmiiibriuun ratio data are expected to fall on a straight line.tinnnncnrs .18 ((.32 0.r rae)i.00 0.737 174 ‘tIre munterunuml commsistcncy of tire nnmeumstnrcsl comnmpnsilionai dmmta can also be cvalruated by plotting tIre edlunilihrituunm numlio vs.uide Menlnane Fnhumnn~ .18 116.64 1)37 0)17 03)9 I).52 1.1) 203)) 0) ((1) (1.3 I 1.72 79.00 0.37 1.34 (1.17 7.plus. It rummy eveni lead to negative mass of liglrt counrponents imn Pg V initial mass of gas condensate total mass of gas produced density of gas at equilibrium with condensunte totuni cell volunme tIne condemmsuntc.71 80. wlnere: nm n 8 Mg Yn Yn. tine slensity can be measured in—situ by miscillatiung tribe densitonnrctcr 1321.94 4.28 5. Rn sinnnws the nrnost connnunnonly umsed plot. I’V7’i’p.ut.76 0..64 .21 10. Figure 2.48 ((.728 66 2.I 0.28 1.0) 211 .29 0. h’n. and the boiling point temperature.14 1)45 22.22 ))4m) I Iyulrmngcni Snullisle Ninrmmgen (‘uirtmnmn’m Dioxide Mcnlnunne llhuminc I’.85 6. ‘l’ine above problem can be alleviated by direct sannnplinng of nIne guns umnrd conulemrsau(e pinases at equilibrium.44 Propane i.24 11.75 3.61 0.5 401 . 471.3 3.62 1.23 ((.51 1. mmnmuunnc t)nniunnme nnIlnniunnnc i-l’e.34 0.4)) 1)25 1. The loss of Ireavy connpounds in the produced gas resunits mm umnn umurreunlistis’unlly lnigln coinmdcnsumle slemnsily.0 31(45 14 I .52 01.33 1.53 (1. Additiomrai to tIre conmsrpnisitionnal anmnlysis of line Inigln tnrcssrmre sanrnple.31 2.2F.02 2I.j)p~yi / [nm —~nri _(V_V. condensate volunnie The condensate cotrnposituon can be cunlculated by the cominponnenl urnurncriuml bumlumnrn.2)) (0. (‘nnnn.35 05.7)) 0)43 (1.5 I 1. ‘lIre compnnsitiomr of both phases lmas been measured directly in a CVD test at 373 K.1 0)58 0.84 0.33 0.0 271 .25 27. (onnipositioinnalunmmmilysisof_renrraitnimngdl8l bar in constant volume depletiomr test.32 1.48 0)00 0.50 33.55 0. 13 0.’I6 (1.1 (1. A rcumsonnahie deviation fromnn tire straiglnt line for non-hydrocarbon compounds.c 2 2.nnanes Decaines Undecanes-plus Molecular weight Gas specific gravity 3. amnd higlner concentrations of lighu connrponunctnis inn line cnnnrdcnnsmmte plnumss’.%) 0.33 ((SI) 0) 52 I IS 1) 32 1)48 I IS 11.s mmnnd (‘flrre/(rfio.8 0. 24.5)) 0)00 ((. nnin ~mg = = = = = Reliable ressnits fur the condemrsunte phmssc by malerial balance calculations can only be obtained by mnmn acciurate amnalysis onf prodmnccsl guises.311 1.1) 0.00 01.5 (relative (ci air) 0.25 0.2E.cs n Pcnnunnne Ilexunncs I lepianes Octannes Nnnmnanncs Dcu’uuncs ~m(n~çcum9çs-.50 3)’) II 49 1.66 4.93 7.n.03 1.s 59 = [min_~m~_P~(v_VoJ) /V 0~ (2.si.0 ‘ 3.~ critical tcunrpermmlumre.%) ______ -.22 0.46 0.’c’ mis.1 Mu.58 2.55 (1. willn knw concenlrations in the mixture. 1311 sltndiecl (TVE) dumlus of 80 experiuriemnts anrd foumid uregative couurponnent fractions in 71 cases and condensate densities lncumvicr (burn wun(er in 45 cases. such as nitrogen ansi canhonr dioxide. Tb at tine alnnrosplncric pressure 1)1 P.36 0.n.4 (1.lccuutar wcigtnn Guns specnlic grunviry (retamnve tnn ant) Msnlccutar wcigtnu ml “0 (ndccunnes-plus” I) 01) (1 32 1.889 207 .. Time cunnlnposition of prodsnced gas as measured during CVD test by the conventional method is gerrerally fumr inferior to tIme rcqmmired accuracy for describing a phase which is after all time prosIunct.79 1(2 ((. IS 21.0.18) where. known as tIre Hoffmann 1331 plot for a North Sea guns cuinnclensunlc.797 190 Mm’Iccnmlar weighl of “tindecanes-ptus”: .943 231 0.36 01. 1 V..30 1.7W) 180 0. ‘Fine repou’tcd cournpositionmmml information is seldom used in evaluation and tuning of plmurse helmaviour models due to tine lack of reliability.03 0.72 111 (ml 7.

2D P.4.21) 2. neglecting compaction. h1nnle’31’ in I’lunec (LnngPc-lungPa)(I T1’b.171 Sx 0. line produced number of moles.4 21.15 .-F 2.22 40.1 The linear variation of P/ Z and total production is expected as. is proportional to the gas volume at standard conditions (I kgmol=23. The volume of one kgmoie of gas.3. 211 -4 -3 -2 -I t) I 2 40 611 80 ‘l’nnual l’rmndmncuinnn.1)056 0. Itn a reurl reservoir in the mmhsence of water advmincement.3 25.=100x27. (mu) Basis: I t)0 kgnnroies u)f gums run the inilial reservoir pressure of 49. using tIme measured compressibility factor. 15=7.71 8.3.32 10.15 40.2F.31 27. molar volume. N 0.2.5 23. 0 “S MI’r~~ 0.0767 0 4. of the cell Conteni in the constant volume depletion test reported in Table 2.53 10. Calculate the two-phase compressibility faclor. MPa 47...1 22.86365 0. Mi’a M 5 Zr lOOx(V.974 inn (Example 2./V) 47.33 1.113 1. — np).11 21..1 57.1 14. and (RT/V) is constant. Variations of PIZ with total number of moles of produced fluid. and compare the resmnlns winh tlne omeasunred values.8988(1 0. Hence the above trend can be shown in terms (nf gas vol umurme produrceci.07977 37. (b) Calculate the conmposition of condensate am 81 bar by material balance.971 m’ The differemnce in caicrulated reservoir volume by the two methods is due 10 the accuracy of reported clala.28 11. When the produced flumid is only gas. An average value of 7.. The conslant volunmnne depletion test results of a gas condensate fluid are given inn Tables 2. (mm) t)eterimmimne the density of conrdensate phase by nmaterial balance calculations results. V= I .1 14..48 16.3/49. So(nmtion: Euamp!e 2.64 MPa. equnal tcn 7.21).I (I’)( I Ills I[Ic) Figure 2. at the initial reservoir pressumre cmun he calculated.00731 0. plot.80 34. Internal consistency cineck of measured compositiomr in CVD lest by lloffmnmannn Figure P.17227 5 P/Z 40. using the measured Z for single phase gas.82676 33.972 m’ will be used in the material balance calculations as follows.9171 0.! Correlnrrisn.9476 7. V=nnZRT/P=97 .1 82. Table 1.m. Z=(PV)/(nRT) where V is the reservoir volume and remain.8 1. U 0.1 Number of Motes 97.1 21.49 34.1 .s 2.1 24.60 2.82 23.34 27.1).18 11.0 21.1 39.0083 l44x394. Solution: The two-phase Z is calculated as. lIne uotal produictionn unmnnJ comment on the observed trend.~ 1.1 70.33 9. l0 mz. Table Table ‘l’ahle Tumble 2.85 28. = (~i)(n.14 23.16.64=0. Piol PTZ vs. .07974Q m’ Substituting the volume in the above equation produces the two-phase Z as shown in the following table.2.sts 61 100 0.95 mm’..3).9176 0.0083 144x394147. Z. The (constnmnmt) reservoir volume is calculated. Exannple 2. PVT Tests (inn. the volunre can be treated as constamm(.83 Z .1 .94017 0.2D 2.21)-P.. P. n~. PV’T l’e. Usinng the reported number of moles and the comnnpressihilily functor at the dew point results in..1718 1.2074x lx 0. with nrm. 8.3=2730 kg.1 27.9479 0.83x 1.s constant dunring depletion.1 90.

06076 ((1127)4 1)1)2(135 (1.331) 0.50 7.293 86.07 293. except for nitrogen.620 1.53437 11.82852 0.66 ‘1.11 In.49 I 00 0 (13 1./M.977 1)470 1. 100 0 1)300 97.06(107 0.299 1L456 0.676 0.5 611)) 733.170 7.447 0.227 18.34 2. unnsl tine shrinkunge of cnnnndensate mIre nsneumsurcd. Vr. 59849 ((. Clearly the CVD data cannot provide adequate murfornnmatuonr to evalumunte mmmd tune the plrmnse behaviour unodel for sinmiulation of such a build—up test.=flim.6(0 7. n~ =n n~. 17 slnows the results of methane cyclnnng of a Nornh Scum gums condensumte.000 97.1 315. Xm~ meas. mole. Note that line hiqumid volume fraction decreases by 20% unIter connl mmcliung twin lnnnre x~ mlninnies nil imnjccled nsnctlnunmne.4 6.sured Km des’nmntn. 0 0 nhe following table.qn) 6 Nitrmngcin ‘arFsm I)nmnside Mellnanc Unlnumnc t’rmpunine l)nnnmnnc nnltnn)umnnc n l’cnnmunnne’s 1)0(6)) ((329 1. inmslead of gas-like.4 2 2.457 6.460 0.352 0.758 ‘ 57.928 2.p..5 19 0. 5 V( I -V.1 11.s 2.119 nmnsle % mole % -0. ‘lIne belnaviour of tire mixlure composed of a high liquid fraction coumlsl be liqrnid-inke.086 ( 1)395 1)2(7 1)332 1)161 ((.499 0. —11.31 76.93 6 27 5. and the flow area is reduced near the wellbore.00() 0. cum.830 0.38824 O.64 47.1 21.1(8 10036 55. TIne produced gums volume and comirposition.2 172. kg/rn’ 59.11)0 39. PVT Te.33 82. hut using the original gas instead of the lean gums.1 pore volunre of gas.329 0. imn~.)) 1712. 10.149 6.318 3.97 164 1.36668 2.550 1. follnnwed by stepwise pressure increuuse can simmrulmmlc the above process and provide phase tnu’tmunvumnnnr dmntmm for uls munodelliung.914 1) 306 1)71)) 33.1(68 I 453 1) 260 O.7 t).n . 0..2 1935 195.204 (.683 77. Winen tire well will be shut-in or the rate reduced.393 0.mtnane Prnmpane iBuniane n 76..946 I 354 1) 22)) II ~.8 I 34)1...352t I 0.356 ((.102 kgrnol 0..2 ().5 362 I 4.1 14.595 0.75 1)34151 ((.1) 2.6 6.46 2.8S 628 5.36 (1.238 1.311) ‘0. gas density. n~ mole in cell.2Om) 1)1)45 (1.36439 0. At conslitions near the producer within the condensate ring.02 6)1.354 0.63750 0.17 7.l -1.207 1.8 0.2 in t’ennirnnnc I Iexumnncs tteplunnics 1 )ciumnncs Nn.171) 0. This will result in a nunpid flow of ricin guns unto tine near well region and a liqumid build-up in pores at a fraction much Iniginer Ilnan Ilnat mnneumsunresl in CVD test. 16141) 0.42 -7. n .710 0.1)47 (11)77 11.223 0.25)) 1)360 0.563 0.219 0 509 1.425 0. and connnpmmred svmtin of each component in the guns phrase camn he of moles of each connponenni inn the condensate The calctntunus’sI resmnlls am mhc lumsi sluugn’ mire givcmn inn line unucasur ru’d ‘cmi mmcc.0(106)) 3-5)) 33.282 2.255 2.452 7. ‘rime recyclinng process below lIme dew point can be simulated in the lmnbormmtory by iunitiunlly comrducting a CVD down to tire recycling pressure prior to introducing line recycled gas into tire equilibriunmm cell.The number phase is then deternnined as.397 16... The cell is retumrnred hack to its initial volume by expelling the equilibruitesl gas at comrstant pressure. uns tine rich gas keeps flowing towards the low pressure regnon sleposiling urmore condensate. with the number of moles of condensate calculated as.153 1)32% I).607 0.110 ((. kg/mn’ mass gas rem.n~ nm.8 2477 3 221(1.60 1.239 0.c ~nnnd Corrm’!nmnioni.40) (1.303 2.249 ‘l’lrc sleposited conslensunte in a reservoir can punrtially be recovered by injecting a lean gas into Ilme reservoir. As tine guns volumnnre irrcreunses at lower pressures.830 0.323 (1.75 I 5.603 .661) 0474 ((.~/V) V-V”n p..5 186711 muuss C(ifld.62 Table 2.5 (1.3 I 2 1)548 (1.720 79.34125 1.271 Cmimponent Nilrnngen Carbon Dioxide Methane P.168 2. lIme pressure grumdiennt svill increusse shutrply as tine well bore is approached.951 82. vol.754 23831) At each stage the number of moles determined as.220 1. V.815 I 709 0.456 0.340 0.66 97.789 (1.21) I00.201 100.392 0. n~=n~yj.83 90.18)) I .l)) t3ni)mnne i-Penianes n-Penlane 1.682 0.246 62.82382 168.131 0.1 3.18 100 03)20111) 0.m~ kg 2670.99 335.844 0.l’i (1.5 (not). The fraction of pore occunpied my conslensumte iurcreascd irounn 28 % to 63% due to the inflow of 1.1)4 Km nn—mnn.848 70.2 1091. V 1 2.15 40.113-I 0.157)02 0.695 0.96 4. Figunre 2.8 2235..498 Hexanes 1-teptanes Oclmnnes Nonanes Deeanes tlndecanes-plus Tonal 0.s 63 gums 298’) 42. A laboratory test siminiluur to tinat of guns cycling.-Em .02717 -0. nm.434 7.1 -3.760 2.66667 1.521) 1.2(17 55.=n-n . Component mole in mole in cal.751 0.67 17. rn/V.644 0. 10191 0.5 1999.119 (1.23 1301 200 45 154.262 1.44 3 3.0 343.57692 0.imun.9 70.8 2825 286. The produced gas is stripped from its imrternmrediate annul heavy componeumts at tire surface prior to being recycled huuck inrto tine reservoir.312 4.227 ((.7 413. ‘I’Ine mnmninnlier of mrmoles 1~ of each component is then calculated as.982 44.569 1) K. Note tinust tine accunrrulation of condensate did not significantly change the mixture 11.1 18.79 4.. and producing time gas enriclned by the vaporised condensate.274 1.3)) 27. kg rn.6113 5.2 Consl.061 90. I 7 23.0 241.470 (1.83 7.418 65.057 ((. wlnem’e qumasi-steundy state conditions may he assumed.11) 12.273 (1.1 2671).023 5. rn’ 7971 7627 7371 con.238 6.293 0.554 71. n’ calculanect 5 nrnea.431 1.7 689.51st 1.71)) 11.nm’’.6 1)11(5 (n 7159 7072 7068 81(4 8991 n%)’n ( 1442. Figumrc 2.369 OXOfl 49.61 8 1)1(95 (1 227 71(5 (n) 2. (h) tonal nnnass in cetl.11 57.111(2 (1.09 The CVI) test can be considered to siunulumle tine fluid behaviour in tire reservoir hulk. (0)11 (1.r9 ((.250 2.94298 1.29 3m) 71 cmnnd. kg gas vol in cell.nj.1 34.0)0060 1~ TIne results are as follows: Pressure.01 085 2 28 1)91 1.165 0.m.648 3.29 281)6 4.: ~ ninyjin —~n~y I )ecumvmcs Jnmlecaincs phms ‘l’nnnal (LIII 3 1(00(4 (1.10210 11.1 27. PVT Te.7 -(1.2 mass gums in ccll. where the connslemnsale cmnnr be rcmmsonnunhiy assurunned imnnnrrohiie.39 15. 18 slnows tlnc variatiomr of fluid saturation pressuire mncmrr tIme wcllbsmrc fnnr mu Nnrtlr Scum gums cmnmndeursate flumid in sumclm a test. I) 061 00’) 3 0.0) 253 . n mole gas rem..000 0.4 —1.7 703.5 1695 (1.0i63 1(1)21 The number of moles of gas phase in the cell at any stage is delernniined ms li.721 0.ni. kg 0.139 1)3.76 3.37209 2 .911 0. ‘IIc flow of Iluinds lm)wmurds tIne wellhnnrc will establish ur pressure gradient within the reservoir. in cell. ‘l’tmc per d’e?mmumgc I tm’V I rut minim In I calcnmlaled equilibrium ratios fronnr mIne nnneasnrred valures imndicuiics (Ire reliumtirlnny nil experimental data.01)4 6.530 (1. MPa rnmle gas in cell mole cond in cell 49.290 0.978 0. the CCE test simulates the helnavioumr mrrorc clnisely mis Ilne connslemnsate flows willn the gas. m’ 0.2 7094 5561) 686 I 62)5 (m9l 3 (0) 2 (..678 29.8 5 .538 1.94 41)3 IL 81) 2.293 1) 2. prod.326 0.9 2.827 (1. the pressunre will huuilsl-urp agurin. den.17 9.48(1 3.193 1. and time mixtuire composition rennnunitns umluriost connstmnmnt. TIme recycled gas is introduced at constant pressure by mullownng tine cell voltnnne to expumnd.

provide sufficient conrpositional uumrd vnlunmmretric dumlmm for Iumnirng of a phase behaviour nrodel. 2.30 0 • 60 — 25 I U 30 35 40 45 50 Saiuration Pressure Liquid Fraclion 0 Pressure. a large volunnc of the gas is prosluiced which unnay altuninr mr nnnobility exceeding Ihat of the oil..5 Volatile Oil PVT tesls oim volatile oil sunmnnples are imot well detiimed aund slocunneunted.nnc 2.17. C Altirouglr laboratory datur gemnerated on gas condensate fluids can be used directly in reservoir studies.’rj’Iani. however. similar In) that for gas condensmute is sonnetinnmes eourdunctcd. Note that the addition of methane to the rich gas has resulted in . The anmount of condemrsate collected from produced gases in separator and differemntial liberation tests should also be measured and reported.19. U’ 20 LI 0 0 50 100 51) 200 C a o is > ‘a a a. imowever. tire differential test seenms to sinnmumlate ttre process. Figure 2. resulting in a large gas production and leaving the oil belminrcl un tire reservoir. immcreasing the dew point. PVT Te. - ‘5 30 • Bubble Pmiinn > 0 32.18. The systenr.% 5 1. Tests simrmilumr In) tinose described for black m)ils mure commnurmonnly comrducted on volatile oils. However. winen tine injeclion will he stopped unnml line remaining guns produmced by depletion.15 40 ° : - ‘ii a Sm 0. it will be limited only to tire 7.25 0.080 o A X Cum. % Figure 2.2.20 32. Tirerefore a constant volume depletion lest. instead of a dew point.401 1. ‘l’lne tests should. 32.fPore Vol./iniiial Vol. As tire cvolvcd gas plmase below tIme bumhhle poiunt almnnost imnmmnrediately becomes immobile. The overall nnixlure will becourmc progressively leunner.64 2.nis 65 saturation point for this tested rich gas condensate system. simulating pressure maintenance of a rich gas condensate reservoir by methane injection. rl Fignure 2.47 Cuinnulamive (‘I linjecled DO • 0033 25 ~ ‘a C C C 20 .10) a (I.one near tire inrjeclor. Section 9. Variations of the fluid saturation pressure due to gas inflow neuur time wellhsnre. PVT Tests wmd (‘o.05 32. wimere metinmmne is rnnixed with the original fluid. 40 35 30 35 30 25 CI Vol. if the reservoir pressure is not far above the initial dew point. The constant comrnposition expumnsion test at tIre reservoir tcunrpcrature provides most of time required data our the oil behaviour at reservoir conditions.00 zmi - 0 50 100 150 Total Gas inflow. no o • 0 0068 0.133 0. MPa 32. however.3. 19 shows the results of a laboratory test.749 Figure 2. i-hence. As tine pressure falls below tIme bubble point. The model is then used convenmiently mm siirninlation of time recovery process. . CI Added/urinal VnnI. changed from a gas-like to liquid-like fluid. at 34. It is a common practice to inject sonmre lean gas into a gas commslensumle reservoir to cmmptlmre mis much as possible of the pressure declimne and possibly nmumintain its presscrrc atovc time slew point to avoid the liquid loss by deposition in reservoir during pressure depletion. it can promote condensation. tine immobile gas’wlnicir is produced with the oil heiraves as a ricir retrogrumsle gas ummmd contributes significantly to the collected liquid at the surface conditions.169 0. Time production of volatile oil by depletion is not an effective method for optimum oil recovery. None of the pressure depletion tests commonly conducted in laboratories can sinrulale lire fluid heimuuviounr mrs occuirs inn lIre field. resnnlling in a lower liquid drop-out during late stages of produiclimnmn. Ilmey are often used to time a phmmse belmaviour nnodel. cm 32. showing a bubble point at the last tested slage. instead of preventing it. 32.58 MPa. Vol. Vol.~! 50 ~. 15 10 I. Reduction of condensate volume in methane cycling at 373 K aurd 27. Varimn(ions of dew point and liquid fraction in CCE test with methane injection.2.

however.c 2. Western and Mid-Continental United States unnsl Sourtir Amrrcricun.367 ‘lIne sclcclcdi correlumtionrs are presenmtesl inn this section using fneld umnrits as follows: P : Prcssumre. Ammmcd 1441 unsent tIre cmnmnnhi ned rcporteml duun mm of Glaso and Marlnosun to develop a cuinnclmnliomn I’or sletermnninniung the oil fn’rumnmu ron volunnune fmncnor. Ia evumluale pumblisired correlatuons.9-51.0242. Tine clrmnnmge of slope mO hunfiblc poiurl is less pronounced for volatile oils in comparison with limat for hlumck unil s:nurnples. gas. cm 3 2. unnsl field ulumlun. “API Guns Specilnc (iravimy 0.588 90. umsi ‘I’exuns-Losmisimmmnun.(2. The second group consists of those correlations which use tIre flumisl conmiposition. psiun lcnnnpcrum)mnre. mr gums cmmrreluutiomns: Eqs.1 i~gg~.c 67 An on site simple pressure-volumme test of tIre collected oil smnnnrplc is un umscfunl gnnidc Ia iulemntify the oil type and decide on the required tests.abedi [461. Lmmsumler (40( prcsernted mm htnhble poinrt correlation usimrg 158 measured bunfihle point dmuta orn 137 crude oils frornr Canadms. Africun. ~I tm.I tuac. Ihnnm/fI’ (= I 6.() IX kg/Inn’) I~.1602 19. ‘Iuutnle 2.58-76). TIne slope clnmmnges tm so gradumally for very near crilicmnl oils tinumt tine huibble poinnl n nnmmy nrot Inc deles’teul. All time mrsnllrors lmumve unsed un large nunnnber nil experinrmentunl clmmta to regress the parameters of theiir proposcul correiuitisnurs Inn umniuninnise tIre slifferences between tIre predicted and measured values. Sonne of them.n: l(nnlit.5 60-565 26. Stunnidmug 3~) tusenl mm lunlmil of 11)5 ulmmtmn pmninnts on 22 dnfferent crude oils fromnr Califonmna to develunp Inis cmnrrelmnnioums. S(’F/hbl (=5.:I )icsnnlveul nnr litneruulcst gums.67).1)28-2. Tine reliumbility mif tlnese correla(innns sigunilrcantiy depends on the reservoir flurid cinaraclerislncs.l0 0. mini acceptable accuracy can be expected.. ‘rhe first approurcin. a Stumndinig 39 13(1-7(118) 1011-258 1.. degrees Rmnmnkiune.4-44._J~laso 141 42 5. ‘fine correlun(ions can he classified broadly into two groups.276 -. to estininmnle 6 7 the fluid properties.48. Black oil correlations simoulcl cununlioumsly he usesl for volatile oils.025-2. and Bcggs (411 developed correlations for the solution gas to oil rmntio mnmncl fornniuntioun volunurre faclor ursing 6004 data points. to devclnnp generalised correlationrs for estinnnating properties of reservonr fluids. A number of tlnese correlations Inunve unsed dala of certain localities. . Comparison of pressure-volume behaviour of volatile oil and hlmuck oil. mnnnd t’etrosky-Furrslnmmd 1471. have slrownn tincnr reliumbility in vmnrioums comnrpunrativc . If lIne flunnd is “lypicmml.6 1)574-I .22 IS 605 1)51 u-l.mmralnnr ‘lenmnns ‘ 265. Sounne correlatiomns hunve received lnigimcr attention and wider acceptability than others. slescrilncd in ‘rable 2. Vasquue7. guns and oil specific gravity. a visunal method.106 0.59-)).3. stimulies (34-38(. It is not uninsunuml.5-(. hence. Marlmoun (43] used 160 inuibble poiurt dmmtui nnnm 69 Middle Fmmstennr crunde sumnrmples to develop a bubble point pressrurc ceo mel mit our.062428 unr ‘/kgmol) p : I )ensity.nnnn.1. Africa. De Ghetto Ct aI.151) Sepumrunnnmr l’rcssnirc. TIne correlations ypncmnlly nrnuntclm lIne eurnploycsl experimental data with an average deviation of less (Iran a few percent. liunwever.S(’F/Sllt lank Oil (Iraviny.351 76.032-1.[45J. no observe deviations with an order of rnmagnitude higher when mnpplied to nlher flumids. “F (= I .nm. and the solution gas to oil rmulio (0 de(ernnnimne nIne properties of smutunratecl oil .752. unsesl sluntun Inn lluids ~ronrm reservoirs inn Western Canada. typically identified to C by discrete eoinnpounds ansI tlmc rest uns C +. There are many fluid property correlations.226 - 165-7142 8tn-280 1. resulting in no clear superiority order amongst time correlations. psimi a’ ‘F : Temnrperuutnmre.1 Black Oil Figure 2. All tIre corrcluntionrs unse tIne reservoir temperunturc.nnnmi t’nm’ssurc. and modified some of tlnemin Inn innprove predicted resiults. ft ‘/Ibnniol (=0. the stock tammk oil and tIne collected dry gums at stamrslard coirditiouns. sk’grees Fumlrremnlneil.6146 nnn’/nnn’) Vmnlunnc.[38] used mnbourt 370t) nnnemnsumne(l (luntun psiiurts nor 195 crusie oil smmmnnples from the Mediterrumnean Basin. i.8K-459. . their application is limited. be expected. sinmilar to tinat for guns cmnnrdcunsuuns’.8K).3. density.3 provides infnrmnnmntioun our time raunge of data used in tire correlations to help selecting a correlatioum for a specnlnc cunse.Ie I’. !~nnnpnn meal (‘mnrrelanna. The correlatiours inave been reviewed ammsl compared by several investigators. 415 125 0. Inowever. Asgarpour et al . 1.66 2 J’VT Tests mnnnm/ (‘.Several autlrors have provided correctioum fmncnnins to iunclunde tIne effects nil nnnnn—lnydrocmmrhonr counipoumrds and separator conditions.95 1. those wlnichn consider oul. gas solnrhility. Fmrst.1.3. Pcrsiunn Gunlf.3-59.997 II-2t99 15. ‘t’hnc numinn properlnes whiclr are sietennnined from ennnpiricmnl correlatiouns unre ilne hunhblc poinnl. Ranrecs of data used inn bluick oil correlations. Figumne 2. annd treat a reservoir fluid as composed of tlrese pseudo components.nrrm’!mnlim.unsunlcr tI) 48 57811 82-272 32905 17. .n Ret N.21) s’mimrnpmmnes the pressure—volume behaviour of a North Sea volunlile oil willn tlrunt of tIme black oil.1. in oil and water correlations. ‘l’ineue arc ml Imurge ununrrber.20.3. and falls withiun the range of tested fluids insed in that particuitmur corrciationn. Glaso [42] umsed data fronn 45 oil cmnlniplcs mnroslly frminrn tIne North Scum megiuinn Inn develop Iris correlamions. i. is pncfcrmu’nl.6055 162-181) 1. and water as three pseudo components.15 211(425 l6. A few of tIne nrmorc widely used correlations are givemr in this chapter. v : Mini umr voltmmnre. and viscosIty. (‘nmtnchniim.61/Sn II Guns/Oil Raiinn. umnsl Non-lb Seum. Mumny investigators Inave umsed PVT lahormmtony test resunlts.e. Euncim comnrponent is clmaracterised by its specific grmmvity.n.of correlumliniurs to detemmnmine properties of a typical black oil..1 Murrhoun 43 130-3573 74-240 1.650-1. 1 mnr sunc hr mm fluid. psnrn Scn. is the connnnnour orre. respectively Inn develop vunrious cnrrelationms. 2.Vm. “R (=1.465 101) 36. Ann accurate prediction of tIre phase behaviour of complex multi-component systems witir only a few vuuriumhles slronntd not. Table 2.3 EMPIRICAL CORRELATIONS Blmnck (nil comrcluntionns (remnt line oil ums comrmposed (nf two connnponeumts. vnilurmnnc factors..2637 22. cousnpressihility.

°F. amnd lemnnperumlnnrc (“F).= ~R.i0. psia = solution gas to oil ratio SCF/STB = Temperature.nn AI’u<3( ) 27.4 S.IF. atusl lIne v. a=.(2. °F hence. pressure.786+92Xl 5 .nlures of tlre coefficreurts are: ‘n met ticie. As the selnarator pressure is 100 psig. its vunlue slnould be estimated and added to the gas volume evolved in tire separators.18 (0. the authors tised the gas gravity normalised to a separator pressure of 100 psig.’u 69 The main application of these correlations is the estimation of reservoir fluid properties uusirmg field data.=2~R. Solution: The evolved gas is estimated using the separator pressure and lemperalure (75 ‘F). including the stock tammk oil if infornraliomr is available. S Example 2.327 log(P ) -0.00091T . are calculated R. calc.84246 0.30855 Bubble Point Pressure Standing initially produced a graphical correlation (39] for determining lIme humhhle l)oilrt pressure.823 0. and later [49] expressed the graph by the following correlation.902 log(S ) +1.393 S =~R.822 0. and the stock tank oil specific gravity as follows: P~ 65 I IS 215 wimen’e t’. 9 mn=t). can be used to eslimate the bubble point. = -C (API)/(T+460) 3 where. Sgin = where j refers to the separation stages.786 0. Eslinmnate tIne hmmhlnle point of Good Oil at 220 °F. amrd gas specific gravity.respectively.s 2.732 R. Time solutiotr guns vented umt the stock tank can be estimated [48] from the information on tire last separator hclire tire stock tank. umsimng Eq.3818 -5. % dcv. Salrmtio.6.using the measured separator test dala at 1(X) psig.3631/768=0.).=(676X0. Example 2.62 - - A I’l >0)0 56. R t is the stock tank vented gas in SCF/S’l’B. I’VT l’e. S~I~R 8 1 5 (2. ~ is tine stock tumumk oil specific grmtvmly. 0.~ mmnrul ‘I’s mire (Ire muctumuul sepuurmulor pressure. 5 Sgs~ P~and T . R~ incas.n: “API 40.7/680=-0. 1 = . ansi gas specific gravity data. - .62205 16 T P =274 I psia 5 ‘The nneasumresI value is 2635 psia.2[(R~/s8) a Pb R 5 (2.20) a ) (I ~yn (2. iudl. 45 80 148 41 92 178 tO -12 -16 ‘I’Ime notal gas in solunlionr. g’ by. mmmd tcmnrperrtture.22).704 217 246 -II ‘lIne bubble poinil ms cstunnnmuis’d using tIne Stuumnulnmng cminneluiuion.41 P =2503 lsimn 5 Alternatively.2 I).68 2.(2.. Compare the results wimln mnneasured values.se. psiun.5 40.0l25(API) = bubble point pressure.506 log(S ) +2.000 I x220-0. Vassiuez and Beggs [411 point (nut that the gas gravity depends on the sepunrator conditions.914328 11.5. are the separator gas specific gravity.m.7355 log(T ) 0 85 5 5 T <l40 un}m 5 (2.~ 12 (or ) (API~l~ lnng (P / 114. As lIne ann’noumrnt of vented gas could exceed 10% of the total dissolved gas in the reservoir oil. Hemrce. The gas evolved at the stock tank is often vented and not mimeasurecl.23) whnere. 5 The gas gravity used in lire correlations is the avermuge vunlunc of mmli s’nillecled guises frommn nIne separators.1 0.823 S~ 0.23). 0. log(R ) 51 = A deviation of about 15% is expectesl fronr the above correlation (37. [(C R.t) I 25x4t).(2.855 ~nn= 18.n amid (‘orrelatnn.172 5 Sgn is tine guts nororahised specific gravity related to tine separator gas gravity..840 0.lE.7)] 5 (2. S~.22) where =0. Eq.7 40.S /~R.24) Estimate the evolved guts from Good Oil at mIre stock lzmnnk coumnlitisnnis svitli selnuurzitmnr pressures equal to those reported in Table 2.825 0. Table 2.0.st.7=-0.=S~=0. Fnipiriea/ (‘arrn’latian. 083 1 (1o)~— 1. 8 5 [t+s.=676+92=768 SCF/STII S.38].. tIne Vmmsques-I3eggs correlation.2!) 11.393x40.855 315 40.

588 90-2637 22.[45J. Ibumn/fI’ (= I 6. is preferment. and modified some of I lmc urn Inn Inmnprove predicted results.226 0-2199 I 7.squcd.investiguntors.nun ‘Iennnpcrunminre. Aim accuraue prediction of tire phrase behaviour of complex multi-component systems willr only mm few variumbles shnourld Imot.e.. It is not umunustimmt. Figure 2. v : Mnlmmr volonnne. a visunal nretinod. 21)1425 16. unnnst l’elrosky-Funrslrmmsl (47(. ummn acceplunhle accuracy can be expected. 134-381. Sotnne of tirem.4.025-2.l Fac.Vn.n. have simown tlreir reliability in varioums conmnpuurmmtive .650-1.1.367 Sernarator ‘I’cnmnp.240 (iuns/OmI Rmmuinn. If time flunid is “typicmmi”. amnd falls ~vithmnthe range of tested fluids used in that punn’ticulmnr correla(iomr. be expected. N.9-51.smnu’tn mm fluniul.997 26-164)2 19. l’hcrc are un luurge nnununrher cnf correlumtionms to detenmnine properties of a typical black oil. slundics Tumble 2. in oil and water correlations.-rsiumnn (4nmlt’. “F (= I .(2.s 2.22 15-605 36. Lahedi [46(. “R (=1.21) cmnnnnlnmmres time prcssure-volurrne behaviour of a North Semi volumtile snil wi(ln tlnuml of Ilne black (nil. “fu tm. resunlting in no cleuir sumperiority order mmmnnmngst tIne correlations. however. !‘t’l’ Tn’civ mmnnd ( ‘nmrnm’latimm.6)155 165. cnn 2. Ranmges of datum used irr black oil correlatnomns.’t. I.1)28-2.6 146 urn ‘/mnn ‘) Vn.63. and water as three pseudo components. gas.3. Ennnpinca! (‘orrelamno. psia 0. Inowever.258 1. to estinnnmnle 6 7 the fluid properties.8K-459.062428 unn’Ikgmol) p : I)s’mnsity. descrilnesl in ‘I’ahle 2.272 Va. S( ‘I :fIilnI (=5.58-76).3 EMPIRICAL CORRELATIONS Blmnck oil corrclunlionrs treunt lIre oil uns conrnposed of two conrmponeirts. Time rehimnbihity nil tlnese correlmn(ions smgunif’ncantly depends on the reservoir flurid cirunracterislics. Comparison of pressure-volume behaviour of volatile oil and hlumck oil. The second group consists of those correlations which urse tIre flunid composition. ‘‘F 1(8) 76-ISO 125 ‘lime selected correlumtionns mire preseurled inn (Iris section usiumg fueisl utmils a. ft m/Ibnmnol (=0. Sturund imng 3i) umsed mu tnnluml nnf 11)5 duu(mi points ann 22 different crude oils from (Talifornnia to develop Iris cmnrrelum(ionrs. . First. is the conrmon one. i.. Time correlations typically nnuntclr the euniplnnycd experimental data with an average deviation of less (Iran a few percent.18)) 80-280 43 13)1-3573 74.s follows: a- I’ : Pressure.574-1. inence.7142 162. and treat a reservoir fluid as coumnposcd of llrcsc pseumdo components. typically islentilned to C by discrete compounds and the rest as C +. Ilnose which conmsider oil. A few of time mnmorc widely used correlations are given in this cirapter.8K). ansi field dluntmr.3.5. no evmmlurale pumblislmed correlations. psna degrees Funirremnlneil. Pn.106 15.018 kg/urn’) I )nssnnlvcul nnr libermmtcul gums.3-59. and viscosity. Glaso [42] used data fronim 45 oil smmnnrples nnnosnty frnnnmn tIne Nom’tln Sea negiour to develop his correlations. All time coruelunlions unse tIme reservoir temperunturc. AInunrcd 44( uuscd tIre cnmnnrhimmcnl reported slmutmu of Glumso and Marhoun to (lCVCIop a corrctuntion t’unr delernmniuninng Ihe unit funnnnnmmlion voln.1 0.511-1.Bcgg~Olaso 41 42 15.6 0. mn gas correlmmtnons: Eqs.351 6))-565 1.unsr 4)) lt.n’ 67 An on site simple pressure-volume test of the coliectcsl oil smnnnmplc is mn umsefunt gnnisle nun idcmmtify the nil type and decide on tIne required tests.: 19 I(ni)’liIc t’nmnnn( I’ncssnnre. Africa.Several authors have provided correctiorm fumc(nirs to iunclumdc tine effects nil nnnrr-Iryslnocarhonn compounds and separator conditions.66 2. Sninnme cmnrrehumtionns Inmuvc m eceiveul Iniglier atnentnonm mnumd wider acceptability than others.(38] used umhiniunl 3700 mnncasnmmc(I dmntun pnni nts mm 195 crude (nul suuu(rples fromsm the Mediterranean Basin. their unpplicmmtiomn is iiuinited. the stock taimk oil and tIne collected dry gums at snandumrd comndilinnns. t’ennnpermununre. line conetalions hnunve bccnn reviewed mnnnsl comtnared by several. 90 tIll) I III 12)) 1 1. 2. “API (las Spccilnc Gravily Separaim’r I’rcssnirc. Each counporrent is characterised by its specific grmtvriy.67). however. Many investigators have used PVT laboratory test restults.n. Afrie’mm. ‘rhe first approacin. 1(3 develop generahised correlations for estimating properties of reservoir flinids. volsnmnnc lmnctors. De Ghetto et aI. Marhoun [431 used 160 buibbie poimil dumma mm 69 Middle Emistermr crumde sunmniples to develop a bubble point pressure eorreluuliomr.1 (0.44. unsesl slmrtmu on flunds fronnn reservoirs in \Vestern Canasla. There an’e many flm.3-48.iunc fmrc(or. The clnannge (if slope u(t buninble poiunt is less pronoumnccsl for volatile oils inn comparison witin that for black nrl sumurnples.276 415 1. ‘FIns’ slope clrmmnges so graulual ly for very nemnr criticunl on Is thunt tine humtmhlc pun mm nnnmmy mnot inc du’Iectn’ul.3 providcs inforunmumtiomn our tine ramnge of datum used in tIme correlations to help selecting a correluntioum fmnr a specific case. detmsity.3. Black oil correlations shouidL caunliously he umscsl fsr volatile ouls. ht’I/SFl) 13)1-7)8%) 11%). Vassitnez unnd Beggs (411 developed correlations for the solution gas to oil ratio anmsl fornimmtion volunnrme factsnr unsing 6004 data points. to observe deviations wutin an order of tnmagnitu(Ic higher when umpplied to ntlmer fluids.032-1.20. All the unuthnors Inave umsed mm large nuinnrbcr nnf cxperinmrental clmutum to regress the paranreters of their pnoposed correluitiours to unninninnnse tire slilterences between time predicted and measured values. l’hc correlations can be classified broadly into two groups.024-2 IS 48 5781) 82.. SCF/S’I’I3 ‘lank Oil Gravimy.0(1 (1)1 degrees Rmnmrkimne. (‘narcluniiminn lumindning —. Table 2. siunni tar to that for guns coniderisalc. gas sunlunbility.nid property correlations. mnnnul ‘l’exmms-Loumisiumnimn. respectively tnn develop various correlationrs..5 0. umumul Nnnu’lhn Ss’mu. compressibility.tunsnc.465 3-2905 1.nnmn.1 Black Oil Figure 2.752-1. gums and oil specific gravity.8 059-1)95 265. Lumsunter (4(11 presented un buibble poinnt correlation using 158 measured bubble point dmmta (nun 137 crude oils fronn Canmasla. p’. A number of these corrclatiomrs Inurve nnsed slumnum of ccrtainm localities. Asgarpounr Ct al. I nir . Western and Mid-Continental United States ansI Soumtin Aunrericum. The nnumin properties which are determined fronm ennpiricmtl correlations are tIne hunhhle point. and the solution gas 1cm oil uumtio 10 sleternmnitne lIne properties of sumtuirated oil .

is lIme slock lammk (nil specific grunvity.912 5 (or ) (API)’l~log (I’s /114. are calculumted R. psia = solution gas to oil ratio SCF/STB = Temperature. S~. psium. a = -C T <l40 °F 5 where.822 Sr 0.n “API 40. Example 2.I sepumumitor pressuire.cn’. }Ci = 0. 51 Sgs.7)] (2.855 Bubble Point Pressure Standing initially produced a graphical correlation [39] for detenniining tine bubble poinl pressure. 69 The main application of these correlations is the estimation of reservoir fluid properties using field data. The gas evolved at the stock tank is often vented and not measured.38].1n2 0.914328 11. II) -12 . calc.m. frommn lime 27.= 2R. can be used to esmimane the bubble point.4 40. Hemnce. log(R t) 5 = Vasquez aurd l3eggs [411 point out that lhe gas gravity depends on the separator conditions.840 0.1 0. Eslimnnumte the hunhlnle point of Good Oil at 220 °F.IE. 45 80 148 217 R.786+92xl . and gas specific gravity data.704 R. Example 2.r?’e!alun. Eq.u 2.393x40.363~/768=0.() I 25x40.18 1)84246 10. Compare tIre resunlms with nnneasured values..2 I). where .7355 log(T ) 5 5 (2.5 40. are the separator gas specific gruuvity.83 = ‘I’lns’ tiulihlm. Solution: The evolved gas is estimated using Ihe separator pressure and lemperalure (75 “F).732 0. by.41 8 a Pb R T5 =0. Sg. Salmmtio. Tire solutiomm gas vented mit the stock tank can be estimated [48] from the information on tIme lmmst separator before mIme stock tank.Ilected gumses separators.2[(R~/S ) (10)a _1.usiung the measumred separator test data at 1(X) psig.(2. Fq.855 Hence. °F (2.2 I) wherej refers to the separation stages. 0.7=-)).62205I6 P =274 I psia 5 ‘tIne mnieursumred vunlue is 2635 psimu.0l25(API) = bubble point pressure.23).S~I2R. Sn. Estimate the evolved gas from Good Oil at tIne stunck mumunk comndilmunmns svilli ss’pmirmltnr pressures equal to those reported in Table 2. the authors used the gas gravity normalised to a separator pressure of 100 psig. I’VT l’e.n aiim! ( n. amrsl temnmperuntuni’e (mnrm).327 log(P ) -0. and the stock tank oil specific gravity as follows: P.0009 I x220-0. Sgnn = S 8 [1+5.23) where.1.506 log(S ) +2. 5 arid lime vuilnues of line coefficients mire: mel tncicnnm (‘2 C 3 Al ‘1<3)1 A ‘I >0)1 — 56.IE. 41 92 178 246 Sim dcv. Enipirü’aI (‘orrelatiou. incas. a=-IO.7 S. Table 2.. arid gmns specific gravity. As (Ire separator pressure is 100 psig.24) wlmere P~ mmmd ‘I’s mire tIme mmcluru. As tIre arnoumnt of vented gas could exceed 10% of the total dissolved gas in the reservoir oil. R is the stock tank vented gas in SCF/STB.=676+92=768 SCF/STB S. P~and T .(2.’ Pnnnimi us cslinmmumlcd nnsimrg tIre Slunnndunig cnnm nclmmiinnnr.823 0.) (io)~ 3 (API)/(T÷460) (2.(2. tIne Vmnsqures-Beggs correlation.c A deviatisnn of about 15% is expected frornn the above correlation [37.172 S =~R.7/680=-0. uu=O.20) i(~nR.5. pressure.823 0. its value slmould be estimated and added to the gas volume evolved in tire separators. is8. including the stock tank oil if inforunnationr is umvailahlc.68 2.393 The gas gravity used in the correlations is the average valtne of mill cm.38 18 -5. and later [49] expressed tire graph by lime followimmg correlurtion. S~/~R 8 1 5 (2.respectively.=S~=0. using Eq.0009lT .16 -II ‘I’Ime tolmni gas in solummion. °F.0.786 215 315 40.22).30855 l’~=2503Insimi 18. 0.22) Alnenranively. 65 115 Sgn is the guts normalised specific gravity related to tire separator gas gravity.=(676x0.6.=2R.902 log(Sgs) 0 + 1.825 0. mmmd temperumture.

whiclr accounts fur time scpumruilnir prcssnmre is mms follows.1 B.28) lire mnvcrmuge value unt 4515 psiun is esiunuml to I .05 + 0.1) + 5. = I .=7(n8 S(’F/S’IE3 S.32xlO psi T~ta/(Tw(.ve correlationrs (37. = fisunig tine pressnrrc-volnime durta mmt 40()0-5000 psig. (2. Table 2.(S /S )+ l. 24). (‘. C . ii 4000-4500 psig : urn 4501).ncIT’ncient C1 C2 C3 Fstmnimum(e lIne isn)tlierinmuih connipressihility coefficient (if Good Oil at 220 ‘F and 4500 psig.caiurated oil is calculated by correctinmg lire estimated formation factor at the saturration pressure for its conmpressihihity urn tIne reserv(nir (emperalurre.0 R + 7. we ohiain.70 Gas i.n 2.‘no/nmiio.28x I)) ‘psi’ 3 C. guns grmnvny. and later [491 expressed tine grapln by the follownng correlatnnnnn.0005 R 5 (2. (gas to oil runnmo). mumnsl Pun is tire oil density umt the prevailing pismnn~ umunml Icurnl~°urre inn I1mm/f t~. = (1433.i : ‘FIne nsolhermnnmnl coninpressibmhnty cmiefficiemnt is estimnated using Eq.c 71 All the bubble point graphs and correlations can be used to estimate the announnt of guns in solution at a given saturation pressure. I lie mm.. to P.= 0.29) ‘lIre tinlunl fomnnnumtnmnmn v. (P 1 where.-P/ra. nnil grulvily muurd 5 reservoir temperature as the correlating parameters..9759+0.000l20[R.) 0 1 80 2 (2.~?!n’hIti(’nnS 2. = (—AV/V)/AP TIme oil formation volume factor of an under. R. Eq.25T] 0 0 2 wlnen e tIre pressurne gimidicmrl .rrelaiionn.1180.n (50] can be used to roughly estimate the oil formation volunnme faclor wlnemm the properties of gas and oil are not known. /~n~~. de Ghetto et al.. 1’:ml. !‘VT if.61 APi) / (10 P) (2. can be used to curlcur late mine 1)11 cnnrnpressihilily.Ol36RsSg)/P. (2..r Solutio. 0 5 C.30) 5 lime unbove correlumlmoum us helneveul to getmeraily unmmdeupredict tire coummpressibility.= I .+(T—60)(API/S )(C +C.4 S.7. = 0.. B 0 = ‘tine result of pressinre-vohnmunre test ml tine reservoir conditions. Glaso [42] proposed the following correlation.7Slxtt) 8 -l. Standing iniliunlly produced a graphicunl conelunn ionm (39] for Cs) immrmnlinng tine oil fnnrnmnum( mum voluninic faclor. Tine oil isotlnermal commnpressibiiily coefficient.( 2.27) = )V/. C. 5000 psig : C.855 “At’I=40.5e) Fonnnatjw. lu .2 ‘1’ . particularly at Inugir pressures [37]. and foumnd the correlationr (nf Vursqumez-Bcggo. [38] comrrpared tire corrclationrs for preducting the solution guns.32) Ltainnple 2.. 1 line valunc (if tire isotliennnmml connmpressrhihily coefficient.26x10’ ~n’ui The Arps correlaiic.677x10 API>30 4. Oil Fornua ham Volunie Fin c/or is Ihic oil fornmuilnonr vohunnine fumclor mul tIme ~mrcssunre p..7 T=220 “F P=45 IS psia APR30 4 4.. the oil density is cnnnnvennicmntly cuutcunlmilcd froini.rnl(! ( .(2. 6x It) psi (2. is nm ps/fl.=l.(2. where Sgn is the normalised gas gravity.67OxI0’~ I. Va/wire Factor — (2.nrin a! ( n.. dp/uhhn. wrtln urn average unbsolute deviation of about 25%. 1.0 Sg + 12.I00sl()’~ 5 I.~P)/V)~.0+C R.26) (62.~= B. and C is tire average oil isothenrmal 0 s’onnrpressuimmlnty coellmciennl over lIne pncssumre range of P . . rcstnllinrg inn. +0. C .8IixlO I.5%.23). = The Vasques and Beggs [411 correlmmtion. .6.31) The nil formalion volunme factor of saturruntesl oils lnas been cmirrelunleul by mm numnnrher nnf investigators using tIne gas in soluntion R .38].ilunrnie funcuor of oil unt a pressure below the original bubble point pressure cant be eslininated frnmnn a nunmniher nmf correlations.R. moore reliable tinan others with a standard deviation of 29. cuinn he stclernnii med by the trnunlerial balance equnation for mimic slmick tummnk barrel mnf mill. .337x10 9 l’he oil fornmnation volummne factor earn he cslinnnuulcsl witln mn slevimutmann less IIran 5% fanmnn time mmimn. is nclunlcsl to the oil fornnmatiuimn 1 volume factor as. can be estimated from 141]. or B.25) tIne miii fm mmin:mt mum vohmnnne fund m nr. (‘. 1. anmd the values of tile coefficicmnts unre: C. exp[—C . B =l. B. 144 (dp/dln) (2. (‘omumpare I Ire resin hr wi nh lIne imnemisinned s’mmluue. Whmu’nm time pre’usunre grmmuliennt of mm stmll ic nnil (‘uilumnninn wit Ininn tIme reservoir is knowmr.30) with the data cunlcunlaled iii Exunminple 2. Tine Iiberaled guns is cumlcunluited mis line difference between the gas in solution at the originnal bubble poinmt nnninnuns that ml lIne opermmlinng pressure.

16)..’d vuilmie by tIne Muirliunnnmr cuirreluml man. Compare the estimated values with the measured data. 2 (2. The nnemusured value is deuerrnined fromni Eq. P = 6 wlrere p. 6 . 1.724874 (T + 460)2~062I i(s~° ’tp~ ° l I~) Note that R.9/l0°~°~~’ The Marhoun [43] correlation is.52 x l0~0o326 °At’t + (94.I3). Table 2. Eq.ns 73 log Bu 0.ul ———=1 . (2.22).07621 RsS 8 + 1St) S. Eq.mrumted oil.35)..445x 1.07621 RsSg “Pal)] .(2.474/1.474/I (‘00=1. is tine oil deursity unt pressure P.275 13=1.33l+0.(2. with R.IE-I).72 2 2. Pam. as a hypothetical liquid.=410 SCFIS’I’B is equal to 1.331 B Bm~lh where B~is a correlating number defined by: 5 3 B~= R T° S~/ (s~ pr. B~=0.61 + (0. in the above correlations is the original oil gas imn solution. as. = 0644516 79 4 76 9 A = RS 0.38) wlmicir ucdtmces to.(2. PVT Test.(b) oil fornnalion voltnme factor. Katz [SI] sievetoped a clmmsrt for estimrratimng lIme apparent liquid density of natural gas. 0~~ Pun explCmn(P— P )) (2.61 x 62.(2.u. wilh R. witlm partly still dissolved in oil at the prevailing pressure and the rest evolved as the gas phase. 0 with R.(2. Empirical Corre!aiio. Solution: (a) Using the Standing correlation.l735l(logB~) (2.23).=768-(854—544)xl .279. Pun. Example 2.‘orrelatio.4S )]/[5.msitv ‘TIre demnsity ofsattnrumted oil cunnn he estmmnrmnted I’romnn Eq. at a saturation pressure of 1615 psia.(2.=768 SCF/SI’B.35) A= 128671. 15). Eq.l06253x l0~A+0.080135+0. which was later described by the followinng correlation 149].8.l. Tine oil density can be estimmmunted also by calculating the mass and volume of the oil at reservoir conditionns.db — R .. B. R )/5.. Inn this approunch tIme effective volunnme of tire evolved gas.889 TIne predicmn.~ . = .34) B.482)/56I=I .(2. inclunding the dissolved gas. is estimrmated aurd adsied to tine stock taumk oil volummme at the standard conditions. and (c) tolmul formnnmmumon volume factor of Good Oil at 1600 psig and 220 °F. = [(Rs/380)(28. The isothemmal compressibility coefficient can be umsed to adjust the calculated saturated oil density due to compression for an ummder satm. Eq (2.dJ B.36) R. is tIne appumreol density of guns inn the liqunid state.3l4693+0. is as tolknws: (2.02277288 B.96Sg) + 5....600=482 SCF/STB (b) Using the Standing correlation.47257 logB+0.61 -l-i(Rs/38O)(28. R.. •~ Bun + Bg (R. we esniunnunme time oil formation volume factor.6I=I . B.(2 . The measured value is determined by commibining the reported differential hiheratiomr ummnd separator test data.. 1 B~b winere p.26). = [0.3. Paun.—. is eqummml to 410 SCF/STB. Estimate: (a) the gas in s~Iution. estimate the gas in solution. Pal = 38. at tire standard conditions is determnnined by dividing tire total mass by the apparent volunre for one STB of oil.75— 33.33).32) using time calculated oil formmratiomr volunmrmc fumctom from unny of time gcmreralised correlumtions. as described by Eq.= I .37) ROb — (R .79902831 I1:=2. Ibm/fe.994 Tine nnemmsumred vatume is deteiummiimu’d fronmi Eq.0l034x(768. 115.456 SCF/S’1’E3.456 SCF/STB The estimated value by the Vasquez-Beggs correlalion...m089) 5 and C = 2. = Ic) ‘lIre loImnI fnrmnmmnn arm vnilimmnne fmmclunr cumin he estiunnumted frunnmn (he GI mmso correlat ion.l8883xl0”’A where. Fq. Assume a 100 psig and 75 oj.9fiSg)/Pan 0 ‘1 (2. aiim! (.93 log ‘API )logSg (2. P .309 ‘Fine appmnrent denmsity of tIme oil. separator.c 2.=I .858 5 Oil I)e.25).33) Tine esliurrated valine by rhe Vunsqiuez-Beggs correlation.

74 3

2 !‘VT lu’ui.u amid (‘u,rr,’!aui,,,.s

2.3. Enrpirical Correlatia,,s


‘lIme mnmetlnod lmrcdicts iniglily mn~uunnmnlc ulemrsily sluntum fmnr lIne stock tannk oil and low humhhle poimrt where Pa,, is in lhmmn/ft , The apparent oil density is corrected for pressurre, and therm temnperatunre uns folluiws,
= +




pressure oils. ‘lIne rcmlsmrmrs for its stncccss unre line dimcct usc of urmemmsurcd C + density, which 7 assumption in ollen counmprises hulk of tire mnnmmss, mind tine validity of the additive volume imydrocarhon liqutid mixtuires. Tire nmethod also provides a reliable estimate for oil samples with lnigin bubble point pressure. Pedersen et mit. [53] uuiso presenled a set of correlations representing the Standing-Katz gm unpin icmnl nnmetinod. A simmni luir mmmcllnoui, hmnscd ann tine volumnmnc adclitiomn at the stamrdard cotrditions mnnnsl correctiours for puessurre annd ennnpcruunnnre has hcenr proposed by API [543.

where tine correction due to pressure is,

Ap~ = (0.167 + 16.181 x I ~ and tirat due to tcmperalure rs,

)( P / 1000)— 0.01(0.299 + 263 x I tr° ~

)( P / 1000)2 (2.4)))

l:namnnple 2.9.
Fun immune (Inc (‘naomI Oil (‘Fumlnle 2 I )

ulcmnsity at is hnntnhte poimml. rising the Katz equivalent

[o.o I 33 + I S2.4(p~,,+ Ape)


1,0) - [8. I x I 0~ - 0.1)622 x I)) (uo7Mu



I ns~mmmdvunlmmmmmu’ nnmu’Itrmml

(2.4 I ) Eqs (2.40-41) were proposed initially by Slandnng and Katz 352] as workitrg chumrts, annd lumtcr nunmerically by Stansling [49]. When the oil composition is known, Standing and Kat7. [52] proposed Ia calcuiluinc time unppunremmt oil density by (he following method.
it is assumnnned that hydrocarbon comnnpounds heavier nhnuun e)inumne (includimrg II S) uelumnTn their

lIre umppmurcnml density of ihe dissolved gas in hiq,nid state is calculated from Eq.(2.37).
6 p,,=25. 5 Ibm/It’

‘lIne muppmnrenrt density of lIne unil, immcluchimng the slissolved gas. at nine standard conditions is euulculaied frunun Pc .(2.38), p,,,=44.66 Ibm/fl’ 1
1 tnc dcnnsnly carredimoims mimic nun lnrcssmirc annd temnnlneratnnre are ealeumlated from Eq.(2.40). mmmii Fq.(2.4 I), rcspectmvely, as fu,lluiws: APr=)).92 Finn/it’

inmdividuiumi voliumnies as purre in tIre unnixture. determined from.

Timercfnre, Ilie dcnrsi)y unf mm


nnnixtmnme is



Ap,=4.55 11mm/fm’



~ u’






xM /p,



wlnicln resurlls inn, p,,=4 1.03 Ihmmm/fI’ ‘lIme estimrmmmlcd vmnlure mnnatclmcs lime mnneasunrcd value of 40.97 Ibm/It’ (0.6562 g/cnm’) within

where x is the mole fraction of component i, and p~is the density at the stanmdard conmdi(ions 1 (‘[able Al in Appendix A). Time measured density of C~,fraction is used in this unretirod. ‘I’lre contribution of ethamme and mnretinmutie to tire appmnrcnt (nil density is linen cunlcunluntcd un turin l)y considering their effeclive volume as dissolved in the liquid,

nIne expernnnemmtuml uuccmnrmmcy (Tumble 2.11)). Wlmenn lIme oil conrnposutiomn is kmmowmn, lIme mnrethod of Ala,mi mid Kemredy [55] can be used witim cunnnfrdcurce to predict dcnnsily evemn for highly volmntile oils. The aurthors used experimental density data to devekip a cubic equmutiummr for time oil molar volume, v (R(l’+460)

p,.,,(l —0.01 386w~


— 0,000082w~2) + 0





0 0042w~



and P.,

+h v


+ miv / P — mmb / P






P~ ,( 2


0.0l2w~,—0.000l58w~.,)+0.0l33w~., + 0.0(X)58w~.,
ibm/ft tm
Wc,< 16

(2 44)

wlneme, v
= = = =

mnnuntmmr vunlmmunne, ft’/lbmnmnnl
lcnnnpera(urrc, ‘I’ ~ psium

40< ~

w,.,< II)


where w~ .and w~,are the weight percent of C mr C +, ammd C in C (tnlal mnmixtunre), 2 2 2 1 1~ respectively. The apparent density is lInen adjusted for pressunre mnnnd tenniperumlure uns inn Eqs (2.39-41). If CO2 is present at a low concentration, it can be treated our tlne additive voliumnne basis, umsmng an effective specific gravity of 0.420. The mass of nitrogen, if present at low concentrmntion, is added to we,,


10.7335, (psnun)(ft’flhmnol)/’R

mu mmnmsi b clepemrd aim lIne connrponmemnt mnmmul tennmperatunre, anrd for pure conrpounds are given by, 4 a = X c”°’ ” (2.46) h = tnm(T + 460)+ C where time comnstants in Esls.(2.46-47) are given in Table 2,4. (2.47)


2. PVT Te.st.c mumd correlaiimn,n.m

2.3. Enmpmrnca! Corrdatno,n,,
Cnnmnpnunent IOOx

77 a I,
ft7342478 0.8727392 1.0551130

Table 2.4. constants of Alani and Kennedy equation Component X C (70.300’F) 9160.6413 1 Cl (301-460 ‘F) 147.47333


9.67 6.95

10033.56 25767.48 26784.27

ax hs 3659.240 t).2677802 2491.7 iS 0.0843939
1861.507 1)0733304

M 16.1143 30.07


585.1 290.8

~ 61.893223 3247.4533



- 14(172637

(1.51)874103 I 83261,95
(1.52239654 0.62309877 0.90832519

(‘4 mr-C4

1.44 3.93 2.85 4.33

(‘9 41)932.8(1

l.331M69 1.3141589 1.5857214 1.8442812

5(n2.791 1)0191757 1608.659 00516464 1640.404 1)1(451931 3279.81)0 ((.0798574

58.123 58.123 72.15 86.177


228.4 21)5.6 373.1

C2 (100-249 ‘F) 46709.573 - 404.48844 5.152(1981 C (250460 ‘F) 17495.343 34.163551 2.8201736 C2 20247.757 190.24420 2.1586448 3 i.C4 32204.420 131.63171 3,3862284 mn-C4 33016.212 146.15445 2.91)21257 C5 37046.234 299.62630 2.1954785 C6 52093.006 254.56097 3.6961858 132S* 13200.0 0 17.9(8) N2 4300.0 2.293 4.490 CO2~ 8166.0 126.1)0 1.8180 The constants for these compounds were calculamed tamer by l,nnlnrcin,. en ml. 1561 For the C 75 fraction: 1


57558t(3 7574596

N2 C02

1.1(113834 1.1168144 1.4364289 1.59294(16 0.3945 (1.3853 03872

C7+ ‘l’m,nal

31.29 100)10

43 n4.52 0.6901,2(10 6.91)3 0.001 050 9828.37 0.510824(1 89.438 0.0046485 176019.35 36344215 58596.841) 1.2098989

28.01 218

73797 297

I 8370294

25.5 7257.2 936

2 45 Substituting tIre mnnixtnire parmnmnneters inn Eq.( . ). witir tIme pressure and tennperuilumrc equal nun nlmose at the bubble point, restults in lire following cubic equation: v’-4.60696491 v’+2%.0065645v-5 I .448883=0
‘lIme uihmnve cnulnic eqnnunlrain Imuis u,mme mcmiI oat ( Appeindis C), v=2.266 Ii ‘/Itnnnnuil

a~ += exp [3.8405985 x lO Mc + 7 7

9.5638281 x l0~~ M~ /S.~ 15 7~ +l0.7535l7J


line densuiy is cmmlcnrlmuicd p=M/v=93.6/2 266=41 32 thnm/ii’)690 kg/m’) TIme estinunmited vmulune deviates almomnt 0.8 % fronn the measured value of 40.97 Ibm/fl’ (0.6562 g/cmrn’, Tunhle 2.1 D). Oil Viscosity

+ 2.6180818 x 102 /(T+460) +7.3104464 x l0~M~.

2 4 b~ + = 3.4992740 x l0 M~ — 7.2725403 S~ ÷ + 2.2323950 x lO” (T+ 460) 7 7~ 7 2 —1.6322572 x l0 M~ +/S~ + 6.2256545 7 7 The values of a and b for mixtures are determmnined by molar averagimmg, a b


l’he live oil viscosity is often estimrmated fronrn correlations whicir account for the effect of dissolved guns and pressure omm time viscosity of dead (stahilised) oil.





(2.50) (2.51)
The viscosity of gas-free crude oil cunn be estimated frotmi correlations of Beal [57], BeggsRobimrson [58], Egbogah-Ng [59), or Labedi [60], to name a few. Beggs unnd Robinson 3583 correlated viscosity data of 600 oil samples within a wide range of pressure and temperalunre as follows,

1 When Eq.(2.45) has more than one real root, the lowest value is taken as the Iiqunid demnsity.



it should be noted that the Aiani-Kennedy equation of state can be used only to determine tIne hydrocarbon liquid density, and no other thermodynamnnic properties, as its pumrameters Irave been optimised to match only the density data. Clmapter 4 provides a detuuiled coverumge of cubic equations of state. All those equations can be used to predict tire oil and gas detrsity wincn the fluid composition is known.
Example 2.10.





— 1


wlrere, logA = 3.0324—0.02023’API — 1.163 logT (2.53)

Calculate the Good Oil density at its bubble point, using tIre Alani-Kennedy method,

and ~

is the dead oil viscosity in cp at temperature T in ‘F.

Eghogunlr amrd Ng [591 modified tire expression for A, as

The two parameters for C~-C are calculated from Eqs.(2.46-47), with iC, and nC, added together. The parameters for C6 , are calculated fromni Eqs.(2.48-49). The resuilts are as given in the following table, with the 7 mixture parameters amid nmolecuinr weight caicuilmmted by mmiolar averaging,

1.8653—0.0251)86 (APt)—0,5644i iogT


Tire correlations wlnicln estinmate tire dead oil viscosity fronr the oil gravity and temperature only are not very reliable and errors over 25% are expected from tire above correlations [38].


2. PVT Tm’ un c unnnd (‘orru’!atnu,nu.s

2.3. Ennpnruea! (‘rnrre!aumoni.c


D=0.40886446 Beggs and Robinson [583 proposed tIre following correlation 10 cstntnnuntc lIne cifect of (Inssdnlvcd
(n,,=0.46 I cp


C ft,,~’


‘lire reported i.uuhcdi cmirrclunnuonn, Fq,(2.57), cslmmnnumtes ‘lIne nnrcasuired value is 0.45t) cp. rime viscosily at 5015 psia equal to 0.422 cp.

where, 2.3.2 Natural(as C B

10.715 (R


+ 100)



5.44 (R. + ISO)

Whereas tIre pinutse behaviour u)f black (nil is controlled uniainly by its content of light cuunnnlmunurcnnts (guns), tIre bchavirurr nsf rich guns slepends strongly on tire concentration ansi slistrilnnmlim,mr m,f its iremuvy coinrponemmts. Ilcnee. reliable estimtnation of phase change and time umssmnciunlesl Inrunpcrties. nnsiimg tire sununic umlmpi(iadin as tlnal for black oil, cannot be expected. Single Inimumse gums prmmpcitrec, lnmnwevcr, cumn be cslmmnnalesl reunsomrumbly using empirical correlations. (‘nuts is generunily clnaracterised, in tine emnnpirical correlations, by its .specific gravity relative to air uru anne atmirosplreme mmmxl 520 “R (60 “F). Its nnrolecuniar weight can be calculated simply from F.q.( 1.4). lii all //ne ,ga.c eorrelaiio,m,c jim i/mis section, i/re temperature is in the absolute sea/u’ of Rwmkioe, Riclr gurses Iunrnnr cmnnndensuile mil Ilne stunndumrcl (lunhormmtory) cmnmnditions. Hence, their meastmred ‘ujx’cuiic gravily sln(nunlsl be adjusted lny inmclumditng lIre condensed pirase. In laboratory tests, (2.5(n) when themmmolecumlmur scpmmrumtcd gums mmmd comndemnsuntc mnre amnalysed and the overall composition is known, the nrmixtnmre weiglrl cmli lie calcunlumted by molar averaging, and its specific gravity is (leten mnnimmeul fromnm t:q.( 1.4). Wlnemm lIne c(nm(nposition is nnol known, butt the mass and molectular we i glut of guns mmmxl cuimidemrsatc urIc k nn(iWnr, Eq. (2.8) P~ umvmsles lire mixture nrolecsu lar weigirt
vuu lure,

t anui I’ oh is time sumturui(eul oil viscosity at its huiblmle pomirt pressnnrc. An average deviation of abouut 20% [381 is expected fronmn the unbove cOnTeluiliomi usnng the measured (lead oil viscosity. The deviation will be much lnnglrer due to comirpounrdnng of errors when estimated dead oil viscosity is used.
Vazque7.-Beggs [41) proposed the followinng correlation to accosunt for the effcc( of pressunme

the oil viscosity above nts humhhle point pressunre Pt~~ It.

It,,, (P / ~


where, 1)

2.6 pm


exp(—l I.5I3—8.98x 10 P) ITn lire absctrce of nmneasunmcd courdcunsurte mmnsnlecuilunr weight, Eq.(2.58) may [611, M,,


used to estimate it (2.58)

In the conrparative study of Dc Ghetto [38], the correlation of Labedr 1601, performed mnrore reliably than others with a standard deviation of 13%. The Labedi correlation, whrclm ms based on linear changes of viscosity with pressure ah~ove the bubble point as reported often experimentally, is as follows,

5954 /(AP1 —8 811) = 42 43S,, /(1 .008



+(pIp~ — i)(lO-2455Itoxonspo6nsi

/ 100057



Smmbstitumtiimg E:q.(2.38), weFq.(2.SX) ohtmmimn, in Eq.(2.8). mmmd writing it for one STB of condensate similar to [(R / 5 380 28 ( .OfiSg 5.61 x 62.4S,,)

Example 2.!!.



(R~/3X0)(28.96S )

Calculate the Good Oil viscosity at 5(8)1) p~igaird 220 °F.


—. .





0 42.43S /(1 .008 — S~~)j



svlnmc In will reulunce to,

Using the Beggn-Robinson correlation, the dead (nil viscosily, l:ul.(2.52), us cumlcnnlumleul ums 1.020 cp. The Egbogah-Ng correlalion, Eq.(2.54), results jim a deumd oil viscosily uif 1.152 cp. l’he measured value is 1.29 cp. The viscosity at the bubble point is calculated using Eq.(2 55), wittr R,7(n8 SCF/SI C=0.328590l3 B=0.542l982 ft,,~=O.3SS [~



[0.0762 IR S f 350 Smul/F(Rs /380) + 8.25(1.008 — s )j (2.59) 5 8 0 line ncservoir gums specific grunviy cuumm he cmmlcunturtecl simply by dividing its molecular weight by lhmmt snf muir (28.96). When uusinng fielul produrclimnur datmn, Ilne gas evolved in the stock tamrk is often non nnicasurred. Gold Cl uml. 1611 cxaimniuncd experimental data on 234 gas samples, and proposed tIre follmiwing correlugion to estirsraue gas specific gravity, when only the first stage separator

The reported measured viscosity at the bubble point pressure of 2635 psia is


guns slmn(um is avunrlable nun mu tlnree stunge sepunrumtion process, including tine stock tank,

The effect of pressure. P=501 5 psia. on the oil viscosi(y can he estinnmated using tIne Vasquez-Beggs correlation, Eq.(2.56).




+ ~‘a ~







2. !‘VT Te.c~cand (‘orretaiio,n.s

2.3. !Dmmpirieni (‘orre!a,jnn.s


where R and Sgi are the first stage separator gas to oil ratio (relative to the stock tank oil) and 0 specific 1 gravity, respectively, a is related to the mass of gas produced from lire stock tank,
and the second stage separator if present. V~ is the volume of gmms produnced fm’om the stock tank, the second stage separator if present, and the volunre of the stock tank oil if it were gas. 0 The values of a and Ve are estimated as,
.~ .


6 7

A~ (P B 0


, )Ai S~n(~ AP1)~ (1 14 65


)An (T




(2.61) (2.62)





+ BnPIR2Sf(0API)R4(Tm







-~ ______.


____ _____________ _______


where P and T are the first stage separator pressure. psia, mind lcimnperunlumrc. “F. respeclivcly. 1 1 and T is the second stage separator tenrperatumre, if presetnt. l’lmc vuuiuies oh comnstmimils umrc mis 2 follows: Three-stage separation, A = 2.99222 1 A =-l.l9605 5 B = 535.916 0 B = 1.20940 4 Two-stage separation, A = 1.45993 1 A =-0.934460 5 B = 635530 0 B = 1.58124 4 A 2




. ‘

~ .

. . .-







A = 0.970497 2 A = 0.553669 6 B = 2.62310 1 B =-0.849l15 5

A = 6.80491 3 B = 0.793183 2 B = 0.269869 6

A = l.0791(n 4 B~= 4.66120
= 07


_____ ‘..,, ‘‘_____ .~ ~

.~. .,. ___________


~... ‘~ ‘



6 ,7~ p~.....,..

.—~ - .,~ ~.


~ 1.33940 A 3








______ ~‘ I7~’’


B = 0361821 1 B =-0.79l301 5

B = 105435 2

R = 508305 1

____ ~





The estimated specific gravity by tlre above tumethod is expected to be witlnin 2% of laboratory determined value, increasing to a deviation of 6% when noun-hydrocarbon contcrrt of the gas is between 2 and 25 mole %. It is not recommended for gases containing more than 25 mole % non hydrocarbons Volumetric Data The equation ofstate Eq (I 5) relating ttre pressure volunnie amnd ten’snper ntumre is adequu ute to provide all the requnred volumetric information suclr as Ihe gas fornnatuon volume factor density and isothermal compressibility coeffictent The key parameter is the connpressibmlity factor Z which can be estimated using a generalised chart Figure 2 21 shows the clrart for sweet natural gases as prepared by Standing and Kati 3623 TIre cin-mrt w’ns developed by using data on methane binary mixtures with etlrmnne, propmnne, mmnd hurtanc unnsi otlrer nuuunruul guises over a wide range of composition with a maxnmumn molecular weight of 40 The success of tire cinart has motivated many investigators to reproduice it by numericunl correlations. Takacs (63), compared eight correlations amenable for counrpnntcr cunicumlatiomms, both for accuracy and computational effort. The correlation of Dranchuk and Abou-Kasseimm [64] was found to reliably reproduce the data with an average absolute deviation of 0.3%. The correlation is basically the eleven parameter Benedict-Webb-Rubin equatiomm, modified by Starling [65] as will be described in Section 4.1, with the parameters determined by fitting the equation to the chart.


~ ..,.:. .,



:‘ :
,.._~ ~ ~__ ~ ~. -


—. J .
. ~ —.

‘ _______




~ -



..2~.. 4




1o~ r,~1:
““ -‘

I ‘~








~ ‘~ -— ‘—‘_ ___ —


== =




\ :


= =






ii 2 3 4 nm’~ ~




2 ~


I. Compressibility factor of natural gases. SPE Cmipyrigtnm. Repnsndnnced


1621 wimlr


It initially estimates lIme guns vnscosiny attire mutmnnosplicric pressurme amnd lIre pmevumiling tennperature. in Ibm/ft . M is the gas molecular 1 weigbml.4— 0.0S~— 3.188 x l01_6.6.)) and the constants are. irray be increased by I ~p. unsung Figure 2.69) 1 Inc irumlunruml gums cmnmnmpm’cssmbnl ny functumn’.SO/imtmOn lIre gums s~nec Inc gi mm viny is r initially curl cnn lined to csn i rnnunle its critical lemrrperalure and pressure.4) Imnr cunclm 5 nnmnnlc % unilrogcn inn lIre guns 251. wlnereuns it increases tIre guns viscosity at low and nroderate pressures.c Vi. uip to 80(X) p51mm.2.(2.smute. Ennpnrieal Corre!atio. tIme gas vIscosity hehmunvmourr unpprounches thrat of liquid as slnown in Figure 2. At high tinessuire.0 1569 A =-t). frnnmnn nIne mnncuisurrcd valime mnf I . ‘tine estimated value deviates only by I ‘7. = 5. ansi p~is lIme gas density umt prevailing pressure and temperature.286(n.5 S~—74. = S. ()tlmcr nnrmxunmg miles nun calculmute the pseudo properties for estimating time connnpmessnhmlmly funclor mmmc urlso uuvummlurlnle.1844 (2. ursi ing mIne genmeral ised clmart.( 1.~)exp(_Auufr~) 9 7 8 1~ = (~ ~ )‘E ~ ~t~°’ + y where pOr’ the pseudo reduced density.379+0.+ A /~T.3265 1 A = 0. Wichert and Aziz [67] defined a critical tenrrperunture adjuslnmiemnl fumctor. 2 2 E = 120 (Ymm~s+ Yc.=7990/630.OlOO9M +(986.68 TIme unlxnve redmmu. as. (2.639 P.=432.8— l3l.661. = = TIre umbove correlations inn St units are.=0. ‘lIre correcliunmr factor 11.2h = c = rs lIme gas viscosity (cp) urt time unbsolute temperature of T (‘R). 1691 ummeunsumrcd tIre vnscosity of four nalunral gases over a temperature range of 5608(X) ~iR.l psia t’. TIre increase of temperature decreases the Inutuid viscosity.<30 0.63) — = A (A /~T.22.27I~P.2~P.218 ~ .n c annd Cunrrelauio.2 ~ I9.31.6S~ 169. particularly ior gumses conrnumnimiing srgni ficumnnt mmnrnounnts of noun—hydrocarbon conrpmnents.05 165 4 5 A = 0.26M +T) 3.5339 3 Ag= 0.=(250÷4. mund proposed tIne following correlation. PVT Te .(2.0l60M) ‘I’ ‘/(209.709 xt() — 2. + Ycom )i 6) + IS (vnums~’ — 5 tIne pscumdo-critical properties.9427 l. 0 90325 g —0.=630. reported in Table 2.5475 6 A = -1.91 ‘R =1. A = 0.63) is valid over tire following ranges: and 0.00+194. . aurd proposed to use nIne fohlowning correlations.n.(2. 1 YH~S) is ursed (9. or Figunre 2. 25 (l — Yin ) F) 5 (2.66) Ga.22 [681. The corrcctiunn rnf gas critical properties due to N2 amnd C02 cmnmmlu’mnt svuus igmiunred in tIme unhove examnple. A = 0. 17t)I ns mmttern usesl to esl iunmuute the natural gas viscosity.2 S~ —41.7361 7 A = -0.2996.7210 9 10 1 Fstmmnimutc lIre coinn~nncssihiIimyfunclor of tIne gas coindein. belnave differently Iliumur timunt stmowmi in Figure 2.59.l mnTmd ~ <I TIre pseundo critical temperature and pressure are often calcmmlmnted by mmrolmmr averungimng of lIne critical properties of tire gas conrponcmnts.0 S~ (2. is defined as.1056 A = 0.71) .96=0.7<~I. l.=27. ku(rnmip/e 2. Kay’s muxinrg rule Eq. svlierc mu In = Even wlren tIne gas conniposition is known.6)/432. winch is a function of CO and F1 S concenlratiunns in time unixtunme. respectively. F.63). Nanural gases which contain significant quaumtities of sour gases.c 23. 1= 12.s ~t’i’ ‘lIne guts vmscosmty gemrerally mnrcreases svithr pressuine.68) 1=” (2.9t l’. tIre unse of above correlatiouns t(r cslirnrumle Ilme pscmnlun critical properties is meconnmended in preference to ursing airy rmniximng rurlc.u 83 (2. respectively.0700 2 A = -0. at the n eservuni r teimmpcrunium ne mind l’=55t) hmmrg.66ui) rTc = 94.63) resmnlns inn 7=1.22. The above approach results in eslinnation of the conmpressibility factor with a deviation less thunum 2% 137.3/28.82 2.’ed values resumli inn 1=1.062 xi() 6 S~ lIT— 460) + 8. misming kml.65) (2.65mm) (2. mis cuilcun luited frmmmnm Figure 2. It simununlsl be empinasised that the calculated pseudo critical properties from tIre above correlmitiomis shunuilsl be used only in calcunlating the reduced values for estimating 7 from Eq.6134 A 1=0.ee et al.67) to umdjunst lime correlumt morn iii Cmmn’r en mul. Substitution of the rculnnced vaknes mm Fq.i.448+0.43)c I (2.65) anmd Eq (2.2 + 349.(2.i5 x l0~logS~ (2.4).12./(Z CT. Sumnnon 166J used datum omn 264 fluids to hack catcuilumte ttreir pseundo crnlic:ml pi’mmpcrties lunr imnmproving predicted 7 usimrg tIne above equmalioun.cca.21. 06 = wlnere y is the commmpomrenmt mniole fractiorm inn tire msnixtuin’e.66).4/T) 2.~ )p~ + Ano(i + A p~ )(p~/~T.0248S~ (2.22.n2 )05 — (y~. Eq.70) wtrerc the pressure anut temperature are in MPa mmmd K. 756.1 S~ 4 10 un cxp lb (Pg /62.

n.i~=0.74) (2.2866x I 0.s nine! (‘orrehrtrmn.j= l.97054714E-00 un~ =-3. + an . E. mis. H++M+l++4++Hw-mi+f+t4t. using the guns pseudo redruced temnmperature and pressumre.05420522E-03 a~ .70)..464652 h=5.03367881 E-02 a~=8.(2. I’V7 7ent. respectively. Fq.(2. + mm . anti tine vuulunes of tIne coefficients mire un.3. p=MP/(ZRT)=27.4l0l55l2F-03 a =-6.+uumpP.59 + 8. The three pmmrmnmeters are emmlculated mit T=(250m-459.60373020E-0 I a =-l.13.rs*v1 Solnmtimnpn: Tine gums viscosily cumnn he eslinnuntesl using [ igure 2.76) 1 .lmiced froinn 1681 wulh .86264054E-Ol 2 a6 = 3. 1 lnn[r1.+a rPr2+alpP.08 (2. Ann mmlt~mmralivemmretlnosl is tine Lee et al correlation. 3x7990/( I .Deron.s x ‘l’Ine calculated viscosity at the atmmrospheric pressure.11353592 c= 1. 6 .0372 cp.’:rd~m1st61.. 10 P. Ennrpi real (‘orrelacimnns 85 For guises containing non-hydrocarbon compounds.uu~ r P.‘s~ 1 ohtaimn a guns viscosity nnf (1.3.8 permission. i. Itm = Pm.22 at 251) “F and 7990 2 psia.73 + 8.39387 l78E-02 mit = 2.l’.rT.’(mui.48 logS~ ~< l0’(6.n~ logS~) a 1(1 ‘(3.84 2. as follows: 11=128. Viscosity of natural gases.~. (2.~.39643306E-00 a~ ~=-I .006895 xpsia innPa.e.~4. the following corrections to the calculated untmnospheric viscosity mnrust be included.4~)logS ) 1 umnrsl y is time mnnole Frunctiomr of mron-lmydrocumrtnon couurpomncmmt in tIne gas.~+rTr(un +asrP.72) wimere.s 2.12.i (mm + mr. Hence. and was converted to Eqs.49144925E-Ol 10 aI4= 2. [71). over ranges of 1-3.~~]=mum.2+uulrP. i l~ is then adjusted for pressure. McGraw-thu Companies Copyriglnm.75) = )‘c.462i l820E-0() ur4 = 2.peronrn’R.’ )-t.22. ~nins = Yim. P mire tIme pseuidlmr teduccd temnrpcrumlure and pressure. aund to Eq. [70). 4e9 F 200 300 400 500 K=(°F+459..=-2.8ansI S =I . 459 F +:l. tm linmerpolmulinng between the ctnarrs at S~=O.sannple 2..IIliuIIiIlIiIlnI!I~~i 300 400 500 (2.0443241 3F-02 a~ ~= 4.s=cp ‘rIme gas dennsity is calcunlated nisinng Z=I .6)5r 22.1) 4 6 0 moO 200 .P.1..6) ‘R aurd M=27.86408848E-0I a =-2... + x~42+ X(nn~+ ~mm1c (2.04347cp Figure 2. 3 + urn ‘~~+ mu wlncre I~mmmnd .67)/l.37729282 o moo Te.+urnrP. Reprom.8t)860949E-00 umg =-7. P.’~.49803305E-00 a.2866.’) re.93385684E-0l uil2= 8. > Estinmmmte the viscsnsity of tIme gas condensate described in Example 2.71-75) by Standing [49J.262 lbmnn/ft’.94 7.24 + 9. ~N2 = y~ x 10 ‘19.0 for the gas with S~=0. respectively.73) (2. MPa=0. and 1-20.761 by Deummpsey.732X709.09579263E-04 15 TIre correlation was originally given inn graphical forms by Carr et al.

m I’lma.24. As tire solurhility ml Imydrocarhon compounds in water decreases with increase of water salinity. Is .mlu’nt of IIn’u/roearl. sonne investigmmtors ignore tine dissolved gas. ‘l’he presence of salt reduces the mutual soluibility of hydrocarbon-water.n(T +459. i mrclunding cmrn ms’cn ionms fnnr lIme nnrurlecumlmmm weight of gas and salinity of waler shows the hydrate fornmation conditions for natunral guns-waler systenrrs. ‘lime reservoir formation water may contain salt. umuisl inn nnnmnst cmmses nIne hydrocarbon phase belraviour can be studied inndepenrdcmntly of tIre wumler plmumsc.4u.2856E-06 E=2 .. = exp[t’. tIre dissoliutimn of lmghi hydrocarbons from the oil mb the water will.6) + (‘l. which is not in equniiihriunnnn with time reservoir inydruncunrhunmr plnunse encroacires into a reservoir. A thermodynamically consistent approaclm ~5 10 lremmt water uns just another component. lIne prcssunre rcquuircul to form solid hydrates increases with teunmperalunre. Figuire 2. sec Section 3. Sloan [72] covers tire subject comprehensively. given enougln tune for dnffumsnotn.. Varialiomms of oil bubble pount pressurre contumcted witln fieshr wmnter. sunch as in a wunler injection process. Water formed by condensatioim fmounr lire gums plimmse is smnlt free. where the irydrocarhomr-waler nrutural sm)Iuhility is smnnall. TIme vunpotnm pressure nf puire water. In conventional applications.HiIl Companies Copyright. can he eurlculaled by lIne following relation (74).86 2 I’V/ I . This approach will be discunssed in Seclionr 4. by time prcvailiung pressuire at low pressure conditions (Runounll’s law.3. amid to determine the system behaviour.24 Waler Co. . ‘Fire effect of pressure on liquid—liquid eulimihibmiun is gemmerumbly srnmunll.latmn.t. mit lime prcvmmilimmg teuimperunlmmme.se ‘lIre sunltmhiliny of water un liqinid Inydrocmnrhomns utl tlmeir vapour pressures is shown in Figure 2. As time temperature increases the volatility of water increases.3.p’n . Figure 2.0 0 em = S S TEuprpA.s 87 2.2). /:trn. .m. + B/(’F + 459. 1731 line mnmmnlc frmmclimnmr nil ss’umlcr mm tIne guns plnumse cmnmr he estimated by dividing water vapour pressure.3037 D= I . 2..s Is’ . Rcprodurccml fromnn 1681 svnnlm pcmnnssnsnn. reduce tIre oil hurhhlc point.s.23 stnows lIre reulunctiomn of lIme bubble poinnt pressure mni mm Nmnrtlm Semi black oil at 293 K.o.25 73J. ilydrumtes are nnot reviewed un this book. v/v Figure 2. no almost being saturated with salt.26. Ilydrunle phrase boumurdumry willm natural gas.6) + D(T + 459. 103501 131)64. the weight percent of salt/brine is often used inn the correlahions. and propose to use brine physical property correlmmtismns for tlne lunmurnuntimum water. n m’lati. 0 2 . ‘lime solimlnility imncmcmisc. I Ins’ wmntcr vumtnommi cinniteint mnf mimmitmiumt gases inn eujumiIihniinnnnr witir waler is commonly evalunated I mommm Figumne 2.~9E •F S ‘p 12 Fignnre 2. mr sinmrply Inydrumtcs.. from its ircezing point to criticunl poinnt.6)°) (2. P inn psia and lIne cunnstumurts are. fronir less Ilnan Ihunt of the numrnruul scum wmnter. When water. .s willm lcnmperature.snn ns nil I .77) wlrere T is inn F.eI u .76 C=-7.4 4 Waler/Oil. unsung equations of state. 14 3 S a0. simnrplc emrrpirical correlations can be used to estimate the water plnase properties. 5 McGraw..23. wmlter mmmid somnre guises mommy Imrnni smnhiul crystalline conrpounds known as ciatlnrate guns lmydrmnlcs.’. Under certain conditions of pressure mmnd temmmperuut4nn’e. and mIs contriburtionr 10 lIne gums plnumse inn the reservoir becomes significant. Contnate water in a petroleum reservoir can be mnssuuned to he in equuilihriummn withn Imyulrocunmhonm phases.i.c I 16 0.0 . along with hydrocarbon ansI other non-Irydrocarhon connmpoirenrts. amnd tIme water content of hydrocarbon phases. A=69.3 Formation Water The mutual solubuhities of wunter and Irydrocarhonis are smmnmnll. Althoungim various utrits are enmnpioyed to describe the salt content (25]. wlmen contacted with wmnter.

\l- 600 000 071 I .88 2.r.00. permission.002 — — -________‘____.m.I.. 75 trmnmnn ‘ : -50 -nO ________ Wehe Hyd. F 60 nO 20 89 0 20 no ~o 60 04 .i • 0 1450 — pa. (WA Cnnpyrighi..7 06 800000 0 ~ __________ he. 0 a 0 .n. John J.ru. ‘C 0 in I’ .Water content of liqunid hydrocumrhons..r.n in.elal”e d..... wane.9.on Io. —— 00____ m i:: ____________ 0. oonnenn.3. P~oces. Acnuai equiiib. PVT Tees and C(nrrelatia.25. Ennmpirieal Correlatio.um sown. Water vunpounr conmtcimt of mmaturmul gas in equiilihriuimmm with water.. 20 nO 60 80 so mrs ins Figure°~2... Rcpmnnduceml 1731 wirln Figuirc 2.. 2 000 a 6 000 Wnrning~Dashed lines are menastable equiiibrium._ p 0.. Mcketia University oi Tenas 45 50 55 60 65 70 .o 2. ‘F = )“C n Ml+32 ______________ 60000 .. 0. ‘‘~ 30 35 40 Adapted no St by GPSA Original Irom Dr..on..e. ab. . s’_ S.-------~----- 04 ::: —— ‘00000_~ ~ MoI~cnjIarens. 0.a0160. (WA Cmnpyriglim Rcunrmnmtuuccul frommm 1731 wnilr permimnssimsni . J1~ 1 Z~ ~ ~‘ S ____a00 0 0 6 S a 800 U! 600 1= 600 ! 0O04~ 20 ——~/— . Aeg~e 5 a injection of cemposnn.40200 2~O 250 Co..26. ________________ 20000 __________________________________________ .20.0 j H cosOrcIor ~OP SOnItiT6 moooo~ ~ I~~ii I _____TI C 0 0 Li 0 0 J~ 0000 ~v• ~- ~‘ ‘‘S. _______________ 0 0’ I ~~~~______ a o ~o~e_______________________________ — 0000 ____- ~ o’ . --..n.qost 1555 0 OOi no 15 20 25 80 -30 -20 ‘0 Temperaisnre. ~..4 a.m T.60.0O3___—__.~’~/_——_—__.n.mnn.00(.

02505_0. by weight.=4.=430x0. is ums I’mnllinws. as m~=(l8/23. lIre amoumnnl of ulelermmnined as. mms. P in MPa and ‘F in K is as follows.90 2.r wmnler 2. ) for the salt content of 10%.l654x10 T A.8 F MPutO. Time soluhilily ol Imvdn’ocarbonc in svunter cmun he estimated by applyiurg henry’s Imuw for sliluute solumniuins. ‘line correlation of McKetta-Wehe.stimate the waler conlent of tire above gas condensate umi its dew poiirn rn cqnmilmhrmnnmnn with watercontaining 10%. ‘I’lre gas soluhility decreases with increasing carbon number. I II” z 0 I0 llvdrocarho. 0 TEMPERATURE.95) P~/P kg/m (se) ‘lire cxtrumpolaliomn of tIne smmhimmity corrcctimmmr Imuelmnr inn Fugmmme 2.89 g/m’) prior to any adjumstment for the gas molecular weight ansi the wmmuer sumliniry.3.14 MPa) to be 430 lb water per nnilliomr It’ of wet gas at the stunnrdard connditiomns ((n. 5 4 qn =l—4. Reproduced from 1751 wimh permission. / R ) 0 .1. Solution: pm’c.1.93384 lb water/ mnnillion ft’ of wet gums mit the snuummulutrd comnditimuns (6. Iieumce. .2 1 F—2 wincre F is inn “F.649 B-7258.t)00 ansI 100 oF<T<340 OF ) A=7 3..7672xl0’ w~ 1 5 where w is the weight percent of salt in brine. I 5 g/nn5.i653 x 106 7.l2265X1() ~T+l.53425X l0 T —2.26 shows a correction factor of 0. Solunbilily of tnmethunnme inn water. saIl. F.( . as described inn Section 3. 5 F. mnr~=( 18/380) P~/P lhnmISCF The above correlation mr SI units.n.l’ ‘~‘‘ (2. SPE Cmpyri8lmm.28 funr rnnetlrmmrre (74]. = in guns is A 0 = 4 2 8. I’l/T ic no ann(I (‘a.IIH’II)ôSSw. represented within 5% mmccuracy (25) by. cain be expmesseul as (25). lmng(R.37049x I0 T ) l000<P<I0.28.006895 x psia Figure 2.671/1.78) 0 —5 The water vapour content is read fromn Figure 226 an 250 “F (121 “C) mnnmml (n8 ~7 psium. developed from water vapour pressurre depression sluc to smmlt.u 91 As one lhmnole of gas occupies a volume of 381) SCF.96 for the gas with molecmnlmnr weighn of 27.2.34122 x l0~T +2. A 2 78 correction factor of 0.80) and w <30% 5 70 °F<‘1’ <251) “F (2. Figurre 2. as slmownn in Figure 2. rehntjo. Figurre 2.14. ‘lire coefficients depend on nine temperalunre.920xl0 w —l.I30237’F+8.n.u Solubility in Water The soluhility of hydrocarbon gases in water increases witir pressure umnd decreases witln lemmrperalure to a nminimurur value before increasing.27 tin high smmlt cmnmis’cmitummlnmnmms is believed to underpredicm the wunter vuupounr commtent of mm gums mm cu1umi Iihritnmnn witin hnriure. R~= A + it 5- -i 0 lIne clmmurt cmsnr be 2 AP+A P (279) 2 3 wlrere RW is time ft gas (sc) shissolved inn a bunrrel of water unt pressure P inn p. \V.15839-6.93 is obtained from Eq.9I663Xl0” T 1.ss’nrtcuh by Mc(’mmmmr 1251. lIre presence nsf smut inn wumler rcdinecs lIne gins solumbility.marnple 2.siun.27 is often used to estimate the soluhilrty of nuntunral guns inn water. Table 1. A (2. m K=(”F+45 ). The graphical correlation.94883 x IOmOT 1 106 exp(A+B/T+CLnT+DT m 2 = 7 4 2 3 9 4 —10 (9. .05553 x It) T 7 2 — 2.. ‘t’Ime graphical correlation of Katz (68) for the sumlinity correction factor is reconmnmemmd insteumd.3037 D.= (I.01021 x 10 ‘— 1 3 —2.77ur) Ccc-7.96x0. Finnpm rmcmnl (‘onrm’hmlun.44241 x 10 “F + 3. (47.

.~V~~)(l+AV_T) 0 (2.86) .004 12 mmnole gas I mmmoie water)=3t). Conmpressihility of Water 2 5 1)=I. and (h) mhe ismnmtnernrral commipressibility cuneffieieint.and the coefficients depend on the pressure.77xl0 P C =3.ranmple 2. ‘lIne effect of presum~rru~ 0mm tIme binmre viscosmty is estimated.3 133 l4w~ + 8.82) 60 is the forrmiation volume factor mt the prevailing conditions.438603w. Water Viscosity ow —1.0041 )=0. °F.is 2 .s and Correlai’io.000 psia <P C =3.‘n’u.483E-07 (2.1 xl 0’. 1.8x10OP 2 where P is in psia.9267xlOS_8.=-2. The following multiplying factor to correct the isothnerinal conmmpressibility coefficient due to salt has been proposed [77].72213 x l0~w)T° i000F<’fcz400 wlmere. as presunnahly.83) ‘lIne viscosity of brine (ep) at the atmnosplreric pressure cmnnm be estimmnted fronr 125]. unless from highly undersaturated reservoirs.27 slrows lhe nmnumie frmnctiunnr of gas in water equmal to 4.=l . the water density cuun be calculated. 3 C~=C~i(l+8.88) 9 — (2. ~ ic /~t.58922 x I0~ -I.87) where ~wP and AwT are the volume changes due to pressure and temperature. The isothermal compressibility coefficient of gas free water (C 2 l0~(C +CmT+C T ) (2. I’~~ = (109.000134P 0 7 C =—0.61 in’/hhl)x(t).60074 x l0~w~ (2.1$.447265 A.004 12 1 R_ =(38() SCI gums/murole gas)x(nrmnle wmmter/I 8 lb water)x(62.. WS.4 SCF/tthh (5. The dissolution ofgas in water increases its compressibility. + The volume of water at reservoir conditions when brought to tire surface gemmerumily decreases. as. and pressure expansion. Fstinnunte: (a) the anrotnnt of dissolved gas in water. (c) density. PVT Te.2.84) 0 2 1 where Cwf is in psi. Neglectiung tine nmunss of dissolved gas in water at reservoir conditions. Figunre 2. .574 — 8. is 10%. i~ =p 60001 /B.47hi9xlQ w—l.72834 x 10 nn’l.9994 + 4.~ 1 ow 0.)598559 A.052 + 2.4 lb water/ft waier)x(S. as.sitv ‘l’he fonumalion water density at the stunmrdard conditions can be estinnated fronn [25].9Xl0 R ) 0 (2. m1 F anmd w <26% 5 (2.7946lxI0~w~+5.. thermal compaction.and w. 6 2 9 5 = I +(—0.92 Water Formation Volume Factor 2.0(.0001 x l02 + 7 2 1.4 Empirical Correhrtio.81) 1. (mnnole gas)/(imrunle waner)=0.40564w~ + 0.m. respectively.90) 14.89) The correlation is vmulid at T < 260 °F and P < 50(X) psimu. ‘lIre water sumlinnity. over a wide ummnge of omit concentration.41 nn’/mn’) The dissolved guns cumin attemnunlively he calculated fromnr Eq. The uiissolved gas damn be coirvemned mr let iris of SCF/hunrrct as where R~isgas water ratio in SCFIbbI.8546—0.l2l66—2.1062 x 10”P 86°F<T<l67°F and 2 (2.25341 x Ion wimeme B + 1.85) E.121 x lO T )w. where T is in °F.33391 x l0~T+ 5. is the weight percent of salt un brine. B =(1+. as.7 x l0~T—1. as follows: = —(3.ut. due to the combined effect of liberated guns.Irutionn ( ui Assnmmmning the imunturral gas solmihiliiy in water is apprsnximrrately the same as that of methane. McCain 125] proposed the foilowiirg correlmmtiunur.ms 93 Water 1)e.50654 x 10 T (2. the effect of sumlt on tlrcnnmmnl expumnrsiomm nsf wumtcr no cuunnceIheul by its effect on the gas solubility in water (37]. is urt esluilibriummn with the reservoir waler.368 + 0.004 I /( 1—0. reported imr Tunble 2.14 x 10 T + 1. ow 62.(2. as.55586xl0~w~ 601 )cmumr be cuulctnlmutcul fromnm 1761.79) Au 250 “F the vmutues of tIne cmreflicicnmts mmre as follows: A.95301 x 10 T)P (2. at temperature T.6395lxl0 ws+6.01052÷4. Tine gas condensate..0295 x 10°P+ 3.=0.)pr (2. mmmnui (d) viscosity of wumler an the gas In ydrmncunrbunii (Ic w inmmm inn cmnumd 1 nomns.

JPT. 7. tempermntuire of 250 “F.. Wmelansl.sls minim! (‘.0383=64. Ilorstunsi. 15-18 (Dec.9384 Cow.E.90(1986).. IS. Aimneris’mmmm Pen mmnlemnmmm lmnsl tunIc: ‘‘AI’I Recmnnnminemnrled Practice for Sampling Petroleumurr Reservoir Fluniuls”. ACS. 16.s csnmnmm~mnm’nt In m’mnn Eq. W. (Dcc. Rn’fm’.4523 cp (mPa. i). 6 15-622 (Oct. F’Vi’ ic.. J: “Cotrsistcnrcy Cimeck and Reconciliation of PVT Data frommn Sumnmrples Obtuninred wihir Fornrmunhion ‘I’esters tisinng EOS Models”. Rcnmslcllmulrer. 4.G. LJKOOA Report (Marcim. linmmmniurhuuii. D=0. mine cmulculunted compressibility coefficient is adjusted for R =20. JPT. The reduction of sotubihity due to the salt content is estinrated umsinmg F.=2.I Munlunrily Controls on Oil Field Petroleum Column I lelesogemrcity un 11n’ ( . inc lund i ng I 0% sumlt. Theoretical Calculations of Equilibrium Comnnpositions”. usnnsl Alexannder. Fq. unmnd Runcklucrmrm. 13. llunhbuurd. SPE t’ornniuutioim Evaluation. Coirf.(2 87) equal 10 66.. at 250 “F unnul 6837 psiui. Johamrsen.6 SCF/bbl (3. 4. Bjornvik.. MS. I. Sinalr.C. 2. ‘l’urnrcr. APt 44 (1966).~=20. Kikumnni. lIT: “Measurement of Bubble Frequency in Cores”.6 I76 iiemnce.(2.20xt0 psi” at 250 “F.86). 1..3 1854 cp The effect of pressure on viscosity 6837 psia is estimated. rind Vein. 181-183 (Nov.1.. P.umnlcr.4 REFERENCES Remideilnurber..007259 6 C =3.79x 1(10 5~ psi’. At 6837 psia. 122-125 (1957). is cmnlcintmmied mm si imp ‘rIme water fonnnaiion viniume factor. 2. .0: “Better Scpunralor Smnmpling of Crude Oil Reservoirs”. SPE Res.eyllmmneunser. Applying Fq.. 1 6. Oil and Gas J. ihe coefficients are cuutcrilmilcd as follows: C~ow2. unnsl Dukter..icr. B. 232-245 (l9’tl). h4. F.=0.85). 1992).42 Hence..6SCF/bbl. 8. ummnd Olsinmr.~ Ifmuks I 4elnl. 5: “I)egnuuduution umnn. 1475—1482 (Nov. I it. RjR~=0. A.’rc!atiorn.=0.c 95 resulting in R. (Junne.. I). umnrst Pumrks. 1996). 210. 1986).9 1/1. ACS.34x10 psi’(3. 1954). l. t)y~mvik.0.76 SCF/bbl at 6837 psia.. and Yeh.84).. Ottescmn. A1MP.67 nn’Im’) (b) The isothermal compressibility coefliciemmt of the gums tree w. annul Kennnedy. Flail7. The reduction of comrrpressihitity dune to salt is eslimnateci from tiq.c 2.0I83454 AV. 138-140 (June. 337—344..i40). Oil and Gas J. Trans. ‘lruunns.. with the volumisne changes due to pressure and tenm’iperuilnnre ums follows. 46.(2. uunmul Rmnlulowski. J.91 lbnn/fi’.89).9648084 p~~=0. AM. AV. munot l0’7c sam is calculunned using Eq. A. Trunmns. Orgumnic Geocimcnnnistry. J.E: “Anmalysis and Prediction of Mininnuinn Flow Rumle fm)r tire (‘ommtinuoums Rcnmrovumi of Liquids fr(nmmr Gas Wells”. usinng Eq. I —3. mmmd Fm mksenr.q.. Keimmrcdy. Hence.. AIME Proc.94 2... resrrllinmg inn (‘~=3. 6 C_. is cumtcnitumiesl mnsing I3q..(2.A: “Sammrpliirg Gas Conmdensate Wells”. R: ‘‘tJtrhlrle Foriunmtliomn in Supersmnturated Hydrocarbon Mixlunn’es”. 21192i23 (1989). 1:0: “Suimmmplinrg l’rmmcedumrcs for Oil Reservoir Fluids”.=30.‘n. 5.8i).39 xlO’ MPa) (c) The wmmter densim y am ttre stanrdumrd coinditionns. M: “Mea. R. B. Enrg. 1954).. 27278 (1952).R.. R.s) . SPE 36743.0. Aagunarsl. 1986). J: “heterogeneity of Oil Conrposition within a Reservoir mIs mm Rciicctuunnce of Accummnunlatnon ilistony”. Ycin.V: “Vapounr-Liquid Equmilibria of Non Electrolyte Solutions in Smrnall Capillaries. AIMF. R. McCusinn Jr.0: “Sepurrator Sampling of Gas Conslensate Reservoirs”... Nmnrwcgimmmn Nortir Sea’’.0383 I lence. 10.M.II.. I 2.S: “Sunmrmphing Gums Conmdensate Wells”. 6. of SPE Ann. 195. 49/-5 It) (1990). 1957). II. p. A.325x 10’ 7 resulting in C~. R.4. p=66. Geochemrmica et Cosmochimica Ada. 53. G. 2.(2. Reundelhumber.90) 1.(2.mler i.e. SR. I learmr. G. (cmnmnrpiied by): “Smnnnrplnng mmmd Analysing Gas/Condensate Reservoir I1unids”. mmmd Mikkelsen.=3.6707 2. 1992). 358-362 (Aung. P. P. WI).(2. 9. 1960). MG.=-0. I. Yein.(2. 60th Colloid and Surrface Science Symnposiunm.05776263 B~1.44 Ihmmm/ft’ (1(132 kg/inn’) (d) The viscosity of formnmation water at the atmospheric pressunre.V: “Vapoumr-Liquid Equilibria of Non Electrolyte Soluntions in Snmrusil Capillaries.S.surenrsent of Supersatuiration and Crntncurl Guns Suutumruulionm”. Experimsmenntal Determination of Equilibrium Compositions”. Proc.C.

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D. 1-10 (1953). 1980).F: “Evaluation of Empirically Derived PVT Properties for 19.B. ‘F: “h-Iydrocarhomn Phase Behaviour”.. Snunnnulimrg. AIME Trains. 1990). 9mln I’rimrtinrg. 1988). 379-381(1958). Proc. iC.M.D: “Reservoir Fluid Property Correlations”. Conf. 43. and Petrosky. and Prod. mmcl Farslnad. 927-938 (Aug. 1221-1233 Gulf of Mexico Crude Oils”. 35.. of 5th Europ.L: “Deirsity of Crude Oils Saturated with Natural Gas”. SPEJ.. Drill. Slunmrdimng. 145-154 (April. Tulsa (1990). Almnred.. AIChE. of 56th Ann. Sutton.. A. Kortekaas. Rollins.. 1970). SPE Guns ‘I’cchmmrology 32. 101-102 (Feb.. of CIM. 1986). mmmd Villa. Proc. 213.. 1983). McCain Jr.E. Luisunler. Robinson. 30. Conf. R: “Use of Production Data to Estinnate Volummue Factor. Drohm. and Mayer. and van Poelgeest.. P.5-287 (1947). 375-90 (1990).. 968-970 (June. h’eferm’. 42. JP’h’. Todd. W. 0: “Gemreralised Pressure-Volunne-Temniperature Correlations”. J. Moulu. t)milI. Danesh. 46. 325-330 (1990). 52. JPT. 1973).C: “Petmoheumnr Prosluiction llanndbook”. of Pet. J. E. Moses.. Soc. Density Conrpressihility of Reservoir Fluids”. N.M.H: “Application of Laboratory PVT Data to Reservoir Engineering Problems”. AC.. CL. Dept. Trans. JPl’. Eng.L: “Engineering Applications of Phase Behaviour of Crude Oil mmd Condensunte Systems”.H: “Fluid sampling: a better tecimnique”. 52. F.

8. 27..nnncs N.nn 5 2.Tlnarunclcrmsi cs: M=265 S=O. New York.N: ‘‘A (‘mnrielmntiomn for Wmnler (‘omnprc’ssibilnty”. New York (1982).. Trans. AIME Trumns. P.E. and Dcv.timmm. 1985). Beggs.. 146.’pnunmmes ()mn. Kobayashi. 67. BE: “The Viscosity of Naturmnl Gases”. N. Oil and Gas I. 566-573 (1984).. 2. Dmnnhcrl. 66.. ansi Clark. Marcel h)ekker Inc (1990). 64. (Sept. J. AICIrE.4.m mn:nd ( . 1 muhcsli. JCPT.’ I tcxunnnes I t. Ml!.. Crude Oil mmmd nts Associmnted Gmmscs at Oil Field Temmmpcralunres amid Pressures”.. D. (II 3. ilysirmncummhmnnns mmt I ligln 1 71 . 1977).R: “(‘omnmpuitcr Runmutine Trcmmts Guns Viscosity as a Variable”. AIME. mmn.L.O.immn. D. and Engng. mmmd McKcttum Jr. Petrolcurnm Rcfinninmg. Annerican Petroleum Institute. mmcl I)mmnncr. K.sitionrs”.. 1976). J. J. Water. MB. Beal. and Burrows. Des. 2. Katz. and Gonzalez.Solmmlmility of Menhnummre mr Wmntcn mit I’mcssuircs to I O. Sci.1)5 3. E. A. 201 (1954). 5. mmd Rohinsomm. Tlrommnssen. (. Egboghah. Conf. Bmmry. Tech.R: “Estimnrurtinmg tIme Viscmnsity of Crude Oil Syslemnrs”.C... mmmd totmnl formrnation vohunme factor at 2277 psig.5 6t). 54. and Katz.~ 57 I 2 0. (‘onnmpmnnnt’mnis -. and Eng. Conmnpounsls”.minc SPE 14265. ‘ftc PV’F lest mesunlts (slum reservoir (nil mire givemn inn (Inc following tables. McGrumw iIill (1959).iglmt (‘mimIcs EXERCISES I. ( imnl I i’uh. 141 (Aug. Sutton. G: “Conrrparisons Made for Computer Z-Faclor Cmtlcimiationms”. LIT: “Volumes of Liquid Temperatures and Pressures”. dimnxmmlc Mcnlimnmnc I ‘19 51. 55. with tIne irrtcrnnncuiiumlc sepmmimmlmr opermmtnnng at tIne optimnnsmmrr pressttre. Clrenmr.!). Technical Data Book. 63. et al: “Handbook of Natural Gas Engimreering”. 72. J... \W. i.’nV: “An Imnnprovcsl Method fnrr tine 1 t)eternnnination of the Reservoir Guns Specific Grusvity for Rclrogrmnde (immscs”.E: ‘‘Fhnid Thermmrodynunmrnic Prmnpcrl es finn I . I. and Eakin. 23. 41.A: ‘‘‘lImcrmmnmndyni:mnn miss mnf 1 n. Slommnm. Proc.’))) (‘mmmt. 115 (1946). Oil mind Guns I.54 t~iImmnmic t’n’m’ mmmnnc 1 6. umnrd Jennnimrgs. 1171-1176 (Oct. mm l’cn.221-234 (1992). 73. WI). 272-273 (Nov. Gas Processors Suppliers Associmmtion: “SI Engineering Data Book”. (1973).l-1: “Cunlculumtion of Z-Functors for Nmrttnrmnl Gutses using Equmation of Slmute”. ii: “Phumse Equilibria in 1-lydrocarbonr-Water Systenrrs Ill . Inuitimml Resem’vmnir l’ncssmnre = 5712 isIg 62. Nummnmlnere. n.82 69. E. Golsl. 1989). 1960). PR! Report. 57. (‘unlherson. 997-1000 (Aug. C: “Time Viscosity of Air. KS. B. (nI . Takacs. Loiirenz.. Jh’I’. Standing. and Azr7.95 t (‘6 . I’rcssunre Relanive i)ensiiy _. lIrigirumnnn. Trans. JPT. Lee.mnnunmnt’s I )ecmnmies I nnmlccmmmnes l). 0.57 4 1(3 (I (...... AIME. 11G.(XX) psimm’’. Ml): “Correlmstions for Phmysicmnl Properties of h’chroleuimi Rcservunir Br immcs”.. 192.P: “Compressibility Factors for hligln Molecurlar Weigint Rescrvmnir Gases”.nmnn~’ mm. Calculate the gas inn solunlruin. 140-49 (1942).’troleumnnm Mixtures Containing Ilyclrocarbons. 1975).mm.M. 70. 59. md. Wnchert. 1966). I).e t’m’nnl. re/a(n. iT: “An Improved Temperature Viscosity (‘unrmelmmtiomn for Crude Oil Systems”. 1972).8 65. Trmnns. Pctroleunn Engineer. mmmn(I Snuunrulinrg.96 I . McCunin Jr. 1981)) 77.igirl h’etm mnlernnrm Systc’mmns’’. J. — Mn’l’X Nnmnmngcn 1). JPT. 2 (‘n 0 ‘0 n 17 2 Ii 41. 58.. J.. 64-66 (Dcc. Flash and PVT Calculatiomrs witin tire SRK Equmumtiomr of State”.. mind Kennedy. atnd Frcsicnmsl timid. t)cnnrpscy. Ilydmocambon Processing.~tecmmnncs+ (‘~. 34-36 (Jumly-Sep.98 2. 747-752 (Jurly. 1965).. 2. FE): “Cluntlrrmnte hiyulrmmlcs of Natturunl Gases”. hI. 197-200 (1990). Reservoir fluid connmposntnon. JPT.. Eng.. Alumni. API. R: ‘‘I improved Correiumtions for Predictinng tIre V iscunsily unf I . K: “Calculate Zs for Sounr Gases”. I).(1980). F’VT Tm. P. Naturmml Gums. 119122 (Mumy. 7(n. D. Refn’rennces 99 53. R.B: “Viscosity of l-lydrocarhon Gases Under Pressure”. 1964). (nil fcnrnnnmnt imnmm volummnie fmmctunr. I’d r. RI’: “DIPPR Dumta Compilnmtionr Tables of Properties of Pure 56. Sci.mm. Reservoir ‘t’emnnpermmlsnrc = 195 “F. and Ng.883 Prcssure-volunnrc test mrt 195 “F. 223—226 (1951). Jh T. (1985). DL: “Density of Natural Gases”. Proc... of 60th Ann.~psig vn’lun~c_~j~/m.L. Starling.K. AIME. 1140-1141 (1975). Carr. 125-126 Nmnv. A.. mnnd Abou-Kassemni. Dranclmuk. Pedersen. Stumirl’mnrd thmniversity (Nov. R. 68. Mccliumnr. Pet. 94. 75. CR: “Calcunlmmninmg Viscosities of Reservoir Fluids from nlmeir Compo. 74..98))’) 645 .

5077 642 639 635 632 ‘i’wo slmuge sepuirator test mnn 84 “F.5.00 1.89 1.31 72.13 21.94 3.‘orrelm. Pressure Oil Vol.807 5137 1.31 (1.m. 566 2t4 (1 Pres.86 Mm’itmam.895 1.Sti 8.89 1.93 0.520 (1.40 0.36 Propane 4.38 21.72 78.49 11.49 (1.12 2.76 1.984 1.79 0.58 80.57 0.47 0. psig Nimn.759 (1.95 0.71 21.e millumimmnc II 0.845 2707 1.77 SG 0.82 3.422 680 ‘ (1.46 0. 10).723 0.24 2 24 72.1189 3556 1.4i2 lliihttc pm’imii 2.27 1. mire mrs follows: .9947 1. psig 3983 355 3136 2707 2277 1849 1415 986 N2 2.1’) 7.5(15 0.29 4.c I’r~ mmmiii.32 15)2 0.44 0.(2.52 n-butane 2.57 0.nerem’.15 200 1.9.614 1092 0.833 1474 474 1.76 0.0000 1.58 81.0456 1.9897 0.67 1. Sol.2 I 1.480 806 .72 6.7’) (1.848 Reservoir oil viscosity at 195 “F.311 82.045 11.960 0 1.20 4. pug factor SCFIbbh Factor 5712 1.’ lt.gt’in (‘mmr(nmmmn .835 40(1 1147 1342 I .21 1.25 4.320 451 0. I’resstnre. 2.03 1.60 0.17 9.749 0.2.25 1.873 986 1.58)) i).0011 1.42 0.542 939 0.57 0.4t) 0.704 I .95 3. with tIne optimmrummnm separator pressure.46 0.63 1.59 1.14 Hexanes 0. cp 640(1 (.67 (1.37 0.271 344 0.48 0.38 0.re.20 7.11 1)22 (m 1.1055 1.58 2.52)) (1.98 14.00 2.34 0. as reported by mn lumborunmory.06 I .64 1)55 0.46 81.897 566 1.73 28.44 0.645 0.565 0.01 0.815 4850 1.729 0.54 0.931 214 1. 0.17 0.100 5427 5137 4850 4566 4544 4492 4382 4281 4100 31169 2. (014 ‘i’. I’res’ourc. psig VmsL’umsmny.2)5 ‘).4.15 19. II) (1.25 2.13 0.46 0.51 1.74 12.806 0.41 Heptaimes + 1.605 ((.67 0.852 1415 1.97 7.0278 1.9(1 ((.10 4.50 (1.8.059 0 1.n’sm’ tiiiml (. definned in Eq.0159 1.674 19.47 t).c 101 3618 3314 2940 2641 2331 1924 0.64 0.23 3.5 (1.000 Residual Oil SO = 0.2)( 6.5 (1.36 MW 23.370 564 0.60 0.99 6.0038 1.32 0.3242 1.75 0. Gas Compres.00 3.26 (1. What is the implicit assummption in tine above approach’? 2.166 135 0.689 0.32 1.23 2.97 0.65 0.32 11.59 2.89 3. 2.52 44.e n—Pcnuummnc t).29 81.807 0.Immmsj.27 84. II 0. 8 llexumnes Hepnmmncs + 0. E.84 Methane 77.ms 2.798 5427 1. 14 21)39 ((.20 0.21 0. PVT le.38 12.540 0.33 5. I’rc’msmjrc 1st Sep.93 21.10 2..90 6.78 0. lIre laboratory sluntmu is often evahumuted and smnoothmed by tine siiniemmsionhess funcmion Y.733 1)725 0.0 °APt) 2.51 (1.659 0.95 6.~’rg SLI IS II) ~_S~i~t B Vmll’mctor Oil SCi 6(X) 15)76 1358 1. A plot of Y funnction versus pressuire is expected to yielul eitlner a straight lure or very slightly curved.48 1.56)) - 5689 5334 4978 0.m.6 51) 1)725 4566 4267 3556 Composition of liberated gas (mole%) in differemmtial liberation test.mnm.tal Gold Fm’rummatjon Smock ‘lank p.24 21..865 3136 1.26 MW SO 19.17 1)11(1 C02 1.36 (OmIt 15 82 4 65 ((5’) 1.42 0. Cmilculunte tire lrqtrid propamme content of time prcndumced guts in Exercise 2.843 1849 1.500 0.825 4566 L834 1541 Ph 3983 1.40 0.222 238 0.48 8.79 23.39 2.9849 0.01 20.70 1.39 22.(.mti.085 t. Conniposition of separator gas (n’nole%).97 1.37 80.07 1.773 0.840 * Onne smungc separanimn (smock rank onuly).k’ (mill) I (.831 2(X) 1245 1361) 1.93 6. lIme results of consturnml volumimne depletion test otn mm gas condeimsate sannple.13 Differential vaporisation at 195 °F.54 n-Pentane 0.72 79.94 4.48 1.695 1261 0.52 0.53 1)66 1.545 2845 2 133 1422 711 284 (1 * 0.1.14 18.18 2.05 2.99 2.75 1.88 1-Pentane 0.678 (1.839 2277 1. 17 24.21 I ‘1(10 1.36 28.2328 1.55 0.97 2.68 Ethane 6.5)694 1.0099 1.58 55.752 0.3.844 (36.83 i—Pcmnmumm.1660 1.21 i-Butane 0.97 1.

00 (1.49 31. PV1’ lest.31 0.’s nmdccmmnc’. lIne results oi a constmunt volummme depletion test Imave been umsed to calculate the equilibrium n’mutios by trnanermmml halanmce equnanromrs.tcculmnr wcmgtnn Mmnlcculzmr wcigtmm 25 5 97 686.0 (I) 5632 5394 4640 3915 3191) Productnomn J m0l’S~ 9 1)00 2.00 (14(1 2. 1 K (212 °F).256 0.ve Gas.5)6 0.imic Methane Enhanc Propane humane in-Buuane 2.360 0.96 0.0 271.28 171.40 0.12 846.46 (1.39 ((.245 0.nmnec n’ t’enmnmnc I ((.0(1 (1. the Iotuul volumnre of produiccsl gums.0 814.34 7.5 ((.0 lOIS lnniial reservoir pressure.inu’s Nm’nammes I)cL’mmmnes Unmlec.52 8. plums ~ 103 (1.56 7..186 (1.38 0.16 21.12 0.90 24 I - 0.67 It (.20 ((.337 761.0 psig 4641) tlydrusgen Sulfide Ninrogen Carbon t)ioside Memtnane Emlnunne Pr~~pane 0. mend Cm.35 ________ Density.902 0.28 ((II ((.524 78.5 Octanes Nonanes Decanes Ijmmdecancs Duxiccanes Tridccancs 0. I) us mmmc mm.017 0.4 kg/inn’ Constant volume depletion test results at 373. and plot P/Z vs.42 I .58 I)mm Immmmce cmulcun lat iomns.1 870.6 775.5)) ((.57 2.40 2.. Cuulcurlmnte fire slumluc oil pressure grmudiemrt inn Ilne reservoir.5 (1.nleculuur weiglmi 67 .00 (1.38 0.47 22.12 2 (.33 - S~c Inc Gravmiy Compres.923 1.00 0.82 0. witlr mu GOR = 600 SCF/STB.1) 39(5 0.39 ((. Wciglnm n-Pcnmanes nPeniane Ilesanes tlcptanes 0.58 7..mm.mr Volumnre of of Produced Gas of Produced g~s Rcii~gradeLiquid 0.914 000 3.1)4 1(1.21 121 0 I 740 ((.440 1.20 0. )b) Dctcnnmnmre (he denrsity mmmd Commipm.~ ___P691 (I) 389.880 0.Ius 1 Molcumnlar weiglrl C..96 (1.588 0.54 0.40 2. Is Ilmis physically possible? 2465 45.44 79.831 0.330 I Iyulrmmgcmm Smnltidc Nimrmgcn (‘mmmtMmn Diunxidc Meilmane Pitnumnc I’rm’pmmnm’ humane mm ll..923 0.30 22. The K vs.39 2.88 121..120 0.6 8348 83. 7.114 0.2 C. The 5 reservoir pressunre mmmrd tcmsmperalure are 65(X) psia and 210 °F.66 0.48 0.nSition of condensate phase at Pr 71 bar by material 9. Pressure __________ ______ ________ Curnutmmm. 2.758 0.386 2.06 (1.4 169 M.661 1.0 32m. Composition of produced gas. —~ (‘mmmnmpmmnnenns m~rlrmmcmmm’ns Renmmmmnmnnnng gums Remmmaimnisg miiI ____- 783.2(1 4. The stsck tank oil API=40°.0(1 ((.41) (mm) (‘alcumlurte tIne lwtr-plimmsc comsmpi’cssihility fuuctor of the cell content. Pressure bar 321.90 1.39 0.49 067 .’s I ).345 0.11 0. kg/nm’ Mol.8. An umndersmntumraned oil ns produced llnrouglr one intermediate stage separator at 200 psia mumruh I 20 “F.5)) 82.78 (a) (b) Estnnnnur(e tIne out bubble poinnt pressure at reservoir temperature.. _~.0 171.91 19.47 0.9 86 89 102 118 Comimpositnnnn unf m’ciuiaininrglluidsumn7ihumr.40 I .102 Con’unposition of reservoir gas.61 909 8.737 ((.23 7.17 0.396 0.respectively.0 1740 71.277 0.037 -— }lcsmnmnes I teplamnes Ocn.41 I .05 3 35 2.502 0.49 81.00 (1.5)2 3.5. 10 0.23 76.956 0912 (187.mmmmmn.5’) ((.098 798. . M.23 (c) Wirurl will be tIme oil mind tunlal formnration volume fumctor whets the reservoir pressure falls 4(X) psi bekrw tIre bubble poinrt. 271.39 9..39 2.05 0.40 ((.30 22 n 0 319(1 0. 2’) I .‘cmnmm.4 744. Propernies: Molecular Weigtnu=335 Density = 870.80 0.6 789.8 178 0.i 2 (~L’S~ 0.4 260 335 — ((.04 0.0 221..51 82.40 2 5)1 82.9 204 — ((.__t~_.732 1.065 (1.c 2.mmumnc i Ik—inn. P plot shows that the equilibrium ratio curves of C3 ansi rC4 crmmss at mm pressure vmmlue. 2.48 81)57 7. 14 0.879 (1.3(1 0.84 31.62 0.cs I lm’pnummmm’s (cimumnes N.53 7 04 3.42 0.58 6.2)) 0.091 0.5.0 176 0.90 15.63 6I.5’) 1.52 246 Tetradccanes Pennaulccancs Itcsmxiemmmncs lleptadecanes Ocnmxh’anes Nunnadecamnes Eicosanes pIus 0.Immune n— I ‘e I(( muincs mm I’emmnamme I Ics.1 (1.00 (1.43 I-I I (1. (2) Sanuration pressure an indicated menmperammirc (mlew poinu).41 (1.nmnes.45 ‘ (1.4 136 147 ~mpm~’) 0)8) (1.873 (1. Comnmpnnnenn Mole’S’ Niirm’gen Uartxmn dnmi.163 0.m.07 (1.rre(mriio.33 ((.79 4.585 7 029 3.2 83(1.5 2 8360 162 176 190 204 21)5 2.31 3.90 4.sml’mmlmmy Pmmct.787 0. and S =0.1 811.74 (1.42 3 315 (I .12 3.31 0.5) 2465 0.4 (2) 373. Exercise.

are of innterest inn mnmamuy fields.6. I0.. tIne prohlemnr humsically redurces to detennination of tine equilibrium commditiomms for a imnullicomnmponment system.The viscosity of a North Sea gas conslensatc at 100 “F. across its boundary as stated by the first law of tlrem’mimodynuuinmics. 3.6 to conntiirtmmntisly remove condensate in a well with a wellhead pressure of 2(XIX) psium mmt 120 ‘F 7 TIre ttmbe nominal diameter is 4 in. and (d) viscosity of the waler uut tire mubove conditions.n. amnd lIme missocimmted emngineerinng applications.6 mind lire connate water salinity is 200.A gas reservoir is at 300 “F and 6()00 psia.13. mmnrd tlns—r’nnmmdynnumi mnic reluit ions winch mmre fm. A rich gas is produced and stahilised in tlmree sepmmration stages. hunt also t(r formation of 2.4. 2. is broumght into equilibrium witin equal volume of fresh water at the reservoir con(Iitions to simulmmte a water drive process.I2.760. potemmtiunl energy E~. ccn’tmminr concepts. reported in Exen’cise 2. i. The water salinity.nsition.8. 2. ‘l’lmese will brims tIre foundations for mull tIne methmmsuis used to dcternmninc fluid behaviour in tine renrnmmining clmmnpters of tins book. Estimate the density of oil reported in Exercise 2.c lOS 2. 2.7.and kinetic energy Fk.stirtrate time reservoir gas mnrolectmluur wemglrl.’. l’lris subject has been extcmnsively covered mm nrsmimnerouis text hooks amrd pumper collections.104 2. unt tIre initial reservoir condition. umsinng tine gcncrmil used clmmurl.000 ppm.r. tIne cirmmngc msf syslennn total energy F. The second stage sepmmrator temperature is 100 “F. witlr well estumblishnesl primrciples. Estimate the viscosity of the above oil. 2.1 CRITERIA FOR EQUILIBRIUM Iknr mu s’tmnscd sysnd’mnm.mndummmnemrtmmi to Humid equmi I iimria are reviewed. and tine gmus specific gravity of 0. Wlnemr sucim a systenmi unndergoes ann ideal but unreal reversible . (c) density.9.’. sIc finn it ions. 2. using the Lee et a!. unmmd wom’k W. hlenrcc.11 What is the minimum flow rate of mu guns witlm mm specific gravity of 0.1 5. Time first stage separator teirmpcrumtumre mmmd pressure mure 50°Fand 1500 psia.0588 cp. WS. it is rcumsomruuhlc to mtssunne thmmt mill lIne co-cxitimng plnases.1) where tire lmemmt gnvcun to lIne syslemnn mmtud work dome try nIne sys(emnm Inave been assigned positive signs in tIne umbove equmltiomm. 2. is only dune to rammsfer of treat Q. and conmmpumre it witlr mIme mnmemrstmred v. Compare the results witlm the turemisuired vmuitie. moim! ( ‘mm. In tIns chmrpter. References l-2~prmsvide buisrc tinermnmodynmuumnnic concepts of Iltnid plmase equnilil)ria.Estimate the compressibility factor of tIme gums conrdensmnte.e.A lean gas is at equilibrium with water at reservoir pressure of 6527 psnmm amrsl 279 “F. l’imermnodynmunnics Irave 10mg beenn used to inrvestigate fluid equnlibrius. E. ummrd 55(X) psmuu huts beern measured equal to 0.73. mmnd to reduce gcmiermml criterimu and Imuws to prmuctical tools. l4. Estitnate: (a) the anmoumnt of dissolved gums inn wuiter. Fluid equnrlibrium. ‘l’lris leads not only to ctranmges in Ilurid properties.. stunred mrs (ire iintcrnnmml emnergy U. mnur( exclrumnngimng mmrumss winh ins sunrrusumnidi nrgs.1 at its btmbhle point. I’Vl’ 7’. AI~A(I+ Al)~ + Atuk = Q - W (3. tnsitng hIre KatzStanding and Alani-Kennedy methods. respectively. new piimmscs. ‘I’ime first stmmge sepmmrumlor is at 1500 psia and 140 “F with a producing gas to oil ratio of 80(X) SCF/S’i’l3. at any point in llre reservoir. is 10%. utre ins equmililnriunmm. correlation. ‘rime produced condensate specific gravity is 0. Estimmmatc tIne gmms viscosity at the above conditions. or elimrninrmutuon msf sunmnme of tire existing plnases. pressure unnnsl Iemnrpermutsnre. mind (t) tine isothermal compressibility coefficient.’rt’Imili.7. Is there a possibility of hydrate formuruution urt time uibove conrdmtiomns’! 3 PHASE EQUILIBRIA Productiomn of reservour tiumids often is mucconnipannned wills vmmriationms inn conrnpm. Estimate the reduction of the oil bubble point pressure at the above tempermmnurre due to its contact with water. 2. As clnunnges within time reservoir mire oflein quite slow.mlunc. The gas nmolecular weigint is 28. TIne gums specnl’ic grurvnty is ((.A sample of the reservoir oil described in Exercise 2. (a) (b) I-low much liquid water is produced by condcnsmutiomn inn tine sepunrurlor.

i.)nm. The Gibbs energy G.(3.11) It cmunr he slnmswnr Ill. time system energy is at its lowest value amongst all possible conditions. lead to simpler expressions in ssnme applications. mm’.(.17) 15=1 i where.(3.. and (amA) ~ > For mm clmrsed sysncnnn cumnrsislinng msf 0 plmumses.. U tends to decrease as tine state of equnmlnhrmunnnr ns mnpproactned.~dT + ~(V) dP .m ..(3. called a heterogeneous closed systcnnn. (3.i. the above immeqsnmnhity .12) (3. cue n gy.e.X-’)) are necessary.. I’i property (dG /~rr.11) wlncre s denotes emmch plrase.n-~l t=t 6 0 (3.14) Substutunting Eqs. is defined as. (IG = —SsiT+ VdP+ ~t~dn~ (3.5) winere n is tlne nuninsher of nnnoles of emmcln coimnponeint. as described in Sec(non 5. and volunnue respectively. the clmange of entropy is higher than tlnat in tire umhm. including all possible nminimmma occurrimmg in lIne calculated Gibbs furnmction.. wlnere each phase is considered to be a lmommn(ngCneOUS one.~ 5 (3. (aG)~.s 2.7) = Tlrat is. tIne mmhmnvc equnation cmun be written for each phase. tluereforc. is often used to derive w(nrking expressionns.s us collect imnnm of unpen systems. (i. with no changes in the kinmetic ansI potential energy url unnnifusrmrr trcssumrc P uunrul temperature T. =(4A/m~(nn. (iwhl—l’S where II is tIre system enthmnlpy. lire I Id nmmlnoltz. I. Imowever.106 . It should be notcsl that Eqs.4) Inn umnn openr syslcnnr lIre clruummgc mnf Gibbs energy cannot he expressed by Eq. ‘l’lne Ilelnmrlnohl7. is defined as the partial molar of thrmtt connponemrt. tlmumt is. itence. cxclmmtngnnmg trruuss wills otiser open systems. Tlrernnmuxlynaismic relations can be emnployed to develop similar s(atenmnennts anmnomrgst ollrcr sImile properties. ~ =(~UI~n~). mi’. ( ‘rileria for Eqimilibrirmmmn 1 07 process. mis the gemncral criterion of equilibrium. 14) its Eq. dU <l’dS — A = Ii — 1’S (3. aurd remains constant in a reversible process. at constant 1 and P the Gibbs energy tends to decreurse mis remsl processes. A clmsesl systemmm counsisling (Sf mm nunmnhcr of pirases in contmrct. mmnnsl N is tine lolal nnunrsher of components in tIre system. energy isray. N si( = —Ssl’i’ + VdP X(m’JG /dmi.2 Chemkal Po(eritia~ . =(0G/)nr.. tlmunl.~ (3. cans umlso be derived as the requirement for equilihriunnr.13) 11w Ii + PV (3.2) ‘lIne tmnimnimnnmnmnr (iihts energy. we obtain. Further infornrruulion omr tIne Gibbs energy mmninimnuismution to idcnmlify equihihriunm conditions is given in Seclnons 5. leading to.. we obtumin. dG—SdT+VdP which states Onat.3.15) Sumhstitutinmg Eq.6) lIne dcrivumlivc of mmnr exlcmnsive property relative to tIre number of moles of any conmponent at comrstmnnmt pressure. . 1 (3.. 13). in the equihibrimnm stale. lIme systenrn (Iihhs energy is tnminminnmunn. ). 1 (3.(3. At equilibrium.slnr. =0 and m (d G) r >0 (3.16) Simmiitar cx pressiomns using anotimer energy IC rio. the equilibrium should he dcncrtniincd by semurching for line global nnininruinr value of Gibbs energy.6) as the energy cmii) vmury by comnrponrcnrns of mIss’ systenur crossimrg tIme plsmrsc boundary..stunlcs limit f(nr un process unt cm(msslmmnrt S and V. hut not sufficient conditions.(3.)~ ~. ‘l’Ime clruunrge of totmml U ihhs ennen gy md tIme closed systennn is.2-3). tcmmnperatunre otirer mole numbers. (~A). dU = TdS — PdV where S and V are the system entropy. (3. i. 0 0 + 5 = 0 (3.c” Fq. the combined first and second laws Of thermoulyimainnics stunte. sims. TIre partimulmmnnd inrolmmr Gibbs ennergy is called clnennicai potential. can he tremuted a.9) (3.)~ . 0 (3. .10) 0 ~( ~fi s1G = ~(—S). whicln is tine ultitmmate comrditnon of mmny rcmul process. A is the Ilelmholtz energy defined as.4-5) in (3.ve eqnmmmtionr. If the process is irreversible. with (he subscript nj referring to all mole 1 imuinubers except nj. PdV (3 1) Since all real processes are irreversible.1 9 I uu. Hetnce..

lIne fmmgmncmty is eqummi to its pressinre..(3.. Writing Fsj.N (3.(3.8). ‘i’Iue tnmgumemly cumin he relumled rngom’ounsly to mmnemrsimrmmhle properties umsimrg tinem mmnodynmummnric relumlnomssl IJ. For mum ideush gmms. we obtain. respectively.191 p~’ = RU tmm(i’..(3. linerefore. (3. o.24) Irowever.(3.. winer’c ij is tIre nnmmnle I’rmmcluonm of tIns’ comiuponent i.. wills mmli referemsce stmites unt lIre sumnnre temnperatumrc.20) The above general requirement.18) TIre mrhnve cqummlmorm prn~’idesmm simmnple relation for the ctmmtnge of clsemnmical potentimml of a ptnre idcmml gums wlsemn its pressunre clsmmnrges Ironnn P0 to P isotlnerniral ly.2. which leads to a simple expression for the chemnnmcal potential of an ideal gums. ~ ~dn~) 0 = 0 i= I .. hence.28) Simmce mill systdtrms belnave mrs isIeuml guises al Fugacity As relations amongst state properties are independenrt of tire process puntlr [21. is given by.’ — ~t’ = Ri’ ln( PiP”) (3.N (330) ‘l’lnuil us.m~w’iiv(escunping temndcncy) as follsws. ~ 1)1’.(3. we obtain.. suds mis fugacily or uudlivity. For a tnntnlticompornent systdmnn.211 Hence. tlnc cisenmicmul potential. (~11~ ‘~)T = ~(? =~~=- =t-~~ i=l. ml the fumgacmty of a commmpoirenrt in the two asljumcent phases is the same. mmnm)immr cnunrmrpy mmmd mnroluir vmsluuminc respectively..23) Eq.6) fmr mi reversible process can be used to express the Gibbs energy clnange.N (3.5.) (3. TIns is mmclnieved try expm’essimng lIre chemical potential in terms of auxiliary thermodymnamnic fumnctions.(3. As the total system is closed with no chennicai reaction.. = -~ R’ri’v L~~) ~l’ ~ — R’~fVdV—inZ 1 i=l.. tlmenefore. Pinas’ Eqimilibrüm .h~ (I) — — wlsere Iii” ummsml 1~° mime tine chmennicmml pmnnentimml and fugacity of tIre commmponemmt i. Fugmmcity dunn he immnuugined uus mu mmmeasure of tIre escmupinng tcmrsicnucy of inmolectiles fronnn one pimumse to arm asljmucent plsmuse.20).2.”) (3.. In. wlmemr I’ ~ 0 (3.22) ‘t’ire depuurlure of fsnguucmly coeffrciemuts fronrm unmrly us.N (3. in a mnntnlticonnnponetnt systems. the total number of nnroles of eumcin component remains constant within the system. at mm i’ctcmemuce sImile. (~I. and tIre fungacity of cads conmmponenst us eqummml to its parliuml pressure.108 .27) for lIme connnpomnerml i. tIns’ fmngumcily unl cmmclm d’nmmnpmnnncnst slmorilci he eulnmmml thmromrghmmain mmll the plummses helen ogeureonis sysne iii mu ruin nit tin mmiii mm mm Vi (3. witlr lIre pressurevolume relation as. the general requirement of equilibrium. beeotsmes mm practical emsgimseerinmg tool if (Ire chemical potential can be related to nneasurahle quantities. and since changes in mole nummnbcrs of eaclr cmsrnpoiretrt mire arbitrary.v. ‘lire rmmtio of furgmucity to pressure is defimned mis tire fumgmmciiy coefmmciemnt ~. lemmds to. I = 1 (2) hu = (3) i~i — = I” (0) i= 1. Inums I Inc umdvmmmrtumge of cnnnploynng mu function wlr ichm can be mnrore easily umndc rstood mind evmulunmmtcsh as mm”corm’ected pressure”. s’env low pressnircs. change of chemical potential of the pure substance i.(3.25) at cotrstant temnrperuuture. s ansi v are tIne moluur Gibbs cncm’gy. cmilled fim. tIre (3. C’rmterma for Eqmmiiib~’iunm I 09 At uniform and constant temperature and pressure conditions. 1. dIl =dg =—5 dT+v~dP 1 1 1 (3.27) Considering Eqs.Lt ‘~~)T = RT/ P where R istheuniversal gasconstant. 18) and (3. Fq.(3. the two phases will he us cqinnlnbrismmrm witlm no met Irmmnsfer of mmiolecules fn’onss one plsmmse to anollner. (3. .(3. in emmch plnuise of a lmeterogemmeous system.. that is. a nsmeursure of systemir. At constumnt temperurture I Ire above eqummilion rcslumccs to.2(n) for milnlmhicumlioms 1mm neuml systemnus. -. 8 l_esvms (I genrerumlmscd Fq. = where g. .25) lmm~.2. 0 Integm’umtimrg Eq. tIne equnmulily of the clsemniicmul potential at csiuilihriumiur givemr by Eq.2. . given by Eq.. / I. .26) (dG)Tp = ~ )~ = 0 (3. I.19).. I leurce.29) nomr—ideuulity of the dG = —SdT+ VdP For a pure substance partial nn’nolar properties are the sanse as molar properties.20) for rclmmtinrg the properties nil equnilibrumned phrmuses.30) is mms genmemumi as Fq.31) r. leads to. the equality of chennical polenntnal of emucls coinrponemmt throughout all the co-existing phases at equilibrium. by definimig ur “corrected pressure” fummsction ‘f’. Pvj=RT that is. I.5.

et urs :or~smder two ptmumses of liqumisl.3.systenmm is. (join: RATIo Eq.(3.110 :1 i’h.f. P<15 MPmm EQUILIBRIuM wbmere P is in MPa. . defined as the actunal property mmrinius that calculmuted by musstrnruinrg tIne ‘lIme mdtnvity cmmn.6875 Ill where V is the total volume. usnrst mrll properties euro Os’ cmmlcunimmtcul mis mierivuutives of (lie residual 1 Ichmnslsuihtz fumnctiois 131.. or at its vapour pressunre.27).41) .R’U V) ~dVl Jrvn.28) to hurtin phmumses.5x10 2 4 2 P—7. is tIre nrmixtumie 2 lmm~= ~—6..5 x 10 p m~=O.2.35) II is m intuit m ye (hrumt time fungurcily of cumuli cmnmnnponmenrl slnoum Id depend on its concentration in lIne mumxl tine.(3...b.s often seleuned mus (he pumme sumhstumnce mit tIre systems) totmsl prcssumrc. l’Irc use of dcsci itiimig lIre tnchrmmvnunmmr mn! mm systemnr by evmmlummtmng its Iiclnmrholtz energy.(3. mmml conspressihility factor given by.32) u. Or V= infiruily urn P=0 . 5 Z=t V/nuR’l’ whsere.~x l0 P /2l:~= —0. The unrsler of Integralmoms mmmd differenntnmutnon mrs Eq.N (3. resumlni nng Fntlner of ft’ or 1° uslay he selected mumhi(rmnrily as the reference stale property in Eq. 4 2 7. curms he evumlmmmutcd. using ss’nmnr-ennnjnirmcmil s’nlmiumnionrs of stmutc mis described ins ( ‘Iumspler 4. ln~= J(~_~)dP = (Z I) .(3.” (3.35).e. he connsmdcrcd as mu meassure of fugacity contribution or activeness of mu conapomment in a nnixlnnme.ce Lqmmi/nh.~aoupIe. mu.37) into the general expression for the fugacity coefficiemmt.(3..A ~inm 95Cr u’lrmnmcc of nIne mc F’re. wIrem’e v is tIre msroimur vunluimme.. ‘line nmmly limunitation for selecting tIne rel’erenncc sImile is IlnumI its lcnmipcrmmtmmrc mmntisl be equnmml Ims (hue equilibrium temperature. / 1. tlmerefore.028 MPui Activity (3. (3. The furgacity is most often the chosen reference properly.1 I ) nnmmy he rmitcrclnuuurgcsl.mcimmevumhlc tursk. n~is time nummmher of mrrolcs of comnspommenrl i.. 3. V. mit umnry pmc. in preferetrcc to the Gibbs cnnergy.ssmnrc cummn he selected mis lIre rcferemuce stumle. lime mmclivnty c’mncffmcmcmmt is mu very umsefiul mmumxilimum’y functions to describe liquid phases in phase Cdli nil m hr idunn duntcum I mit ions. .sce sImile fmncihitaies the application of then nimmsdyn.lnZ + P)slv (3.2 Z=l—6.(3. Es tenisi ~ sttidies lnmuve been conmiucted ho relate fine activity duel I rcmenit hr millrer I lncnmmnmrshymnmmnmnic funnnct iotrs..mumnnc ru’Immlimnnns Inn cirgilucs’rinrg prolslensis.. provided nhnmut the vmulunc of (01’ I dir.3O) for such a l.) .5 x lO~ P (3.3 I). i-Ielmholtz energy divided by (RT).5.” (3. wills msn muuccptmmhle cmngmneernnsg mms’cmmrmmcy.N I.P~r i=t.32) f=m(o<i’=5. )m v over tine whole range of tIre imntcgra(e. = ideal gas behaviour.33) Eq.5xl0 P Calculate the gas fugaciny an 10 MPa.13’ (‘oeffjcne. often in mole fractions. munch numnncrosns nsrodels have been reported to (helenmnnmmne ml vmiltne for liqunid connrnonmetmls Ill.40) AIipiymnsg Eq.34) In~ = ~IJ dn. — In Z i= I .’ =x..( 1.36) line immtegral is the residsnal. It i. ommc nil lIme uulnmsve two cxptcssiomss for tire fugacity can be sinmrpler to usc.38) — - llcmscc.r Eqmmiiihrimom.2. Eq. us the total nutimber of moles in the mixture with N compommemrls. V mul P. i’ =i’~ Substituting the above expression of Z in Eq..2. at lIne tine summl n mg IC mnmpem mmii) re . ‘this is urn . we ohstmnin: I. = c/s~ (3.3 I) simply yields the fugacity coefficient.n( (—~.. I Icmice.N Inm~ = ~(~_!)dP = 2 j(_6. i=h. Depcmrdmng omm tIme fornnr of tIre eqummul ions of stumle. Ilne unbmnvc eqummul mmmi) stmggcst5 Ihiurt the mmcfi vity slsounld be closely reluuted to the s’omscu’mnln at ion. as pure or in a mixture... i(i 3I ( riU’rul f’. i. = (~x. The aslvmunlage of Ire mmhove frmrmn is tlsunt tIne immtegrationm Immus to be done only omnce. ‘lIne rurl nun of mmcl r vity lo commcc rnlrmntiomn.So(m. (-). I. t. l’lre substance i. ‘the fm. The connpressihiliiy factor of a pure gums at 290 K cain he rctmmied 10 ins ~ us. is called tire (I(tIu’. will lie disctnsscd inn Section 5. Inc n mit nun (ni tIne fsngmms’ nly mm I Inc s(mmte of innIciest to tlnmut mm (Ire referenice state is called (Inc activity.3. 5028 (3.1.39) F. murrul vmupounr.” (3. n. we obtains. Z.ngacmty coefficient of mm pure compoumnd cumin he dclernnrinncsl by inncorpormmlimmg Fq. at equilibrium.L 1~ — ~ ~..

Figure 1. A general mmmd rigorous approach to determine tine fugacity coefficient of a component in both phase..nnd rut krw pressunre can.(3. cmun give relimuble re. by ilne Lee-Kcsler equnafion is mom micceplunhte. Depending on the definition of tIne proportionality comrstmmnl. Raou!t’s Law First. be assuunnred cqtnmml to its fugmucuty at (Ire suuturuutu(rms pressunre. or ansy onhner vzmpour pressurre correlatioms. ‘tIme prevaihning temmmperummuure ol 344.~onmpmmnenm C’ nrC.56 K. and 6.49) into Eq.5. Funrtinermore. — pure — u (3 49) The above approach.(3. line e. The lack of success of some equations of state in describing tIre volsuirmetric helnuuviour of complex liquid mixtures has lead to the use of tIme activity concept to determrmine fugacilies in tIre liquid phase. Eu’anmple 3.2. the proportionality constant slsould. i. = P (3. two widely used methods. Raoult’s law and Henry’s law.46) (. or for dilute solutions. Ij = wiscrc Pt” us tlme suutunrmutmonm (vmrpounr) pressure of the psure compounsl...4. = Hence.50) Eq.25215 (. Considering the above assummmptions. uunnul pure mneiiianrc cmmnmmot exist as liquid rut this icimipermuiuume. it can be concluded tlmat the Lewis nile is valid for mixtures witbm coefficients equal to unity.46) leurd to.37). to obtain the fugumcity of cmucln conmpouremrt in the liquid phase.5 I) us knowus mrs Ruuoult’s lmnw. I Icuuce.46) witln 1 all activity Eq.48) ‘t’lre dIed of pressuure on fungmmcnny of mu eonslensed pimase at low pressm.. Phase behaviour models which use an equation of state for tIre gas uumnd an activity model for line liquid phase may also miss the retrograde behaviour of gas condensmute systemrms.stnmnimuled vunluic of rnretinmmmse vmmtiouur pressure. using an equation of state. The split imnetlsod proposed by Clnmmo-Seadcr 141 has been extensively used in the oil industry to predict the phase behumviour of gmms-oil systenrs. i=l.3 K.2.(3.s fmrr sysleunis wills vapour and liquid phase properties far apart. including C~=t.suill.0025552 where the concentration is expressed by the nmrole fruiclion ~i The above equation is known as tIre Lewis fugmucity runle.(3.47) where Ki is called tlse equilibrium ratio and is defused mus the rustio of irsole frmuctimnir of component i in the vapour phase Yi~to that in the liquid phase Xi.N 3. Cmmnnnpumriimg Fu . lhc vmupouur fugaciiy at low pressure canm be mussumrrcd equutl to ils pressure.2. pure component.~.. An attractive ursstmnunpliomn is tlruut the fugacity of each component in mm’mixture is limnearly proportionmul to ils comncennlrmution.42) For vapotnr and liquid phases at equilibrium Eqs. At Imigh pressures. is gemrerally valid for immixtuires coimn moscd of similar 1 components. musing Rmiouult’s lass’. we obtain.5 I).0053k l”. Equilibrium Ratio 113 (3.10)). l’lnc fugmucity oh mu ptmm’e liqn.51) (3.c fromrs volumetric information.28)..1 ~ .3. Eq. it is only valid at low pressure for .3 K is well above the methane u imicuml memmmperummunre of 190.N (3. particularly at transfer line conditions. tIne cmnlcmmlmmied vmmimour pressure by ulme Lee. the hmqumisl ftngacity can be tmukeii equmuul to tine vapounr presstmre of time stubstance mit tine prevaihinrg temperature.. Suhstituiing Eqs. therefore.(3.112 fVyp4~v i=l.s. K =O f~°/P~ 1 1 (344) Asstunnminsg thsmmt time vmmpmrunr is mini irlemul guns.(3. mmmrsl nC 10 in a vapour-liquid mixture at 344. we obtain.43) xf. The fugacity can also be evaluated by simple methods. (3.. _~__ I’’ 7. i. is given in Clmapter 4.(3. where tlne vapour pressure at 344. the mmhove approacis is not recoumnimiended.757116 -5. he equuml to the fugacity of component i. 11681 Mi’a.39).e.S) is valid over tIre whole range of cotncemslrmution. is an unrreal value mmusd just an extrapolation of time vapour pressure curve above tIre criticmuh temperature.2: (‘mmlcuulanc eqnuilihrimnumm rmutios of (‘I. simsnilar to Example 1. gennermully provide more reasonable values comparing with cousmplex .. TIns assumption. the use of a single equation ofstate to describe all fluid plsumses slmould he adequmutc in mulnnost mull petroleum engineering problems. consider the case that Eq.1)7 0. ‘line funguucmties of sumlurnatesi vapour and liqumid are cqummml.40) and (3. ~I. In getrermul. 1-lenee..68167 ° -4..895MPun.. P/nose Equilibria .(3. uns time Iwo plrutses umre mit equmnlihrnunmum. employing limiting musstmnmptions.(3. as described us Chrupter 4. Solnitm on: The esluilihriunnn rmntmos are calculuited fronru Eq. (345) wisere Xj and C~ are the proportionality constant and the concenlrmulion of tIne comrrpomnent i in the mixture.rre is small III anti can he tucgledlcd.~ (3. Sinssple correlations.(3. f=zf. therefore. respectively. especially close to critical conditions. where the liquid and vapour phases behave sininilarly.Kesher equation. y~P=x~P~ tsr K=P~/P (3. we obtuninn. such as tIre Cox chart..simmrple unmixtumre.48) and (3. instead of Eq. as a pure substance. known as tlme ideal solution. known as the “split” mcthmod..N-lt’a I 16111.3 K is estmnrmmied unsung lIne t_ee-Kesler equmaiiomn. hunt still useful for engineering purposes at a variety of conditions.47). Using Eq. will result..( 1.


.5 l’fmosm’ Eqm,i!il,ria





I I 5

fumnctions that mnclunde parainmeters adjusted by mumtclning experinuenmtmml s’uupouur prcssumre data.
Figumre 1.3 shows muir extrapolated vapour pressure of 48.26 MPmn (7000 psimi) for nmrcttrmmmre

Ilenmry’s comrstmmmmt of mu coumnponenl in a solvent is considered to he independent of its eonccnrtrumtionr. html a fuinctionr of tenrrpcratunre, and to a lesser extemnt pressure. Henry’s constants for gmmseouis comnrponrenrts of reservoir hluids inn water, at low pressure, are given in Figure 3.2

at 344.3 K (160’F),
Suibstitsiting the estinrated vapour pressure valumes inn Eq.(111.51). tIne cmmlculancd cqmrilihriumnn ratios are as follows:

13000 12(800 110(8)




Experinrental values K,.=3.998, and K~(.,,=0.00271271. Henry’s Law ‘I’he proportionality of component fumguucity to its comrcentrmution, as assuimmncd ins Eq.(3.45) is valid for components mmt low concentrations in most liquid msmrxtures, l’m


Pro mumme —

cm 0 cm a


H X 1




where I1~is called flenrv’.s co,n.cta?i/, which is experimentally de(ernmnnned. The concentration of component. i, is generally expected lobe less tlrmmnm 3 tniolc ‘ e for tIre muhove equation to be valid Ill. It is, therefore, a tmsefuml equnmulion Its slcternnninc tire sotumhility of hydrocarbons in wmuter where time smlsnhilily is gemnermully low. At low pressure, where the assumption of ideal gas is valisl, Eq.(3.48) can he unsesl to describe fugacities in the gas phase. 1 which is known as Henry’s law. Hence. K =H~/P 1 Py~= iI,x (3.53)

70(X)’ 60(8)




F thane
— .



cm a cm





Figure 3.1 compares Henry’s law with the Lewis rule, Eq.(3.46). Note that wlnilst the fiuguncity of a component is proportional to its concentration across the whole rmmnge of comicenmtration for the Lewis rule, the proportionality is only linmited to the low concentration ramnge for ilenry’s law. The proportionality constants are generally different.

Lewis rule Counnpositimnn, x,
Figure 3.1. Comparison of Henry’s law with Lesvis rule.




340 360 380 Temperature, K




Figunre 3.2 llennry’s constants for soltuhility of hydrocarbons in water. Reprinned winh permission 161. Copyright (1953) Airrerican Chemunical Sociemy.



l’ha.se Equilibria

.C 2. Eqmmilibrinmnm Ratio


The dependency of Henry’s constant on pressure can be determined rigorously by
thermodynamic relations as, = H~’exp[vr(P—P°)/RT] (3.55)

where Hm°is Henry’s constant at ~0, and v’ is tIre puurlial nmolar vmniuirmc of comnulxrtneml( i ins mIsc solvent at infinite dilution, assumed constant over time prevailing pressure uunnd comnspositioum ranges. Eq.(3.55) is known as the Krichevsky-Kasarnovsky equation t51. Limited information on v~ofcompounds in water are available in the literature [61. The partial molar volume varies with temperature, and becomes pressure dependent near time critical point. 3 An average value of 35, 40, 55, and 80 cm /gmol, can be used for nitrogen, nurethuitne, ctlnamse. and propane respectively. Example 3.3. Estimate the solubihity of methane us water at 373 K, amid 65 MPa using ilemury’s Iumw. Compare the result with the value shown in Figure 2.28. Solution: The Henry’s constant for methamse at 65 MPa is calculated fromnr Eq.(3.55): 3 At T=373 K, H0=6.5xi0 MPa/mol fraction (Figure 3.2), and V’=~.IOMPa. Hm.m(6.5X 10’ MPa/mol frmmciion) exp[(40X hO ‘uns’/kgurrol )x) 65.t)0-O. I 0)M Pmm/ 5 (0.00831 44x373 MPa.m /kgmol)J

components at a certain pressure known as the convergence pressure. Figuure 3.3, This appemurs to suggest that, the consposition of both phases should be the same at the convergence pressumre. As similarity of hotim phases only occurs at (he critical point, it implies that for any petroleum fluid, the critical temperattmre may be selected arbitrarily, which cannot he correct. ‘lire fact us thnat tine comrvergence prcssuume does not pimysically exist, unless the prevailing tennperahuure is the nsnixture critical Iensperature. At other tensperatures, the nnixture will be an under satunated single phase at that pressure. It is however, a very useful parameter to con-elate experimentally determined K-values with pressure at any given temperature as an end point.


0 a

I .4378x I o~ MPaimoI fraci iomn.

}~J~t{1 ~ — .1-~— ~ ~fl1~ -~
~ ~-.


— -—











cm’ 00

The solubility of methane is calculated usimrg Eq.(3.52), 1~m~ = l’Ycu4~i= The gas can be assumed as pure methane due to low volatility of water relative to methane: Ycn=’’ The fugacity coefficient of methane vapour nit the prevailing conditions can be calculated by an equation of state as appliesh in Example 4.1. Assunniung ~ we obtain, f~=P=65MPa= (h.4378x10 4 MPa/mol fraction) x

~~I1ll~ Ii~NJi! ~


‘~\1H}~J ~ f_
~ ~





‘~, —‘-


~ ::,





mole fraction of rrsethane in water.

Pressure, psia

The solubility value is read from Figure 2.28 equal to 4.3xlO’. Empirical Correlations In spite of recent developments in theoretically based phase behaviour models, empirical K-value correlations are still used in vapour-liquid equilibrium calcuilmulions, pmurticularly at low and intermediate pressunre conditions, where the K-value cams he mrssumssed independent of tIre mixture composition for reservoir isydrocarhon liumisis. It is well established that, for a multicomponent mixture, graphs of experimentally detemmined K-values versus pressure at constant temperature tend to converge to K = I for all the 1 Figure 3.3. Equilibriunmim mmutio.s of a hydrocarbon mixture at 322 K (120°F). SPE-AIME Copyrigbni. Reproduced fnnnn 171 winlr permission. l’he preslicted equmilibriuurn ruttios, usiung Raoult’s law, Eq.(3.5l). are also shown in Figure 3.3. As the systemrm tenrpermmlurc is conss(usnt, hence, tire vapoumr pressure of all (Ire components, the lmsgumri(lnmnrnc plmrts of tIne K—v:ulumc.s witis pressure are all parmullel straight lines witis a slope of — I, as deterrmmimmed by Eq.(3.5l). lIne deviations of predicted values by Raoult’x law grossly increases at high pressure commditions, particularly where K-values tend to increase with pressure as opposed to Raoult’s law.


1 P/name Liinninb~ ma

.5.2. b.qnuihhrium Ratio


For a binary system, the convergence pressure is tire critical pressure of a nrnixltnre wlniclr lrmrs mu critical temperature equal to the system tenmperature. The compositioim of sunclr us umuixture is different from that of the system under consideration, utiless it is at its critical teursperaluire. Figure 3.4 shows the pressure-temperawre diagr~mof ethane-nrormmsi Ireplmmnie nnnixlumres mit different compositions, with the locus of the critical points identilned by the slotted cturve. At 450 K, for example, the convergence pressure is deterrsnined to he equal to 8.23 MPmr for all C -nC mixtures regardless of the composition. The composition of equnilibrated phases. 2 7the equilibrium ratio, at a pressure-temperature condition do not slepetid on the irnixtuic hence, compositions for binary systems due to the plnase rule, Eq.( I .2). ‘lIme genmerumlesl K-vuulimcs nm any binary mixture are, therefore, valid for all compositions.

wisere KCI and KC2 are the equilibrium ratios of methane and ethane in the mixture respectively. l’Ise Iladden rtrethod of calculating the convergence pressure treats the mixture as a pseudo hiisary system composed of the Iiglrtest component, and all other components grouped as a simrgle iseavy pseudo comnipomrent. The pseudo component formed by grouping will be, therefore, different for vapour mund liquid phases. Iii (Ire GPA method the convergence pressure is the (Sine calculated for the liquid phase. hence, the calculation of convergence pressure is iterative, except for bubble point calculation, because the liquid composition is not knrown in aslvance. ‘lIre cuilcuilmution proceduure, as sumggestcd by GPA 1101. is as follows:


,,monesn cilia,,,4
mlii me 2 ‘5585 .5 887! 4 7709 S Ssin (, 25.54 7 00

(I) (2) (3)

8 7

Assunnmne ttse lis unid plrase cotmsposition, or use tIne feed cotnmposition in the first trial. 1 Select tIne liglutest luydrmst’umrhotn compssmlent. mmrcttrane alnmrost in all cases., which is Cmslculmrte the weighted urvermuge critical temperature and critical pressunre for tine

presemrt umt least 0. I nuole % in One liqunid plma.se.

remaining hemsvier commrponents to form a heavy pseudo component. (4) ‘Irmuce tIre crinit-mul locums of lIne hinmuury consisting of tIre light and pseudo heavy connuponent on Figumic 1). I (Appendix I)), by interpolating between the neighbouring critical loci.
(5) Read the convergeumcc pressunre mut time prevaiiinmg tensiperature.


((r) Obtain K-vmultmcs for tlue systenr components from the K-charts corresponding to the estimnrmitesl convergence pressure. (7)

Calculate line equilibrium conditions and determine the liquid composition.







Tcuu,pcranucc. K

(8) Repeat steps 2 throsngh 7 uumtil the assumed and calculated convergence pressures check wi(hin an acceptable tolerance. Winen tIre calculalcsl consvcrgenncc pressure is hetweemr lime values for which charts are provided, interpolmutioms between charts uurmuy he tueccssmmry. Clearly, a reasonable interpolation can only be cxpccted wlrens tine rpcmumting pressure is lower Iluans (Ire convergence pressure of lire two charts umscml for interpolmmtioim. Plsmsse eqmnilibriunnr calculatnomrs using K—values will be described in Sections 5.1. (it’A K-vuulnnes ismuve been fitted to funsclionrs of vmmrioums forms for computer calculations 111.1. ‘rIme K-valumc of tIre C fraction (nf mm oil irsixture earn be estimated by various methods. A rule 71 of thumb [7~ smuggests mu vahime equmul to 15% of time C . It can also be estimated as equal to the 7 K-value of a Imydrocuirhon conspounmmd, or (hal of a single carbon group as described in Chapter 6, wills tIre smmnne specific gravity or molecunlar weight as that of the C . 7~ In Clmmrp(er 6 on fluid clsaracterisation, various nsethods to describe the C fraction, and to 74 eslimmmuntc its properties are proposesl. It is nmsore appropriate to describe the C fraction by a 74
nunnrher of pseudo c(rtrrp(rnents. However, tIre following correlations may be used to estimate nIne critical properties of the C frmsction.

Figure 3.4. Detemmination of the convergence pressure for a hinmurry mixtunme. McGraw-IIIII (‘oummpmunics Cm~pyriglnn. Reproduced from 171 wimh perunnissionn. K-vmmlm.mcs in multiconssponent hydrocarbon systems mut inigh pressure depenrsl on comnmpositionr. A comrmmon assumption is, thuut the convergence pressure alone can remrsomsmuhly describe tIme mmhovc depcnsdency. I knee, equilibrium ratios are often correlmuned mus ftunctioin.s usf lIre pressure, teimuperaturre and convergemmce pressure. Tlnerc are a nummsher of corrclmutioiis lun cslinsmuu(e time cquunlihriunm ratio 181, and different methods to calcunlate the convergetsee pressunre of multicomponent systems in the literature. Care slsould he takcnn to use the smmnne metlsod of convergence pressure calculation as used in the development of the K-valume correlmrtiun. TIme Gas Processors Associmmtion its 1957 presented K-value graplsicmul corrclmutiomis for nmrraffirs,s 1 from metlnane to decanme, ethylene, propylene, nitrogen ansI carbon dimnxisie, using tIme convergence pressure calculated by the 1-ladden nnetlmod [9]. The K-charts lrmsve been revised since frequently. The 1976 revised cimarts for convergence pressures of 50(8) psiut (34.47 MPa) [10] are given in Appendix D. The equilibrium ratios of CO at low concentrations canm 2 be estinmated, within ann accuracy of±10%, as,

(KC,KC. )03 5


7~ Standing [121. represented tIre grmmphical correlation of Mathews, Roland, and Katz. [13] as,

338 ÷202 x log(M~, —71 .2)+ (1361 x IogM~ —211 I)1ogS~



3. P/mace Equilibria

8.191 —2.97xlog(M~, —61.l)’s-(S~ —0.8)[15.99— 5.87 x log(M 5 5

121 3.2. Eqnmilibriuuun Ratio it and tinat of C-nC, (kensol), wInch results in a coirvergence pressure of about 41.37 7 MPa (6(8)0 psimu) at 325 K (125 .3’l). K- Value.s at luter,nediate Pressures At pressunres below 7 MPa (1(8)0 psium), the effect of mixture courrposition on equilibrium ratios of isydrocumnhonss is not significant, mlmercfore, K-values can be correlated in terms of pressure and temperalture onmly. Stuundimrg 1161 correlutted (he experinusemstuml K-valuues of Oklahomsma City crude oil/natural gas suuummplcs gcmncuumlcd Iry Kunli, uunr(I I lmuclnminulls 1171. musing Fm .(3.59) proposed by Hofftnann ci nil. 1 hl8l.
log KP
= =

where T~, and P~are in K and MPa, respectively. Other correlations to estimate the critical properties of the C ÷fraction arc also available 7 [14,151. Example 3.4. The composition of an oil sample and its equilibrated guns. at 10.45 MPa armul 125.0 K. mire given in the following table. Component CI C2 C3 1C4

mole Gas 82.14 11.22 4.06 0.42 1.07
0.24 0.30


Liquid 27.36

r~’ +


ha’ (



h 2

(3.59) (3.60) (3.61)




10.93 8.56 1.46 4.73 1.77
2.77 3.87 38.56 S=0.8399


6.53x 10 I’ + 3.1 6x 10 I~


0.890 — 2.46x10 7 P


tm 2 P

C6 0.21 C~÷ 0.33 C7 Characteristics M=210 4

wlmere P is pressure in MPa, and T , (normal boiling point) and T are in K. a’ is time slope of 1 tire strusiglst line connecting tine criticuul point and the boiling point at atmospheric pressuure, Pa. 1 on a log vapour pressure vs. (T) plot.
a’ =

Calculate the convergence pressure of the liquid phase at the above conditions.

[log( P / P, )J // [I / Tb — I / T ] 5 5


The critical properties of C -C are read from Table A.l in Appendix A, and mlnsmse of C~, 1 5 are calculated using Eqs.(3.57-58). It should be noted ihat C is not msormal Inexane, hut a 5 group of compounds with boiling points between those of normal pentane mumrd msormal hexane. This subject is described in Chapter 6, where more appropriate critical properties for the hexane group are introduced. Methane is selected as the light conntr(rnent. with the rest grouped as a pseudo heavy component based on mass weighting, as follows: Component I2quation C 1 C C 3 IC 4 nC IC 4 3 nmC, C C4 75 Total

1~ 1 The plot of log KP vs. a’ ( fb- /T) for conrmponents of a systemsi at a given pressure often formsms a straight lure for inlernnmedimnlc atrsi heavy frumctuons, as showms in Figuure 3.5. Standing nmodilied vmslues of a’ mmnsd l~,for nmrclhane mmmd etimmune munsd unon-irydrocarbon coismpoumnds to lit tIme same straight line mus other comsnpounenrts. The values of a’ annd Tb are given in Table 3.1.

16.043 30.07 44.096

T,, K 190.56
305.32 369.83 408.14

P~.MI’a 4.599
4.872 4.248 3.648


w, xM,I~. x,M, 2 0.03344 0.1)3842 0.0(1864

r K 1,.,w,.
1(1.211 14.209 3.526

MPmu 1’~,’x,
0.16293 0.16321 0.03151

0.1093 0.0856 0.0146


58.123 58.123 72.15 72.15 86.177 2t0.0


425.12 460.43 469.7 507.6 691.2

3.796 3.381 3.37 3.025 1.812

0.0473 0.0177 0.0277 0.0387 0.31156

1)02801) 0.01302 0.021)34 0.03392 0.82422

11.904 5.993 9.553 17.218 569.732 642.35

0.04401 0.06854 or

(1.10261 1.49363 2.173 a(rrr -nrr) 5 Figure 3.5. Equmilihriunmrn rmutios mut 5.52 MPms and various temmmpermnlurcs. SPE Copyrmglun Repmodumccd tronru Il 6j wimh perurnussummmn.

The heavy pseudo component with T~~642.35 K (696.56 ‘F) and P,=2.l73 MPa (315.2 psia) is slightly heavier than flCn,. as located in Figure CI. The locus of critical poimsts of methane and pseudo component is drawn parallel to that of Cn’nCni. interpolating between

with a molecular 1 of 212 is considered to reprcsenrt C .4. with tIre vapour pressure related to the critical properties using the definition of the acentric facor. usinrg Eq. hut for a constant acentric factor of 0.2.6. with a 7 weight nrornral alkamre with tIre same nisolecunlar weight.340 MPa. eilher neglecting the effect of mixture consmposition [20.63) mmnd Fs . the equivalent carbon number of 46 2 C. using the Standinug nnnetiuod amid the Wilsuin equation. Table 3.8. depending on the fluid. )(l 5 — T5 IT)] (3. .(3.59) at 10. .539n 2 where n is the number of carbons of the nornmal paraffin that has the sanrme K-value as tlmmul of the C + fraction. as initial guesses in flash calculations.63) (3. n = (P 5 /P 1 )‘5 ‘(P / P)exp~5. 1 The coefficiemrns of Eq. Standiimg correlated n for tlse Oklahoma City crude oil samples by. it Irums been sirown to be reliable for crude oils from various regions of the world.45 MPa are calculated as.67) wlmere Awl -1(1’- 3. is deternmnimucut cqnnal to 10.Rutane 999 1132 1196 231 262 273 iso-Pennanc n-Penuane iso-tlexanes n-Hexane Hexanes (lumped) n-Hepnanre n-Ocuane 1316 1378 1498 1544 1521 1704 1853 301 309 335 342 339 372 399 Estinmrane cquuilitmrimunn ratios of tIre guns-oil system described in Example 3.5 2. 211 or using a single parameter such as the convergence pressure to characterise the mixture 122.(3.)(i — T . 5 (P / P)exp[5. and w=0. !~xatun pie 3. K Nitrogen 261 61 108 362 Cartxnn Dioxide Hydrogen Sunlphide 63l 184 Menhane 167 52 Euhane 636 168 Propane mmnsd Pk is tIne comrvergensce pressure. using Eq.60) 3 = Alnhouugir the equilihriuimm ratio correlation was based on a limited nunrrber of dmmta.(3.5 and 0. using its specific gravity and nrrolcculmrr weight.(3. mis correlmmted by Stmmnding [12].5526.364n = .01. wlniclr results in (X’22l 3 K and Tb= O.7697. l Mç 29.(3.68) wlncre i’k is ins MPa. Wilson Equation ‘flue esninnmation of criuical properties of a pseudo component.25n -0. I in Appendix A.231 have also been developed by various investigators. The equation has been extended to higlser pressures [22] as.85+ 0. ‘rise expurnremnt n varies between 0.067465. Connpare the results with the experimental values.9).2. umsimrg Eq. P 1 44 0. iso-Butane n. r~’=0. = 0. These correlations would be mainly valuable in generating initial guess values for using in an equation of state to calculate fugacities. Values of a’ and Tb for use in Standing’s equilibrium ratio correlation.- where T is in K and P is in MPa.. Table A. The critical properties of C. It can be estimated by cotnmparing tire molecular weight of tIme C frmuction 7 74 with those of normal paraffins. IT)] 5 (3. K = 167+33.122 The values of a’ and Tb for C + fractions can be obtained from: 7 2 a’ = 563+ l8On .I in Appendix A. as described in Chapter 5. (3. P =l.5 P/mace Equilibria .62) The results are given in ihe following table. is equivalemrl to the above. therefore.5. Staumding Correlauion Suhsmimuilinng tIme pressure amnut tempermnluire in Eq.65).=736 K.0I35T + 0. respectively. 7 esimated equal ~mT. with us sicfmuult value of 0.5 MPa (500 psia): K. Equmhhrusun Raiuo 123 TIme Mollerup equation[211 to estinnrate K-values.. K Cummpound a’.Solum (tam: n-Nonane n-Decaume 1994 2127 424 447 The critical properties of C. C.64) The Wilson equation generally provides reliable estimation of K-values for sub-critical consponents. The Wilson equation basically uses Raouilt’s law.( 1. . huut overestiurmates those of the supercritical components (24].. is described In Section 6.66.-C are read from Table A. Other generalised K-value correlations. Eq.. A simple approach is to represent C . In mInis case. are calculated as follows.0 (3. The properties 5 unf C~. Tb. sonune constaining ssmbstantial amounts of non-hydrocarbons [19].1.65) P~)/(P. are.64). The urhove modification to the Wilson equnation may lead to unrealistic values resulting to non-convergemrce in plmase behaviour calculationrs.2321P (3. Wilson [20] proposed the following equation to estimate the equilibrium ratio below 3.37(l 5 + w.37A(l+ 00. K.66) where 00 is the acentric factor and ‘F~ansd P~are the ahsolunte criticuul teurspcrmttunre mmnd pressuire respectively.(3.

0 .. munrd Vmuus Ness.1731 K.0 0 . Snurimln. to 4. The iloffmann or Wilson plot is thus a good tool for checking the integrity of the mmmeasuremenrts. Anu.8 -0. . Component Equation C. 598-605 (Dec.~ Hoffmann Plot ‘C ..01 . TIme results clearly indicate thrat the correlations igimoring tire compositional effect cmumummot provide relimmhle estimates of tine equmihihritnmnr rmltio at isigis pressure conditions.00(15 0.: “A Gemmeral Correlations of Vmipour-Liquid Equmilibria in Ilydrocarboim Mixtures”.6.60993.4601 1.0 log(l-TblT)/(l-T~) 0.5 -0.M.5947 0. lR amnd Kmmsumrmsovsky.6 . mIne Wilsous dtummnlion. Figure 3. 0. K~..474’) 0. E.0 ~3 Modified Wilson Plon 2.. J. l’/.4170 .2268 (1. with the value of A=0.0274 (1. and de Azevedo. AICInE J. NJ (1986).0 0 0’ n11 0.1478 0. The calculated equilibrium ratios using Ihe Standinng menirod.4 3.4 -0. 1111)1 (1.66 4. Clsensm. 2nd Edition. Liclmtentlmaler.0 3. TIne vmuriation of K for each comsrponent is solely due to clsammges in the 1 ursixture composition by gas c(rnlaclinmg oil.~ 3. which uses the acentric factor.. mire cormrpmired with tIre e. more closely than that of the Hoffmann method. McGraw—I lill (1975). J..5.2727 0.•• 0 0 o~ q° cm 0 1 00 ‘PG Contaci Smage or 0’ Note that although the pressure is above the working range of the Standing correlation. Soc. Altisouglm tIme data at Inigln pressure mnmay umot fall on mm straight line. a: . ‘lIme measumred dmsta at umny overall consposition can. 3.(3.3 REFERENCES 0 Prausniti.1)874 0(1088 0.1)693 0. any mmseasured point tisat is completely outside the general trend could be suspect. Measured equilibriums rmmtios in a test simrmulating oil vaporisation by methane at 34.0086 me: C 0 .4 -1. general. All the above K-value correlations can be used to check the interrsmml consistetrcy of mmreasumred equilibrium ratios.1454 0. it predicts the results more reliably than others. (I + (0. 1292 0.1)162 0.ce Fqniilmbrum . be represensted reasonably by a straiglmt line. K.M.2 0. Equilibrium ratios of intermediate compounds of a gas-oil mixture at 20. TIme modificatious Immus inrpnsved the Wilsurn equation in. ThI’ [25] mind the mniolecular weight 1261 have also been proposed which can be used to evalumate nnscmusured datum amsd estinrnmmte equilibriuns ratios. )(I — T. 4. No. Clmmro. / T) at coisslmmnt pressuire Ior initenmscdimmte compounds of an oil sample.~. aimd Seader. un the following table. -0. K.2 0.59 3.4 -0.0 ‘.001 -2 —l (t+tO)(ilITr) 0 Figure 3. A straight line can clearly fit the data. C 2 C 3 iC 1 nC 4 iCm nC 3 C 4 C .1 . Prentice-Hall Inc.58 MPa and 373K. .6666 (1.. K 5 52 168 231 262 273 301 309 339 460 K 5 3. 1961).549(1 K~ 3.0539 0. Other linear plots between logK and component properties 1 2 sumch as id .68). K.644.1)499 0. ‘lime equmilibriumnn ratios of consponemsls of am oil measuired in a test..3245 0.7.9 -0. Krichevsky.124 .8 -0.0. one would expect them to follow a nronotonous trend. 7 a.94 MPa. ihuird Edit ions.2.. by the Wilson method.1686 0. Vol.79 MPa and 373 K. and the modified Wilson equation. 2669 (1.0 . 57. including non-paraffins.01)22 1. Figure ~. equal to 57.C.1517 1)2855 (1.G: “Molecular Thermodynamics of Fluid-Phase Equilibria”. JS:”Thernrodynansical Cuilculations of Soluhilities of Nitrogems and Hydrogen in Water at High Pressures”.a. I iC: “listrodunction ‘l’lmernnirdymnaunsics’’.~. 10 Clmennicurl Fnginseering a ~ Miciselsen.01)57 (1.67 K.7. Therefore.0661 0. 2 168(1935)..’uperiusseuntmul vuilues. Equmi!ihrimmnn Ratio 125 The convergence pressure for the modified Wilson equation is cimlculmuted frurnn Eq. irowever.6 compares the Hoffnmann plot with that of mnodilned Wilson plot. ML: Private Conrsnsmunications. 5. 3D..7 (t#0))(l’lIl’r) -0. RN. K 167 636 999 1132 1196 1316 1378 1521 2214 T. sinrsulumting oil vaporisuition in reservoir by usmethumne iunjection us tlnrcc contuuct stages at courstant pressure aumd iennperature.0207 0.00(8) 1)32911 11. except for predicting the equilibrium ratio of nretlsamrc.u 02 01 . K.6 -0.. 7. where log K~ has been plotted vs.4 4. ale shown in Figunre 3.1626 0.1351 0 ci 0 0.

45 MPa and 324.29. J. Glaso. 343348 (1992). Gulf Publishing Courspany. Emsg. Kohayashi.41 (1942). Eng.. 198. 4.. J. N: “A Robust Prediction Method for Rapid Phase Behaviour Calculations”. D. Whitson.nnotc%Gas~qwd C02 7(1.R: “Equilibrium Constants for GasCondensate Systems”. 440 (1953). SPE 16943. Cmnmnrphcll. Conf. 19. No.41 CS (523 059 . ammd Todd. I I . at the 53rd Ann.: “Phase Equmilihriuunnr Calculationrs. 8. DL. Lawal. R. Proc. 1193-1195 (Sept. W. 22.ilationm wills Interplmunse Mass ‘I’nmunsk’r”. JP~F 1811-1813 (Aug. . AIME.I plummscs of ur hitrmury nrsixttmre are at equmilibriuns at T=300 K and 12 MI‘mm. Cli: “The Accumruucy of PVT Paramsieters (. Proc. W. Use Raoult’s law.4.31 271 (‘7+ (5.5. 25. Xn. Oklahoma (1980).. Trans. 1526-1531 (Dec. the Standing method annd the Wilson equations.N: “Pirase-Equilibria us Hydrocarbon Systems”. rcspectivclv. 45. 1942). Clmem. 3.I 26 . 13. Dmmllas.69 (las conrp. 24.. (Oct. Oklaluonnmu (1976). IF!: “A New Correlations of Vmupour-Liqunid Equnilibriummns Ratios Internally Consistent with Critical Behaviour”. Mathews.8382 18. A. Sage.. 17. 9th Printing. and Hocott. and Tou’p. No. kglm’ 765.H. [Kohn.q.949 amsd 0.11. DL: “Vapour-Liquid Equilibria for Binrary ilydrocarhoms-Wurler Systenms”. Vol.E. 34. Comrupniners Clmenm. 10..31 072 nC4 I) 88 2.H. C. respectively..‘mulcuuluuted fronrm Computer Flash Separation at Pressures Less Tlsumn 1000 Psia”. 21. tnd.578 Lig. Series 49.. A. Fall Tech. Counpare the results with measured values. Pres. Con~pomncnu. S=0. tIme Stamsding metlnod.9 C’7+ Ctuaracuerisnics. SB: “Evaluating Constant Volume Depletions Data”.59 (113 (‘I 18. I & EC. S. and Silberherg. of 62nd Ann. Conf and Exh. ed. SPE. 20.M: “Gas Conrditiunmninrg ausd Processing”. Dammesh. Crump. 1072-1077 (193. TA.45xI0 P—6.Fng’nmg. ‘I’hc connn~nrcssihiIityfmnctor of comrrponcust I as a pure gas at 300 K cmmn be related to its pressure as. and Whitson.H: “Vaporisation Equilibrium Constants mm a Crude OilNatural Gas System”. Calculmste tlre fugacity coefficient of component I in the liqunid phase. 2 2 Z=l—5. 431-439 (1993). presensted at tlre AtClrE 65tIm Nationrmul Meelinsg (Mmuy.F.T: “Convergence Pressure in Hydrocarbon Vapour-Liquid Equilibria”. 1..2. 7. Fluid Phase Equilibria.(3. J. Katz. 3.093 MPa.uilibria 3. C. Chem. Roland. Eng. Texas (1981). of 56lIs Ann. NGAA. SPE 10067. MB: “Volumetric umnrd Phase Belrmrviour of Oil Field llydrocmnmhons Systemsss”.15 N2 0. mind nC is fimnslscd at 423. and Hachmuth. 27. and Katz. Connf.98 5(1. Application to Getreral Plsysicmd Duuma Calculations”. Cannpbell Petroleum.B: “A Set of Equations for Computing Equilibrium Ratios of a Crude Oil/Natural Gas System at Pressures Below 1000 Psia”.. 12. Predict the equilihriuum ratios at tine above conditions using GPA charts. 1-3 (1978). Gas Processors Suppliers Association. l’ha. (Oct. IS. SPE Res. 14. (Sept. MacGraw hlill (1959). amrd Lacey.-H. D.. AS.ce F. 16.8 K are given in tIre following table. D. tIre Wilson 4equation and the GPA chart to predict the equilibrium ratio of muretlnmmnre aurd nornnruul clecanme at tIre umbove condutmons.1. Ahmed. 3. The University ofTexas at Austin (1971). dcnsiny. What is Easy and What is Difficult?”. Conf. 1981).18 726 (‘2 5. Standing M.4 EXERCISES 3.MacDonald.9990 munsd 0. C. A mnnixture of C. 12. D. Proc.2500. Hadden. AC: “A Grouping Method to Optimise Oil Description for Conrposilional Siniunlations of Gas-Injection Processes”. of the Society of Petroleum Engineers.mr 0. 9. SPE 10287. Katz. and Katz. 7.C5 ((32 5 St (6 ((. Standing. T: “Hydrocarbon Phase Behaviour”. J.n. UT 71-2. Texas. 1982).. D:uta.229. l!ounston. The measured couurposition of equnilibrated vaporur and liquid phases at 10. SPE Paper 7475. 1-10 (1953). G: “A Modified Redlmch-Kwong EOS. JPT. Emsg. Referent-e. Prove Eq. 1968). 26. 1979).35) tine vuupotnr uunnd Iiqu i.C: “Reservoir Simn. 23. Proc. llounston (1989)..3. Wilson.16 39’) 245 378 (‘4 (1.59 26. 9. (1964)).. Report No. 53-66 (1953). Miclselsen.35xl0~P where P is in MPa. M~208. etal: “Handbook of Natural Gas Engineering”.. Vol. Hoffmann. 1981). TIme measured mole fraction of methane in the equilibrated gums and liquid ptrases is t).P. 3. l’ulsa. Ml.1 K amnd 7. iS. AM:”lntemally Consistent Correlations for Predicting Phase comrrpositions for Use in Reservoir Compositional Simulators”. Rowe. (‘tsemsr. I 7 No.3. R. Paper No 15C..7). ML: “Calculation of Phase Envelopes and Critical Points for Mimlticotnsponent Mixtures”.. Voratsis.: “SI Engineeriumg Datum Book”. 1-10 (1980). ‘I Inc nnnolc lrmmcl ionr o I cm nnrnlrtsnucnnl I mnr line equmiI ibrumtcd gas ammd liquid piruises is 0. 5. Michelsen. Symp. Ind.L: “High Pressure Gas Measurennient”. of 56th Ann.c 127 6. 3. 5/6. Eng. Iacu.. Bradish. 1987). Cheiss. OS. Oct.

.~)n. ln4. defiured mis tlsc rumtio of fumgacity to pressure. to imc tIre requireunsemsl for u.. any equations of state which provides reliable volumetric data over the full range of the integral in Eq.5. Ins genermsl. be determined from the above with the aid of an equations relatimmg pressure. Several types of EOS have been suuccessfully applied to hydrocarbon reservoir fluids.N (3.3l) can be unsed to describe the fluid phase behaviour. 4r ..(3.~ Ri’ V l. . an equation of state (EOS). of each component in umtly pisase is 1 related to pressure. temperature ammd volutne by Eq. volume and conspositions.128 129 3... ‘lIre fumgurcity coefficiersi. —RT/V dV—lnmZ i=1. that is.j .(3. Assume (he gas fugacity coefficients equal to one.)~vnj.3 I). in Chapter 3. An equi-molar binary gas mixture composed of etlrane and C02 is us equilihriumss witln water at 350 K and 30 MPa. ±. temperature. and use Henry’s law to estimate the gas solubility in water.’Incmsuical equilibrium ium mntulticonsspomrensl systems. therefore.31) The fumgacity coefficient can..2. 4 EQUATIONS OF STATE TIme equuality of funguncily of emiclu conrnpomnemst tlsroughount all pisases was proved.

v and p are the molar volmunne and tIme nusolar density.528629 = + 0. the equation can be applied to the vapour phase only. and depend only on temperatunre for eaclm compoumnd. in conruparison wulir tire vmrnr der Wmmals type EOS. It is. 356306 + 1. due to their large numrnher of paransseters. anrd canm he expressed ums an infinite series of either molar volume (molar density)... wirere a single equations of state is to describe the behaviour of both vapour and liqunid pisases.ero.3.3) +~s!. the higher terms become more significant muumd cannot he ignored.504087 + = R’l’ = 1. Sinsuple nlumxinsg muiles. 5.322450) = 0. ‘I’lmis subject is described in Section 4. valuable tools to describe volu.. More conmiplex msnnxnnmg rtmles. and P is tIne pressure. For exausmplc. stmclu mis tisose Ilsal unssummne comnpounuls are ruumsdonrrly distributed wntlsun tIre mnnixtuure.0705233 . its spite of their conmplexity. very useful in showing guidelines for applying setni-etsipirical EOS to mnmixtuures. or pressure..+ (lI~I.115449o = 1. They are. sotrse with reasonable success. the equation has beets revised and nnodified by numimerous investigmmtors. hence. The equation reduces to Z=l. are called tine secommd. Nurmrerous theoretical and experimental studies on deterimiinatioms of virial cocfficiemsts.WehhRtnhinm EOS (E1WR) [I) is an empirical extemssion of the virial EOS.28438 0. tlsird. Amongst tlsese equations. valtne to reservoir fluid studies.c 131 The simplest. mms will be described ins lbs clrunptcr.270896(0 . us tIme semi-enrpiricuul vans dcr Wmrmuls type EOS with two or three parameters. Starling Modification of Benmedict-Webb-Rubin EOS (BWRS) lIme l3cncdicn .8(0) p~h = 0. as the virial coefficients can be described rigorously for mrmixtures using statisticuml nrsechmumnics.1) 0. = 0.544979 -0. tlse third and Imigiser terms cuun he neglected. mostly the second virial coefficient. = 0.7087 ho Z= I + B/v + C/v 2 + Div 3 + (4. I’ p 51 RT (lt. As higlr order coefficieusts arc hard to determine. + ~ ~ )p~. wlsen pressumme approaches 7. Otlncr equations with many parameters have also been tused to describe (Ire plrurse heirmnviotmr.A.1 VIRIAL EOS AND ITS MODIFICATIONS = The virial equation is based on theories of statistical mssechmmnnics )2).s..-.dificumliomr of lIme Benedict-\Vclrb-Rubin EOS as proposed by Starling [3) witis II pmrrmmmmseters Imuts heeur mupplied successfunlly to petroleuumn reservoir fluids.) 2 T wlucre PM is tIre molmmr dctrsity uunrd tIne II coefficients can he evaluated from the following genre rmnl i scd equnumt n ours: p~U. which is an empirical extension to tIme virial EOS.349261(i) 0.Sh. svlncnemms (‘ is tluan for tirree nrrolecules and so onm. etc. B. 4. ‘lIne mnsixinng runlcs mrre comnsiulcmi’d 10 dn. and higirly successful equation. or nmetlmanmol which is sonmetumnres mudded to rcscrvsir fluids as a lsydrate inlsihitor. therefore. The coelficjenst B muccounnuls for tIne itrteractiomr between Iwo mmmolecrules. if tIre effect of a tlmird ummolecule (run tIme prevailing forces between two molecules can be ignored. Al tlmouuglm tlsermodynaimsics ngoroumsly describe tine equilihriuunss conmdnl ours ummrd relmulc tluennm to volumtrrctric data.l~l.’scmitrc tIme put’vmnilinmg lonucs liu’Iwcu’mr musolecules of duflerctst sunhstances formsning tire mixtumme. lmngim llexnbiliny.484011 + = 11.().463492oo (1. tire Bencdnct-Wehh-Runhins (BWR) typeE I]. have been reported.(I ÷yp~)exp(—’yp~.022143(m) cxp(—3. can he uupplicd to boIls liqumid amsd vapour phases of reservoir fluids. C. Fqunationc of state mmrc hasicmully dcveloped for pore curnrnl)ourcnsl.(e 4. (4.920731(n) R’1~. and so on.. that is tIne ideal gas equation. A nsrm-.2) t).0732828+ 0. D.0307452+0. 2 3 Z=l+B’P+C’P +D’P +. however.(3. of little RI’.. however.130 4 Iqs~i(ic’ns of . Since 1873.mrretric hclu:mviotmr. mmmc (lumIe mrdcquumnle Ru descrnbc irydrocarbomm mrmixtures of reservurir flunds. when vats der Wauuls iussproved tine ideal gas equal ion by including parameters that represented the attraclive anrd repulsive inslermnnolecun lumr forces. These equnalions provide no additionsal reliuuhility its plrmmse hetsmmviour studies.+ or. respectively. As the fluid becomes nmore dense.443690 + 0. virial coefficients. ums given by Eq. Virial EUS and ill Modmfleotio?u. lsowcver.006450 — 0.754130o where Z is the compressibility factor.. RT’.044448m 0. 1mm :mppliu’d to nrruulnmcmsnusponenl sysne’mnrs by ennnploying sonrmc nnnixnnrg mules to mlctcrnnuinre tlucir pmmn’anmut’tcn’c for nmixlumres.179433o (Z=l+BpM+Cp~+Dp~. 0. it is tIre cmmpurhility of EOS mmmsd tIre mmssocimutcd mmsixinng rules Ilnat determines tine success of phase equuilihriunsr prediction. pmurnicumlmurly of pumrc conmpounds. fourth. It is. mm - + u(a + (4. which is present in reservoirs. urre required to represent the iruteractuon between lmydrocmmrhons mmnd musynmrnnclric conmspoumusuls suuclr as water.3 I).

e. N N N 0~ (P+-’)(v—b)=RT (4.nld. corresponds to that of liquid.g. At a tensmperature above tIme critical point. The predicted volume within the two phase conditions. I in Appendix A. More importantly. respectively. (4. including v~=( I/PM~)~ for pure compounds are given in Table A. h is mulso considered as an apparent volume of the molecules and called co-volumsse. Voluimmctric tsclnmtviotir of l’°~ coisspounmd as predicted by cubic FOS of vumms der Wusals type.3 \Critical Point \\ \ van der Waals improved the ideal gas equation by considering lIne inlermsrolectulusr attractive and repulsive forces. A aP 2 (RT) vi 52 vi (4. the molar volume becotnes equal to h. tIme 2 equal ions provides only one plmysically acceptable roust: For the critical isotherm.8) Hence. As the pressure approaches infinity. it has been surpassed by the siusspler. The choice of mixing rules often has a more pronounced effect on the predicted results.4) P1 N N. for multicomponent systems each parameter must be determined using a mixing rule. The above critical properties. For a pure compound at temperatuures below the critical temperature.9) Applying tIme umbove requmirennuents to time van der Wamuls equation. than EOS itself. A typical volumetric behaviour of EOS of van der Waals type is shown in Figure 4.7) immdicate time pressure limits within svlnich the fluid can be compressed or expanded whilst it remnmains a mclastahle simrgle phrase fluid.1. Equations ofState 4.g. e.6) m I iguun’e 4. tIne equation 1 may give three real roots for volume (or Z) at pressure P as simown in Figure 4.5) Vortunne > (4. hence. which at best is quite arbitrary. where a. v~(or Z ) 1 3 (~ =1~~!’l=0 (4.2 CUBIC EQUATIONS OF STATE 0 . is of no physical significance. This behaviour will he described furtlmer in Section 5.1.2. p~and Co are the critical temperature. and v is tIme molar volume. v I (or Z ) corresponds to that of vapour. The application of BWR type equations demuunds a higlm counpulaliomsal tunic ummrd effort. however. a horizotntusl inflectioms pniumt slson.2. exist at the critical point. at T on the Figure. Bsu-~- RT (4. v2 (or Z~). due to their high powers in volume and large number of parameters.. Heumce.132 4. critical molar density and acentric factor. It sisoumld he always less than the molar volume v. ‘F . The above equation in terms of volume or compressibility factor takes mm cubic forums as follows: N N N N N RT ~+(—)v——=0 a ab v’ —(b+—)v P P P or 1 1 Z —(I+B)Z +AZ-AB’=O where the dimensionless parameters A and B are defined as. Although acceptumble phase behaviour results can be obtained by BWRS [41. tlrerefore. and introduced his well-known equmution of stmmte irs 1873. N N. van der Waals type EOS are often referred to as cubic EOS. tIme values of a atsd h are deterunniured mis: . Cubic Equations of State 133 where T~. The predicted maximnunin and minimunrn volumes within the two-phase region. T2 T=Tc Single Phase A 4.V2 and b represent (he attractive and repulsive ternns respectively.1. yet more reliable van der Waals type cubic equation of state. TIre difference hetweenm lIme limmnits reduces as the tensperature increases mmd vanislses at the critical poimst. TIme 1 highest value. whereas the lowest value. unsuitable for reservoir fluid studies where many sequential equilibrium calculations are required.

— —~—-——-— (4. Substituting the pressure in the fugacity expressionr for pure compounds.78).902574 where the dumnmensmomsless paranneters A and B are the same as those defined in Eqs. In Example 3.1.11) Z=l.(4.-~--~dv 2 RI’ ~. refers to the values at tIme crnlncal poInt.56/4..230274 Ml’mn.55625 Z. A=I. Use vdW to eslinmate tIne fugacity csefficienrt amrd imnmprove . sunch mis quummntuurr gmnscs.40463=0 willr smu ly one reuml roust I IRT h=~-v =_(. where the suuhscrmpt c. and making the equanmon dmnremssmonlcss. ltrm~= (Z I)— In Z + I ~( R’F RT v P)dv ‘~ —J~— — = A simple equnation.(4. ‘FIme above general eqlnmmtion in terms of tIre conspressihility factor is. v v—b v ) — + Integration of the above equation results in.12) v—li v -I.c of Statr 135 a = RT~v.mctlrmmnre fugacity coefficient equal to one. eannmot accurately model tine behaviour of dense fluids particumlarly Ilmat of cotrsplex fluid mixtures.97779 x Ml’~m= (I . 4n=Q97779 ‘The van der Waals equatuon of state (vdW) gives a cmulncunl comrrpressnhulnty fmmctur of 0.= ~ (4.10) Suuhmsnimuitimsg the 2 umbove vunluics inn Eq (4. In a fourparumrureter nrodificalion u and w more related to b and/or c and a fourth parameter d. setnni-emrrpnmicmul.j=(27/64)x(0.—~--. and cinumims of rotators [8). I lcnscc tIre c.13) with the dimensionless values.35).55625I B=0. hluurd splnere fluid usmordels Irunve hcemn selected [5) to describe repulsive forces.l in Appendix A. These equations are.42x 10 nuuolc frunctnonr of urrethamre inn water. onsing vdW. expressed by a constant b.(3. defined in Eq. they have not received muclm unllenmtusn as emmgnncernng tools. The two parameters of mm mrmsd h us tire origimsal vdW c:nn ire determsnitred simply from the boundary conditions at lIre criticmml poinmt.599=0. lno~ = (Z — 1)— In Z + .7) and (4. Solution: f. the solumbility of methane in water was calcumlaled by asstnminrg tIne n. resmults inn the following cunhic equation for Z. Almost all popular van der Waals type EDS lrmrve improved tlmeir cumpahilities by modifying the attractive term. using Eqs (4.. using Eqs.56)’/4.the accuracy of predicted gas solubmhmty. ‘/. we o lain._u~) .‘-I. They can be expressed by tIme following gemrermml form. and/or a third parameter c.134 9 2 2 27 ( R T ~ 4 Equations ofState 4..sirccnsurmnniunmr of dissu. in practice the mnmodification of tIre latler ismus beers nusorc rewardimng. (‘uhic Eqimation. and w are related to) h. experimental data on punre flunids Irurve umlso hecir used gennermully to deterissine tIre parameters.3. F.90257 Z +I .. required mmnore imniprovement than that of the attractive term.2.7-8). 2 2 2 2 z’(l+lt)z +(AB~JtJw )z(ABr3w w )=o 2 = (4. (4.It)) amrd mncthane critical properties given in Table A.. as follows.1. = (Z — I) — In Z + _Lj(.3.6). _!_IRT In ~ RTL v—b vj. lummve A grcmutcm Itnmnmm 0. 2 27 (R T2 ‘~ a = —[ —s.Y1 =Pxn*=65 x(I. such as vdW.(m’/kgnnoI)~ 64 ~ P~ j b I RT —(——-~-)=(l/8)x 0. ln~ =(Z— I)— In(Z— B)— A/Z The parameters of vdW are calculated. anrd . respectively. as. lrnpienrentnng the Inmnmts. Ilnercfone. mndditional to the above. P = —~. whereas very few connpounds.q.Ivcd nscmtn:nnre inn wmnter.8).: =4.0083t44xl90.0083 I44x 190.nuv — w’ Inn mu two-pmsrumiimeter fosrnsm of mIsc equmulion in and w are related to h whereas in a tlmree-p~nranneterforum on. corrected for ilre fugacity coefficient. Nunmerous modifications have been made to imnmprove ifs capahilily by flso(lifying the attractive amnd repumlsive terms. TIne equation proposed by Cartrmrlsmmn anrd Starlinmg [6] imas been used extensively to develop new forms such mis perturbed Isard clsmmin [7]. wlrercmus in nrnosdificd versions.9. we oblain.~I —~--~-. Although vann der Wmumls considered that Iris representation of repulsive forces. In spite of recent efforts [9] to simplify tine earlier modifications in order to mn’rake them more practical.(4.49069 Snuhstitmnnimrg nIne above vumlnic of tIme comnupressihilimy factnsr in the fougurcity expression results in. Example 4.304254 m’/kgmol 8 ~ .599=0.375 for all conspounds. us.4378x10’ Mt’a/mnnol fraction) xx.

20) Witlm tIme exception of Redlicln mmmxl Kwong [10) who originally proposed the temperature 5 depensdency of a in 1948 as u=Tr’°’ recent investigators have uised vapour pressure data to The two-parameter EOS are the most popular equations.(3. Euannnple 4. ‘Fhe van der ‘oWmnuuls type E()S Immuve bccmm cosinnpuclucnrsively reviewed in literature 111—161. the method used to determine tIme EOS putraimmeters could 3. Time success and popularity of certain equations are nsore due to) featmures other than tine selected have a higher impact on the predicted results. 2 a = ~ (4.t. lnmi~ =(Z - Prove Ihat the mureas hetweemm tine saturation pressure lure and the predicted volunme isotherm Imy a cmnhic equations of state mrre equal for a pure substance. Jd~=JsdT+JvdP=~ ~L ~ . Integrating Eq.1U2 A I 2Z. expressed by an equation similar to Eq.15) . F?qmuatuomn.~ t:::::::::::::~:s vv / improve the prediction of density along witls reliable vapour pressure.(3. on temperature and ac depends only on the critical properties of the compound as given by. the inclusion of a tlmird paratmmcter will gemsermnlly form in most cases.35). Imcmmcc.St~ir 137 RT RI (4. but the coefficients lmave been generalised as ~ a and ~ i’Ime ollmeu parameters.(4.’n?i. to he tennperatnrc du’pendemmt. 17). using the same approach as in Exanmple 4. Two (Sr tlsrec parameter EOS are considered adequate for all applications in the pctroleuums itmduistry. ( ‘nmbic &/mmati. a. — p (4. mupplmcmmble in determmsimming tIme parameters of an empirical POS. Although EOS primarily provides volumetric (density) data. known as the Mmrswell equmml murea nile. is not the revision of the attractive termsm functional forums. assumed. a. For example. for selec(iisg a particular form of EOS amongst nmany described by the general form of Eq. lIme mudditioms of tIre Ilmird parammmeter hums increased the flexibility. its msuijor contrihuition as an engineering tool is through its coumpling with thermodynamic relations in predicting phunse belmaviour and physical properties of fluids. Solumt.a (4.2. phase equilibria. The above equality. hut with different coefficients.136 4. — I)— ln(Z — B)+ . where the parameters mure expressed by. hence.19) Figure E4. Note that the expressions for the parameters ins tine mnodificd equumutioums are siunnilmur to llutssc orf 1 the original vdW. Pressure’voluunse isottsermrs of a pure fluid as predicted by cubic EOS. we obtain.o.l2) into the expression for fugacity of a pure suuhsluunce.~:::::::::::::::. The substitution of Eq. are generally of co-volume usunture. The main departure from the original vdW. a=a. lnemrce. in EOS which use more than two.1. R T 2 c tleternmmine a ‘Fine above discussion lmighhiglrts tire siurnilarity between all tire comssmmionly umsed equations of state and suggests tlmat tlsere is very little fundamental difference between them.14) (4.[U2+4W2 n i~i-j3-:~: ‘Jii~4W2 (4. 12).(4.u (nl . Whereas a two-parameter EOS would suffice to predict tIre vapour pressure.l2).(4. Eq. time inchusion of nmmore pmmrameters in EOS makes it more flexible. where tIme inrvcstigmutosrs Imurve dctermmnined it gcnmemmmlly by rmratciring saturusled liquid data.) nvn. S . As tIne parmmmrmeters of mm sermmi-cmnnpiricmul BOS mire determined by matching its prediction to experinmeumtal data.22) from the satnmrated liquid to tire saturated vapour.(4. or strongly convincing arguinments.U_.2. results in the following generalised expression. is counsidered equivalent to equality offugacities of saturated vapour mmmd luqumud ilsmuses.n: where a expresses the dependency of the parameter.r of State 4. which has resulted in the success of tniodified equations.18) There is hardly any theoretical foundation. hut treating it as mm Volume temperature dependent parameter.16) RT b = ~ ‘ b ‘p’” (4 17) All the lwo-paransretcr equmations husve selected a fomm of Eq.2. than the mathematical form of the equation. ammd lmmmve detcrnmntned lime tenmperalurc dependency by matching tIme vapotir pressuire dmmta.

005 (0(0 01(01 002 0.4 0. tO Accnnr.0 The values of ~a and ~b were considered to he constatnt.8 1. 00.2. ttemsce. imence.9). detcrnsnimmed to he 0. Eq. others Isurve generated generalised correlations for parameters by applying tire method. can be used instead of experimental data to calculate vapour pressure mmmd saturated liqumid density respectively. Wlnereas Zumdkevitch-Jotfe suggested determining the parameters when required at tire prevailing conditions. Figure 4. 4. Figunre 4.09 006 0) 07 oh (00)1’. 2 shows lIme varimmtion of ~a and ~ with Tr as derived and correlated with the acentric factor by Yuurhorougim [19). no Ii 25 0)201 4. Eq. Above the critical temperature.2a.6 0. Figure 4.40 or. Reprinted winlm perummission 1191.(l.138 because the vapour and liquid are urn equilibrium.0 Reduced Temperamnice The approaches of Rediich-Kwong.erauure Zudkevitch and Joffe [17). ‘I’ime use of correlations to determine the parameters definitely simplifies the calculation task. ‘rhe sharp change of both parameters near tIme critical point clearly rnnled ounl the extrapolation of the relalion above the critical point. tt P(Vv _VL)_JPdv=0 Which is only satisfied when the two shaded areas mmre eqummrl.c I’acnor 0.0 0)2 0. an approach which is generally used in otlner EQS. Cubic Equations ofState 139 The integral over dT is equal J 0) 50 to zero at the isotlmerm. and modified Rackent. (Iemrermulused values of U in ZJRK. a 0. Copyright(1979) 5 Ammuerucan Chemnrical Srcicuy.I2). and equalisation of saturated liquid and vapoumr phase fugacities. Manchming of the predicted data to mnmeasured vmmluues at saturmut ion to (Ictcrnmsinse E()S pmnr:mismelers has been used almost by all recent investigators. The above approach was necessary as two equilibrated phases cannot exist for a pure compound above the critical poinmt.lO). Eqomotuonms o~f State 4. and tIme parameters are calcomlated only once. A few of the cunrrenntly prevalent EQS will he presented here. (0. [IS] assumed tlmat ~a and ~b in Ilse RedlichKwong equation of state (RK) were temperatumre-dependent. (4. and Zudkevitch-Joffe to imnrprove vdW. lIme values of ~a and ~h for each pure substance at any temperature were obtained by matching the predicted liquid density data to the measured value.(l.2 04 moo os 1.2h. hut reduces the accuracy as any generalised correlation is bound to have some deviations fronri line cmrrelated duntmu. Reprinned with permission [191. suclm as those of Lee-Kestler. and Joffe et al. The mmiellmod suggested by Zudkevitch and Joffe does not significanmtly inncreases lIme calcumlational effort when applied to a petroletmm reservoir where the tennupermntulre is treated mostly constant. P=RT/(v’—b)—a/[T~v(v+h)] and 0. Copyrighu (!979) Anncrncan I’Incunuicat Sot’ieuy . the parameters were taken as constants and eqummtl to their values at ‘Fr = I. Generahised values of Ub in ZJRK.21) 015 000) 00. have been adopted in all the successful modifications of vdW.1 Two-Parameter EOS Redlich and Kwotmg [10) modified the attractive tert3m of vdW as.42747 Reduced ‘remi.(4.08664 respectively.35 a. that is nnaking the parameters of EOS tenrperature dependent and using the smsturated data to determmsine time parameters.45 Acenrnric Facnor vdP = Jd(Pv)_ J Pdv = 0 (1.2. using Eq. Ansy reliable correlation in literature [20).

I’eng-Robin. SRK is ulummtc capable of predictimug vapoumr—Iiquid equilibrium.798 0.24) to improve pure-conspomsent vapour pressure predictions.0.c of State 4.1 fl44~2 + 0.24) the above .037036I~2 / T~=0 Substituting T.(4.0. m=0. / ‘I’.=l. TrMS.55171 to.8). Eq.O8664T.27) 0. Z. 2.7.22 0. Hence. with the results as follows.u.15613 ~2 SRK in terms of time compressibility factor Ztakes the following form.5-3.907 (4. respectively.24).(4. (4.(4.so.823 3.26992u 2 (4.0 0.08664P.42747~ / ‘F~’ — 0.4850) . Cubic Equation. respect ivt’Iy. Pr)’ Compare the result for T=l .7) umnd (4. 2 ac = 0.5 and various P. RK Z. which considers that fluids behave identicmmlly at conditions of equal reduced properties.12) by 2b and h.~ )P/ RT = O. Eqmmaticn.42747T.480+ I .~mP~ liquid density.0.952 0.08664 R T~ / P~ and PR in terms of the commspressibility factor Z takes the following form.(4. )2 ~Z— 0.08664RT~ I P.23) PR is obtained by substituting u and w in Eq. The comparison with the values of Zread from Figure 2.28) 2 2 0.574o-0. and m was correlated with the acentric fmmctor by equating fugacities of saturated liquid and vapour phases at Tr =0.077796 R c / c They used a sirniiuur form of a as proposed by Soave. wiiti the following expressions for A and B according to Fs s. hut it does not provide reliable (0.(4.22) 0.7) and (4. ins = (4. I ~q.(AB-B -B ) = 0 (4.5. 12). and correlated m as. 1 76&’ Soave et al. later suggested to divide tIme value of m determined from equation by 1.3796 + 1.950 1. — (0. P. (‘oil mpuurm ung SRK witIi I luu’ gemrcm’uml I ~()S . - (l-B)Z 2 + 2 2 3 (A -2B -3B ) Z .3. 3 2 2 Z -’L +(A-B-B )Z-AB=O (4. ‘~I~ B = bP/ RT = wlmcre tIme definitions of A umusd B umre given ins Eqs.22 is also shown. results in. subtracting the predicted molar voslume by a constant correction term can improve the The function a was selected. A class of equations relating volumetric properties to temperature and pressure.457235 R T~2 /p and Soave-Redlich-Kwong EQS (SRK) Soave [21] replaced the temperature dependency of the attractive termmm un RK. Volunne S/u uft A comparison of time predicted liqunid molar volume by leading two parameter EOS with experimmmemmtnui data of pumre consspounds generally slsows a systematic deviation..2.42747 R T~ / P~ The correlation was later modified to improve predictions for heavier components [25). in = 0. over a P range of 0.26) The Redlich-Kwong EOS in terms of the conmpressihility factor is tIme smmuime as Fq.22.08664P. 2 5 2 2 71 A = aP/(RT) =(0.(4.778 T 15 b = 0.01 667& (4.48508 +1.0 0.0 0. P=RT/(v -b)-a~u/[v(v+h)+b(v-b)J where.(4. m=0. The deviation is almost constant over a wide pressure range away from the critical point. Fig. [22].903 2. Reduce the Redliclm-Kwomng EOS to a corresponding states form of ZZ(Tr.5 0.37464 + 1.140 4.5422o . values in the above equation results in a ctmhic equations. but used vapour-pressure data Irons the nornmmal boiling point to the critical point.(4.u EQS (PR) Peng and Robinson 1241 modified tine attractive term mainly to improve the prediction of liquid density in comparison witir SRK. Solution: Grahoski and Daubert [23] used the API vapour pressure data and modified Eq. by mm more general function a: P=RT/(v-b)-aca/[v(v4’b)] where = Substituting the above two expressions in Eq.427471’. is that based on the corresponding states principle.23). IT. I Inc val ties of tm=h mind w=0. with that 1 ofthe generalised compressibility chart shown in Figure 2.25) (4. z m — + 5 [(o.’° R T~ / P~)I’/ R i’ 0.8) respectively.30) a=[1 +m(1 5 2 Tr°’ )1 (4.29) b =0.834 0.26).s of State 141 Example 4.18 to improve the results.

The effect on the predicted vapour volume is generuslly insugnificant due to its large value relative to that of liquid away from the criticmul point.IO02 ~0O65Ol -0.2944 I — ZRA) R. resulting in the same value of equilibrium ratio.01540) ~0.c ofState 4. Penelounx et al. At high pressure condition. Hence.2. the above modification will not affect the predicted equmlibriuni conditmons. Stmggested values for the coefficients are given in ‘i’mthlc 4. Sn.2.(t.7. Matlsias et al. and found to he 0. is the mole fraction of component.) u 2321 0.2(6)8 Tire value of for lmemmvy fractiomrs of a reservoir flunid can be used as a tuning parameter to murtcts tIne predicted to mmmeasumred satumraled liquid densities.36). It only multiplies the fugacity of each component in both phases by an equal ansmoumnt. and lrums a mninnimnmal effect on the vapour density at low and immoderate pressunres as its molar volummie us relatuvely large compared to the value of c. deternsmined using experinm’mental data.5. to mnnnprovc tIme lnrcdicted demnsity near time critical point by EQS. x .40768(0. 1 The inclusion of the third parameter in EOS changes the calculated fiugacity coefficient using Eq. EOS are applied to multicomponent mixtn. u’. was also . cnnrnnpunnenn Ci C2 (‘3 IC nC4 4 S~ . who applied it to SRK and found a value of 0. [26] were the first who iumtrodumced the voltunrie slunfl comnrcepl. v c (437) x = — + 0.(4. . 5 S t~’h (4. It was.1.suuggesled immdepemsdently by Cisoum and Prausnsitz [29]. Wimen the fugacity of each conmpomment is calculated by lIne sammue EOS ins both vapouir and liqunid ptmases. = 2.I2).Equation.07935 -0. and need not he mnciunded in EOS for calculating the vapour-liquid equilihriumsm ratio. The shift parammseters for light compounds are given in Table 4. correlated the volumne translatnon parammieter c as.12) = (I / R’I’. with an additional term related to derivatives of time molar Helmholtz energy.31) 1271. x are positive coefficients.T~ (434) wimere ~3. as will be described in Section 9. by defining ml dimensionless shift parameter. Eq.04350 -0. Time volums’se shift generally improves the predicled liquid density.516 0. •ncor = wlmere s~i and Table 4.c ofState Jlmumveri and Yonnngren 143 sinsril:mrly to Penelounx et al. and applied it to SRK. (4. determinmed by regrcssionr of saturated vapour and liquid volumes.3I). respectively..06413 where vCor is the corrected molar volume.sioirless distance. A wiscre ZRA is the Rmmckett compressibility fuuctor mrs develolsed by S memrcer mnnnul t)mnmsner ins tIme 1 modified Rackett equation.c. and c is the correction terum’s delermuned by matching the measured and predicted saturated liquid volumes at Tr = 0. = ~x. particularly near the critical point where properties of the two phases approach each other.pe . ~.nres by introducing fluxing runles to determniime mixture parameters.35) 5 was determined by matching tIne predicted and nmmeasured molar volumes for various hydrocarbons. C’ocfficienmts of slnift parunmnsctcr correlation. The following mnxmnmg rule is used to determine c for mixtures: c = iC5 nC~ -0. Vmulues of slsift parummmneter inn Peng-Rohinsomm equmation of state. Therefore. Eq. l’armuftins Nmn uhotnenscs 1 Atonnnummtics 2 258 3 0)004 ~uexp (- c P / RT) 1 (4. and ~. m. i’R. an additionnutl voluusne correction term scaled according to proximity of the prevailinsg conditions to tine criticuml point.01478 (4. 3 v =(RTC/PC)ZRA (1.33) where ojs~Cunr and ~i are the nnmodified and original fugacity coefficiensts of componcimt n. however. Table 4.36) lIne unutlsors correluutcd tine slnift pmrrunnrieter to the molecumlar weiglst as. as will be described in Section 4.162.1. The proposed method was extended to binary mixtures. lIne dimnren. munrd relumted c to lIne paraumseter Is. is a cusnslmnmml. 1281 pointed out that umpphication of the above method to PR raises the calcuulumted liqomid voluusnc above lime cxpcrinssemital value for almost all tested pure compounds mmbosvc mm reduced tensrpcrumturc of umrotund 0.(3.142 4.43). applied the volume shift concept to predicted liquid density. as. and tire uleviatioms reaches its mnaximum at the critncmml point. However. is a dimensionless distance to the critical point. Cuuhin. Peneloux et aI.) (~)P/nJp)r (4. was related to the slope of the prcssuure-denrsmty isotlrerisu as. the inclusion of c puirmuimneter may nsot necessarily improve the predicted gas density as it is just a correction ternn fosr the liqumid density. Connuponncnmmjy.38) A sinmnilmur uuppromncln. it is advisable to adjust tIme gas phase volume by the third parameter to maintain consistency.2. to match the critical volume by EOS. was proposed. .35 for ~. slnnftunmg tIme volume axis.85.3. in the nrmixturc.41 for PR. NL_. vcor=v_c (4. is the volume correction.. additional to c. irquaoonn. Eq. A. S . the thmrd parameter can he emnployed merely to adjuns( the predicted vohumme.(3.32) I where.04183 _________ -0.

ln4 =(Z— I)— ln(Z— B)+’—~—lnZ+(l — ~J~B 2B-f~ Z+(l+. Cmthic Equations of State Stibstituting the above two valunes of the compressibility factor in the fugacity expression results in.2337603 I Z.f2)B The parameters of PR are calculated. 10557 Z2 =0.29). 0.6) /3.= 2.3 I). Figure 1.825 135 MPa. The comparison of the calculated ftmgacmty coefficiemmts indicates that the assumed pressure is chose to the sumturaliomn pressure. for 0)=0. Eq.22381034 Z. The next pressure nmay be estimsmated as. and Eq.10). and pV= kg/mn’. Substituting u=2b and w=b in the generalised fugacity espressiour for pure conmmpoumnds. hut requires improvenment. amd cmmlcoilalinrg tine mrmolar volume.7-8). results in.2 1405 3 1’Ine unmeasured vmuluues.(4. 05 2 Tr ’ )] 1. and Zn and Z.0508396 v’~”=l. l~qmuutio:n.049349 a=axa.( 1. are assigmred to the vapour amid liquid phase.94089.9458 MPa 071716 ‘I’he cstiummalcd valune by lhc 1_ce-Kesler equmulioum.~V )j The where r is tIme itenaliomn mmuirniser.485w -0.=~=0. TIme aimove mnppromuch restuits un mm pressure equal to 1.025=2.ove pressure is as follows. 4.Hence.23634 Rejccnnmng the ummlernsnedimute root.30 13 at T. is 1. as.l8). respectively.333 by PR mnmsd SRK respectively.=0..6 K using PR.0083 l44x507. = [P(~’. ~(r+O) = 145 concluded that the near critical contribution did not appreciably affect the restults for imsixtures in most cases. for all sumbstances.(4.3 kg/rn’.2.0()lt’u04 mns’Ikgmol wtnucin resulls in tIre knlkswinng corrected ummolar volunnes.457235x(0.t).108539 nm’/kgmnol m Z’-0.( 1.6/3.(4.t’s92273 MPmm. A=0.( I It)).22523ns’/kgnmol TIre demmsmties of tIme suutuurated plmases are: p=M/v p’—)826 kg/nun’ 5 p =70.2279 m’/kgniol which results in the following cubic equation for Z. Appendix B. Fq.812562 a=(I +m(I Hence. 5 2 Z -0. i. The pressure is iterated until the two calculated fugacities become equal.0.457235R Tc 1Pc =0.=op’=0. Calculate the vapour pressure of normal hexamme at 477. 4.3796 + 1.(4. predicts a saturmmted liquid density of72 424. Example 4. and liquid density? Solution: At thesaturation point.0083144 x507. Z~. A two-paranmeler EQS predicts tine susmmse critical commipressibility factor.ts=. defined by Eqs.12).=477.746fs 1(1 For a pure compounsd the eqtuality of fugacity reduces to the equality of fugacity coefficient.4.(mmr’/kgmmrol)~ The cubic eqnummtmonr at tine mmt.IR kg/nun’ Assuming a saturation pressure (sI 1. i~q. more p=423. 10958 Z.3 or Fq. Eq. using PR.l in Appendix A. c=S. and imormuml hexmmume criticuml pusperties.22362 mmm’/kgmnot v”=l. Eq.729704 m~n~4n’=0. iteruutiomn converges to. Eq. for the next step.e.015562=0 The temperature dependency factor of the attractive term. a pressure is assumed and the fugacities are calculated. What are tIne predicted values of the saturated vapour. v.(4.33324353 B=O. 2 2 2 0. Table A.9468 152 Z +0.0142259=0 The above equation has three real roots.35).2. whereas Zc varies within a range of 0.949l604 Z +0. using Eq. Eq. The modified Rackeit equation. ums. tIme two dimensionless parameters.9031 MPa. b = 0. the fugacities of hexane as vapour and liquid shotmld be eqtu~tI. v=ZRTIP Vu=0.(I.6). 1.1 f44w 2 + 0.0l478xt).(4.2 to . m = with the following roots: Zu’~0.01 667&= 0.=0.307 ammd 0. are calcimlunted as. It)8539=.025=0.86 MPun.0.077796x 0.5).936 MPa. is calculated from Eq.144 4. Zna:0.2 ‘lhm’ee-Parameter EOS The intermediate root is rejected.(4. we obtain.22623 nm’/kgmol 0. a.sofState 4.(m’/kgmol) 2 ‘Fire volnumnme shift fusr unonmmmml Irexanne is cmilctmlmuied.0.(4.6/507.60089 Z.6=0.5..62954 Z =0.27).23). musing Figure 1.077796 RTc/Pc = 0.

.2.We.4774 + 1.3 shows the deviation of liquid density at T =0.347w .(4.146 4.15) inn 1 + ons <0. ‘fIre tlnird parumumuetcr is gcnrerunlly determined by employing volumetric data. This was known to the umutlrors.44) (4.9) ts determine use. P = 2 1~ac = [I - 51(1 - P ~.. qfl 3 (4.41) where tIne paramrmeter c is defined by..c of State 147 0.01429 (STr . ~‘.’ Ian ed. by ii = I / 13 (I + q(o)[ (4. whereas PR gives reliable data for conmrpounds wills urcentric fmuctosrs umrotnnmd (1/3).a~a / [v 2 + (I + 3m) by - 3mb ] 2 (4. c.3671 < I I IS mmmd for unmtcrmsncdiumte values of 0. defnmmed as b/vt.4 mrs =[(0.0. Patel-Teja EQS (PT) t’mmtcl utund l’cjui [31[ mnnodilmed tIre attractive ternr by incltndiumg a more flexible third parameter.=0.0 779)2 wlsere.sI point.55 1(w-O. + 0. where these equations predict lIne liquid demmsity reliably. w tIm I Inc mcemrtmc lunclu nr un rd reoltuced Ic unuperatuire by msmatching vuipour pressure (luntun of ~nnrccomsmpnsunmds.izel EQS (SW) wlrere mi is lIne critucal comsnpressibilily fumctor. will reduce it to SW. Isut wmrs uuccepted as tIre price for an overall optimum accuracy in predicted volumes.42) mmmd q.(4.as.536l +0.3 The deviation of predicted fromn nseasured liquid demmsity by SRK uund PR [30). therefore.528os2 for (0 0.43) Figure 4. Eq.40) I RT / (v . = ~q (4. - 1)2 form form 0. and is related to the correlating paruuusletcr q.cl selecteol tIme sumnluc fosrurn of a mrs proposed by Soave. The authors used the boundary conditions at the critical point. be considered a general form sf SRK urnd PR.9).55 (4.51 m C > -~ •• ~ 2 (4.55 -cm)) / 0.39). and amn error analysis of tlue genscruul EQS.48) b = ~ La.c unf.Stuuta’ 4. Note that SRK is more acentric factors.(4. inn.71 (‘r. inowever. ‘lIre nmrclumsiots of m in EQS as tIne Ilsird paraunneter by Schmidt and Wenzel resulted in a vumrimmhmlc calculated critical cornurpressihility. 20 o tO SRK 00 0 0 0000 mnnn m. = t).00375(02 RT / (v — b) . SW can. html curium. trot necessarily leads to unreliable volumetric data at all conditions.1 02 Acennmnc Fzucnor 03 0)4 I I Figure 4.. cx = I - (t).eI EQS (SW) will 3 reduce it to SRK and PR respectively.(4. Based on the above observation. and b. Schmidn and Wenzel [30] incorporated the acentric factor as the tlnird pumramnneter in tIre attractive term as.0217(0 + 0.39) Sclrnnnnuit umurd Wcmni.45) no = + 0. ‘FIre inclusnon of a third parameter relaxes the above liminmmtismi. according to the value of acentric factor.4)/0. Eq. Sc)nnmidt. non. urn nnu mm 1 2 = Substituting acentric factor values of zero and ~/ in the Scbnmsmidt-Wenm7.47) -20 ‘ 00 0. 3 2 (6m+ l)q +3q +3qI =t) (4. and W =3(n)h in tIme generalised EOS.3mm.7 predicted by SRK mind PR for mm 1 reliable for suuhstanrccs witlm smnmmll number of pure substances. Eq. Although the inaccuracy of predicted volummmme mit the critic.46) PR For supercritical consupotunds.23).465 + 1.9593w form>0. a~ R’T. . mrs.h) + a~a/ (v(v + h) + c (v . mihout 15% hmigimer than tine true valumes.3 for hydrocarbons. as predicted by Eq. The predicted values are.i2). ( shun !qunatnuu. Eq.3280)) In T~ (4.u. = 0 25989 0. 2 2 Sunhslituting um=(I+3cn))h.(4. P = witlm an approximnsunte value of.4 0. it dcisionstruites tlnc inflexibility of two-parameter EQS for matching both time vapour pressure mmmd volunrme. Equuatiunru. . is tIne sminallest positive root (sf lire following equation.h)] (4.3671 ~O 0 0 nmi.

and increases the complexity of the matlsematical expressions of the fugacity coefficient.58) 2 for T~ <1 (459) - I m = 0. Note that these valumes are predicted by the two equations mis lime critical compressibility factors for all substances. . Fuurthernsore in nmost reservoir engimmeering problems.2. the critical point is approached by coimnpositionuul variations. by adjumstiusg time relationship between a mind the reduced enmmperature to mmnmrtch tise vunpour pressure data.e. as. contrary to the constant volume shift. imowever.56) Attractive Term Temperature Dependency = 0. The Patel-Teja EOS (PT) reduces to PR or SRK by substituiting the value of 0.4 shows tine insmprovemnent iii predicted density of a binary mixture by including the near critical corrections [34] in VPT.(4.. The volume shift concept can also he applied to three-parameter EOS. if any.38) represents the approach to the critical point for pure fluids.50) Time uthove correlations were developed by matching predicted and experimental data without being restricted by time conditions mit the critical point.54) . PT can also be considereul a general form of SRK and PR which will reduce to either of themn at their prevailing constant critical compressibility factors.s ofState nu = 149 for Tr> I c=Q (449) cPc . m = . ~ 0. to correlate its parameters. It has.46283 + 3. 4.9). Both definitions of the distance parameter. Eq.076799w + 0.(4. A = 312 + 3(1 - 2 51)~h+ ~b +(l 2 3m’1) (4. acimieved its objective as demmmonstrated in Section 9. Timis deficiency can hc corrected using time aupproumch described by Eq. (Kt/Ktn) - I (4. a conclusioum also reacimed by Sclmmsmidt umird Wcni. Eq. It sinould be noted tlnmml time inclusion of variable density correction term in EOS changes time predicted equilibrium conditiomms. ~ .I2). Hence. as VP’l’ does mcml smmtisfy time houmndary comsdition of Eq.2 wimere time pcrforimmance of various equations are conmpared. all the state points along the path have diffem’ent compositions and different critical points.52) ‘fire muhove correction cmrmm he mmppiicd to VPT. Applying the condition at the critical point.53) ) .351) ~h 2 + 21~ 3 3~ h -1’ = 0 . alnsost with no exception in all recent mrmodificmutiomns of vdW.66121 - 0.2. Valderrama and Cisternas 132] and later Valderrama [33] modified PT by using the critical compressibility factor. however. 2 Substituting u=b+c and w rrcb in the generaiised EQS.58230wZ~ + 8. An alternative dinnucunsionless distance to the critical point. (4.57) (4. the other coefficients were derived as. Equations of State 4.022005 (4. or 0. Eq. Hence. Z~.(4. and ~ac = Time dimensionless distance given by Eq. as time saturated density data have been generally used to deternmine tine third puiraimmeter.I9417(wZ~) As imsdicated by Wilson [35]. The authors determined irs. Hence a correction tcrns for time distance pumrammmeter needs to he inclumded [34).(4. instead of including it mnEOS.2959370)2 (4.333 for ii.87080Z. ~ac = . This appears to he a major step mr igusoring time muctumul behmmviour of puire fluids in favour of an overall improvement imm predicted vaslucs by EQS.30982w . . Hence it is advisable to use it only for adjusting the predicted density by the original EOS.329032 — 0. ~ The authors found that the use of true criticunl com’npressihility factor will resuult iii the overuslI loss of accuracy in predicted density. The temperature dependency function of (he attractive term in PT is similar to Ihat proposed by Soave. respectively.32429~. Eq. all K-values are equal to one. and correlated it with the acentric factor. will be expected to he minimsnal. ‘1 + v”” = v+ö.9). hence the proximity to (lie critical stuste cumn he expressed hy.2o868z~ i. = 0. determined by nmatcIming the predicted aisd measured saturated liquid densities. It was correlated with tine acentric factor as. a reliable prediction of vapour pressure of pure compounds by amy EQS is a prerequnisite for its reliability in estimating vapour-liquid equilibria of mmsuilticoumnponcnt syslenms. Cuthic Equation.02119470)2 (4. Figure 4. 1 is an adjusted critical compressibility factor. aurd KIm are time equiIibriumsm ratios of the lightest and the lmeaviest components of the mixture at mummy . Tlmis lsuus been achieved.61) where Ki. . - ~b is taken as the smallest positive root of the above equation with an approximate value of = 0. is questionable.state noint.55) .0. and the equnilibrium ratio (KC) have been used.148 4. It was poimmted ount. that the prediction of these C(ltimutim)mss deteriorates near time criticuul point.51) .23). which is as valid for variable composition cases is the relative value of the equilibrium ratios of the mixture components [34].0. will reduce it to PT. 0 an d = I - 3~ . (4. i. hut witIsout including the conventional shift. C. . .9). usmng time vapouur pressure data of pure compounds.(4. and not by changes of pressumre and temperature. isowever.(4. hut the distaisce parameter A is not zero at the criticuml poimmt..307.3 I 0.76 l05Z~ (4.02207 0. the pressure derivatives (PC). At the critical point.4524 13 + 1. (2 .57765 + o.cI.(4. Its extension to multi-component systems. (4. The improvement.37).

correlated by power tirrcc of lIre acentric factor. 0. 0. Cunbic Equaiionus ofState 151 a = ~i + C. the extrapolation of function to heavy compounds with high vumltncs of lIne unccntric factor earn lead to large deviations. Time popularity (sf an EQS nmnmmy he juidgcd even by the number of modifications to its temperature depenmdency fmsctor! The a function attains generality by relating its coefficients to sonnme properties of compounds.(l — ~‘l~) +C.23). ‘tIne common approach has been. The following three-coefficient functional form was proposed by Mathias ansd Copeman [37]. 52). (4.23). ‘l’wtn ci url.c. as given by Eq. ‘tIme mount hors cvmml ummntcd a in PR aurd showed that It varied linearly with time utcentric factor mmt constusnt reduced tcnmspcrature.nc’u’I. for the same equation of sturle.s ofStat. and reduced temperature have been used.(4. f 38} poimmlcd out mhmmt hue use of lIre conventional a fuumction. 00 0. to imrtrodsnce mm geircrumlnscd cosmn’elmmtnomn fnsr a mum conjunction with the proposed equation of state. a F. Effect of near critical volume correction on predicted density of etlrurmmc-propcure mixture at 311 K. (4.4.2 04 0. Eq.. as proposed by Stryjek and Vera [36] for PR or Eq.xperunueona) XC ucanung — — — n’C sc.5 shows variations of a at several redsuced temmmperatumrcs as deteruirined for PR by nmmatching the ms’ieasured and predicted vapour pressure of pure comnsposmnds.’ 4.o. however. and preferred the original form. Bussed on tIme above observation.u. and (~. to inrprove the muodel for Ineavier comrmpotunds.25. makes a a sixth order function of the mucentric furctor. I.64) whmere a”. higlmer order polymxsmmmials of uucentric fumctor. I’iuc a pmumanssctcr for asymmetric compounds can he related individually to the reduced tem’umperature. gumvrl/cnn3 0. It is reasonable.4897l53w-0.63) where tIre cosefficicmrts C . The acentric factor is the popular choice. it is not unncommon to find different funirctionuml formirs. irowever.6 0. with the slope.g. are to he determined for each compounmmd by matching 1 2 its vump(sur pressure. or correlations for their coefficients.378893+i.onO 0. C .23). Equa:no.0 Acenriric Facior Figuire 4.006 0. e.62) us aC. Correlations as those given by Soave are in general quite reliable to predict tlre vapour pressure of relatively light compounds. Tlmc above approaclm clearly reduces tIre risk of extrapolating the a function to compounds wit Ir Irigim umccnstric factors. in preference to that of Soave.2. . particularly at high values of reduced tctrmperatures. Eq. a single generalised correlation should be adequate generally to correlate lsydrocarhsn conmmponcnts of reservoir fluids.uhuug Somuve [22] reviewed lemm differemmt functions for a.0 n 2 Figure 4.002 • N. a = a” + co(a’’’ — a’°’) . may not he adequate to describe all conmpoummnds of vastly different characteristics.(l — ~)2 +C. mmnnd a’’’ mire related onmly to tIne reduced temsmperature. 2 — —— 0. To improve their capabilities over wider ranges. ilence. Although the same form has been used by most of the leading EQS.29) proposed by Peng-Robinson later.(4. Variatinrnms nsf a witlm muccurlric factor in PR at constatrt reduced temperature [38]. The most consusson fumnctionmumi form is that proposed originally by Soave.000 0. Eq.2.004 0.17131848w +0.. mis cxplmninrcd inn Sectinnmn 4.150 4. lime most direct approacln is tlsuut of Zudkevinclm-Joffc. [38] correlated a of stmh-critical components for PR as. the autlmors suggested time following function. on. to expect that a generalised equation in terms of the acenmtric factor. Examples are: m=0.(4. ‘rwun et al.(4. to improve the predicted results for complex systems. particularly at low reduced Ic unnlsem multin’cs. However.88).. 29. in preference to their original correlation.(l — ~)5]2 .. Figure 4. sunch as Eqs.8 1.0l96554co 2 3 (4.(4.5. proposed by various investigators.(4.008 Murlar Densiiy.

40].2 1%. will be reduced.67) The average absolute deviation of predicted vapotnr pressure for pure hydmrcarbons by PR from the triple point to the critical point was found to be 3. Time predicted dew poimmts by time tmnodified PR.95.2. 125283(1 — T ~‘~‘° )~ 4.65) a0) =T~°”~exp[0. The average absolute deviation by SRK usitmg the proposed correlation. Eq. . where many millions of flashes may be performed in a study. Figure 4. were matcimed to experitmiental data by adjusting the paranseter a of the super critical components. Pro a . arc taken into account to some extent. all correlated by mruatching vapour pressure data. are generally at temperatures well mthovc tlmeir critical points. The results clearly demonstrate the importance of the selected functional form of a. msnrd 12.~~i7n8u3 exp[0. where no vapour pressure data exist to be used iii correlamiing the pmiruumnuelcrs. Eq. with.~C 100 120 Predicted dew point of a mixture with composition: C =82. Whereas Zudkevitch and Joffe assumed valumes of ~a’ and ~b for supercritical compounds to be the same as those at the critical point in the RedlicisKwong EOS.”~° m45 exp[0. Note that tire predictions by lime nmodified a function (shown by rnPR are superior to timose of the origimsal witim and wittmout time use of BIP. hqunatnomn. as predicted by PR. described in Section 4.6.99. where m’=l. using the above correlation without any BIP. Hence the mixing rule sisould describe the prevailing forces between molecules of different substances forming the mixture. The bubble point liquid phase and the compositiomr of tIme equilibrated vapour phase. A few investigators have suggested different correlations for supercritical compounds [30.(4. There is no limitation in evaluating the reliability of any a correlation at super critical conditions if volumetric data is to be predicted. tisat time correlation is also valid for super critical conditions. 4. respectively. Eng. raises an important question. ammd the success of using binary data to determine its correlation for supercritical compoummds. . are cotnpared for a 5-conmponent mmsixttmre in Figure 4.66)._. The umpproach may he immnplemnented in any EOS..152 atou = T. Over 5. altnost in all the leading EOS.51 1614(1 _T.00. 8. is the tool to improve the vapour pressure prediction.-“ 0 30 aC 0~ a S 0 28 —— PR(kijl 25 20 40 . however. The approach has an additional practical advantage. lime prevailing approach is to assume.1.66) a~mu= T.62). Hence.08% using the Twu et al. is emmsploying phase behaviour data of binary systems comprising of one super critical component.5003 15(1 — T~ 6Suss)] (4. and lime vmipour pressure tiusta tused in correlating it. ‘Fhc mmhove cxaimmplc clcumrly indicates the immmpact of tIne temperature dependent term of EQS on predicted results. How reliable their extrapolations are for supercriticuml compounds? Light components of reservoir fluids. The reduction of computing time spent in flash calculations is highly desirable in compositional reservoir simulations.Ol mole %.aasmml)J and for SRK [39). 1 3 nCs=5.6. nCj~p 1.000 vapour-liquid equilibrium experimental data of binary systems containing a stiper critical compomment. An alternative to using vapour pressure data of pure compounds to correlate a. C =8. the interaction between pairs of non-sinnilar molecumles and/or tine deficiencies of EOS for binary systems. resulting in modified correlations for super critical components [39).(4.3. (‘un/ui. 38.3 MIXING RULES Equations of state are applied to multicomponent systems by employing mixing nmles to determitme their pam’arneters for mrmixtumres. m’.42)10 PR.28%. as well as those by the originuil PR.21m T~o.20n ussexp[O 141599(1 — T. mind nCl6=2. There are abundant density data on super critical compounds. for PR.05.5) a- 32 0 0 ._.29) replacing. with hydrocarbons ranging from C to nCl2 were 1 pressure ofthe umsed to develop a correlation for supereritical components. the need for the use of binary interaction parameters (BIP) in mixing rules.’ Eqniation. see Section 5. 229526 )] (4. The optimum value of a for suiper critical hydrocarbon components was found to he reasonably expressed by Eq. amom = l’ise above approach was applied [41..c of SlaIn’ 4.’s proposed correlation. as the most widely used equation in the industry. conmpurrabic wills that of Twu Ct mil. was found to he 3. with amid ~vitimout BIPs. and it is only logical to expect higher reliability when employing any correlation within its correlated domsmain.s of Stair 153 (4. 60 81) Tempcranure.(4. This approach extends the temperature range of relevant data. in spite of apparent difference between tine two equations. particularly methane which constitutes a large fraction of reservoir fluids. m.37%. The a function. The parameters of EOS are considered to represeumt time attractive and repulsive forces between the tiiolecules. amid time origin~ml correlation of PR. the Stryjek-Vera correlation. As binary data are used in correlating the parameters of EOS. This will allow for a significant simplification in phase behaviour calculations. The success of EOS in predicting phase behaviour using various functiommuni forms for time temperature dependency of the attractive term.. resulting in reduction of the computational requirement for mixtures described by a large number of components.

represented in EQS by paranmneter. Tbse second coefficient. 4.) (4.(4.c ofState 4. imence.75) B=~~x.3.37). is of the quadratic form. B.79) wlnerc k’~ are the repulsive BIP. ‘ hnj = ~ . Statistical nsechanics can be employed to derive miximmg rules for lIme coefficicnmts of virial equation.76) B=Iim(aZ/ap) Using a van der Waals type equation to describe Z at low pressures.78) (b +h~)/2 1 (4. at least at low pressures.. is sufficient to describe the volumetric behaviour.1) describe time non-ideal behaviour of a real fluid due to interaction amongst various comnmhinatiomss of molecules. q = ~ . the coefficients of virial equmation (Eq. perhaps with equally valid argunirents. Tine mixing rule for tine second coefficient. (4. ‘tIme suggested nmsi x inrg rmnle for tire aeermtric tmuctmr. a = (a a.1 Random Mixing Rules a = ~ a.73) As pointed out in Section 4. = It is comssmon to incorporate air additional parameter in Eq. On) ~ (4. tIre imnterumction paramsnctcrs developed h’or any EOS should generally be used only for that EQS. i. h’’ + TIne cisc of lsinary insteraction paraunneter for the repulsive term. which is of an energy nature. tIne mmtsunvc mnnolmmr nnrixinng ruulc is’.rlso umsed Err auxilmuury paranreters suich as tIne vsl mm nrrc crrrcct mum . wlsen the additional parammseters are of the co-volume characteristic. he considered as a fitting parameter and not a rigorous physical ternnm. immstcad of averaging their volumes results in.(4.71)) ‘lime repulsive force between molecules i and j. c=~x. treat all the components similuurly.68) Sinnunhmmrly. For example. tIre above equation results in.)°’ (4. particularly in mixtures with Imiglu conscentratioun of C02 [44i. x (a a ‘ . For reservoir hydrocarbon fluids the random mixing rules (whicim oumly consider time interaction between pairs of neighbouring mrrolecules mmd neglect interactions between three or more molecules) are adequate. used mrs lIre tlmird pmmrmummuctcn ins tIne Sclmnrmidt-Wcnrzcl EQS. The attractive force between molecules i and j. ilenmce. Equnation. of binary systems.c. but has not gained popularity. 2 a..72) 2 Applying the quadratic mixing rule for the parameters of EQS . known as tire van dcr Waals mimixing rules.70) and (4. lim(dZ/~p)= b—(a/RT) p-. For gases at low pressures. ‘ (h u + h )/2 = ~x h (4. lsas also been suggested. 1~ tJsinng hIre umbove descriptions.(4. can be determined by arithmmmetic umverage. lIme rumnrdomns mixing rule of the attrachive term becomes. . the mixing rules for a and b.xB. the third and higher virual coefficmemils can he mncglecled. considering the distance between the two molecules. j. can be expressed in a simple geometric average fornsr [43] as. it should be of quadratic form.1. = (a. Otlmer forms. (4. I).e. dc fi mmcd mr I ~qs.68).74) same form as that of the virial equation at conditions wisere both equations urre vuulicl. b~ = Rb +h. referred to as time random nnixing rules. represented in EOS by parulmsreter h . aij. mherefore.)’’ 1 (4.71) to express the attractive termms between pairs of nnomm—simssnlar immolecules.71) Eqs. a. Musing Run/es 155 . .. by the authors is.(4. 4.O (4. cats uslso be considered. . wlmere B is the coefficient due to interaction between urroleculcs m mmmd 1~ Employing Eq.77) wlmere k is kirown mus tIne hinurry interaction parameter.a. 1 I ‘l’lre binary intermuchion paraummeter (RIP) is generally determined by minimising the difference between predicted anmd experinmnental data. b h” ~ ‘ = ‘ (4. should he compatible witlm that in Eq.69) hence. It can be argued that the nsixing rule tnsed in umny EQS shounld attaimm tine h = ~ .)° (l — k. A mnmixiurg rule simmnilar Its tlmmrt of h is also used for otlmer pumrameters in EOS that contain more than Iwo parameters.)/2Rl-k’~p (4.1 54 4. A RIP slsotnld. we obtain. winch 11 has the characteristic of volume. )~(l — k ) (4.3. er.(4. the second coefficient is deternsined as. ‘ x I’m . which represents the interaction between two neighbouring molecules.. nnainly time saturation pressure.71) describing the interaction between a pair of differennt msmolecules are nsore intuitive than rigorous. B = l’ime urhove mixing rules.

are determined for cads EOS using time availumhle binary data. The most commonly used correlation [47] is. particularly variable ones. That.5.3.. (vn/avuhl) 2~ + ~ ~ (4. I — l’hc fnngmmcity coelficicust is lui~=~-J R’l’ ~ v cuulcuilmmted fnssnnn Eq.(4.74) respectively. ~ and. Values of BIP for the EOS described in Section 4. 1 wlnere V is the totmul volume.b)(v+~ b) 2 lime derivmmtives of tIre two paraunnelers umre obmaitmed as. as given by Eq. and composition dependent [521.2 are given in Tables A.5) . and Ii’ respectively. The application of mixing rules in EOS. Eq. ~ and i-~J~ in PR.v. The results for mumlticomponent systemns particularly within wide ranges of temperature and composition may he quite disappointing. and the random mixing rules is given its the Appeirdix C.. i~u j~u 1 ~ = = ~ i~n ~nn a~ 5 mb = ~nx b~ 1 v—b (v+3. and not at constant pressure or composition. Example 4. such as SRK[45] and PR[461. + ~ [(V + ~nt1b)(\” + coefficients. and the Peng-Robinson EOS are the most widely used equations in the petroleum industry.48.(3. and ~ =0. pressure [51]. A comparative study of ten EOS [53] indicated that the Patel and Teja equation as modified by Valderrama. where n is the total number of nmshes. A default value of 0=6 may be used [50). using the generalised EOS.78) and Eq. It shosuid he noted that making BIP dependent on pressure or composition causes additional comnmplexity in the expression for fugacity of each component as the pressure derivatives in Eq. using the above EOS and the random mixing rules is given by.3l) are only at constant temperature and total volume. as well as general ones [47. 2 2 ~(n a)/an(n a) + (V + ~~umh)(V + ~ nh) ‘~ — — ~~ )T.31) ~mr )r. where k.1. There is no doubt that the inclusion of binary interaction parameters in EOS mixing rules will provides more flexibility. The flexibility achieved by inclusion of BIP. The expression for fuguucity coefficietst. can he quite misleading. The interaction paranmeters between hydrocarbons with little difference in size are generally considered to he zero. Ec . It is particularly a powerful tool to tune (calibrate) EOS for a reservoir flumid against the available experimental data.. as excellent results can be obtained for binary systeumis.80) where. Additional flexibility can also be obtained by making BIP -RT/V dV—InZ (3. Mixing Run/es 151 As the effect of third and higher molecules on the interaction between two molecules is assumed to be insignificant.. the equuumion of state is written in terms of total volutnre by suhstitcutimmg v=V/us. 2 n a= The Soave-Rediich’Kwong.VM.S’oInitnon: k 11 = 0.tsh) The derivuutivc of pressure at eonstuuumt totmml volunmme.3l).(4. the binary interaction parameter so determined is coissidered to be valid for multicomponent systems too.l)-ln(Z-B)(E4. ~RT a 2 ~n x x~a.6. is calculated as. and in most cases reliability at least within a limited working range.4 in Appendix A. It is common to express these equations by the following general form. RT V — bin + nR’l’[nJ(mmh)/an ] 2 1 (V — nmh) 2 2 {~rn~s[~(nts)2 /~n(mmh) ]+ (es. as will be described inn Section 9. An improvement in EQS or a more thorough fluid characterisation should reduce the need to use BIP for hydrocarbon fluids which do not contain compounds of vastly different characteristics. TIne reduction of computational time for flash calculations in tine absence of BIP will he described in Section 5. pressure and all mole numbers except n. hut the values of k for 1~ non-hydrocarbon-hydrocarbon components and also light-heavy hydrocarbons are non-zero. Is = ~lii temperature [46]. ~32nsb)12 1 Applyimrg tire rmnumdomru mnniximmg tunIcs tr calculmmte a and b. or adjusted in tuning of EOS for a particular fluid system.. ilence. are constants equal to I and 0 in SRK.. msRT — 2 n mm V_mlh(V+~nimb)(V+~.(3. 49) have been suggested. Equoiion. only demonstrates a successful curve lilting. 1 Correlations to estimate BIP for specific EQS.c ofState 4.I2).1. ~2. will allow tine calculatisn of commaponent fugacity We obtain.3 I). An example on improving EOS instead of using BIP was shown in Figuire 4. where the constants ~ and 0.~ = k~ .156 4.(3. however. Prove that the fugacity of each connponent in a mixture.. without any BIP was more successful in modelling of the phase behaviour of reservoir hydrocarbon fluids than others with BIP.(4. . lno~=~-(Z.

arrd not he quite consistent with the virial mixing rules. wlmiclm is of ur fornrs simmsilar to Eq. Although additional flexibility that is achieved by increasing time number of coefficients in binary interaction parameters. 2~nrum. whilst reducing tisem to tIne samm’se formms as Eq. 59).)x.a. Imowever. TIne mixing nile.82). partncsnlarly wmth tensperature dependent interaction coefficients. Suhsnituting = ~ (4.x. /nuu—h /b x I n V+~ V + mnö~h nb RTb(V+önmmb)(V+ö nmnVh.3.tlme asymnmns’retric tcrn’m clime to polarity. Non-Random Mixing Rules The van der Waals mixing rules are quite adequnate to describe isydrocarhoum nriixtsurcs of reservoir fluids. The assumption of random mixing in systems c(ntumining higtmly polar mund asymmrmcnric compounds is not justified as the existence of pam’ticsular forces bctwccmm snrnrnc unsuslecculcs. as the volumme of a mixture depends on the comrccnstrmution of its conmrponcmrts. with time voltumne uuttaimring a large value. [a(n2a)/anjl will result in.57).x..(4. reducing the mixing rule to the conmventional ramsdourr mrmixing rule amsd consistent with that of the virial equation.5). have been ~roposed[55.xkx. inn tIre general EQS. y~.(4. a=aC + X/(v — b) = (~~~. It also appeurrs to have mmnaimntained the dependency of the attractive ternim to power three of concentration rcqsmired by the local composition mixing rule. This defect is of practical insterest for umnixtures containing significant amounts of very similar commlponenhs. differemmt expressions for tire attractive term are obtained. inowever deceiving. Modifications of tIme cunhic mnmiximmg rules ho avoid this deficiency for mmmulticomponent systems. known as the density depemmdemmt mixing rsnles. [59) tested the mixing rule of Panagiotopoulos and Reid [60]. tummtcss their partiuul nmnolar volsmmes are very sinmilar.78). and Xujk represents the interaction between three molecules by a cunhic form. and capable of describing tIme behaviour of unulticomponent mixtures containing higlmly asymmetric comnponemrt. is not consistent with the quadratic form of the second virial coefficient .e.uatiours of State 4. Local composition mixing rules address Ilmis beImavitsuir by rclmmtitrg lire attractive term in EOS to composition with a higher order polynromials thats quadratic. represent the interaction between lsydrocarhomns and asymmetric compounds such as water. 12).ero. Fq. i.81) where the attractive terns is separated into two pumrts. a” = in the above will result in Eq. as ajj expresses the interaction between two nnolecules by a quadratic form. [57]. Avlonitis et al. tine model cans fail conrupletely for multicomponent systems [541.82) as follows:.(4.(E4. respectively. Time asymmmnmelric term becomes negligibly small as the pressure mrpproachies 7. l’lse mmhove mmmodification sahisfies tine mixing rules of the virial coefficients. tlmamm lose reliahilily of results by adherimmg to them. proposed a mrmixing rule similar to Eq. the eqsuatnon of state. with time cubic dependency on composition suffers also from the invariance condition 1581. This has been observed in prunctice by varioums immvcstigators [56.(4.. if one of the components is divided in two or more comn’uponenmts identical to it. similar to parameters of B and C of time virial equation. nb) v—b v’4unv~w 1 2 wills I lse furllowing nrr ix inrg rmnIc for tIre a(ldnIionnuul parannrcter of EQS..82). Schwartzentruher and Renon [55] have simown that most of them can he expressed by the following general form. Various expressions have been proposed and successfully tested to himsumry systcmsrs br tIne asymmetric term.(a. The majority of mixing rules for the above term can be represented by the following form.158 4. Eq. may provide acceptable resumEs for binary nmixtures containing these compocmnds. or methanol which is often added to reservoir flumids as a hydrates inhibitor. It is perlmaps a sounder engineering practice to use nnnixing rumles of lire type of Eq. (4.k )/(v — b) (4. Eq. Matirias et al.)’’’ a” [~(nb)/~fl~1TV ~.85) ‘the utbove eqsummtion bussically beionsgs to a class of mixing rules.Sc lmwmurtzentruher and Rcnonm 1551 have sirown that the above inconsistency can he unvoidcd by i nit rsdnncinng ann add it isnumm I lmmmrmmmmmc’hcr. The cubic formmn of conscentrmmtinrn is. however. .(4. Muxnnng Rules 159 x. ansd V= nv = nhZ/B and time conventional random mixing rules for the remaining parameters. They cannot. wimich eI’fcchivcly reduces lIre asynnmnssctric tcrumm to mm qtmurdrumtic forum [55j. use. (4.31) and integrating it hctwcems thue two limnnins ‘the above mixing rule is quite flexible. wimich is tire conventionsal raurdoms’s mixing term given by Eq.84) 2 —an = P (V+~nnh)(v+~ nb) 2 — nRT V—nb .s wlsen umsed in us cubic EOS. = = ~ — (4. a’s’ (4. amid demonstrated that this deficiency causes cnrssmnemrmms prcdictionrs of wmmhcr soluimility in henzcume-cyclohexane nnixture. and ~ which is.s tine himruury intcrurctnon coefficient for time asymnmmetric term.83) ln~ =—lnZ(l—nb/V)+~~~+ V—nh ~u RT(~mö~)h 1.82) for binary systetmis. = ~ = 2n~x~a~ 1 Substituting the above calculated terms in Eq. as.x. may restult ins non-unmiform distrihcutiomm unt tIme molecular level.(4. such as those due to permanent dipoles. that is.(3.82).82) where l~j=-l~i. ‘Flme tssixing rule.

equivalent to the vapour-liquid critical point 1591. Fturtlmcrmmrore.1049 0. Eq.00194 where l and Ut are dimensionless constants.1739 0.3. lnv. Note that if only one polar component is present in the mixture.5248 t). sitsce tine nummmher of binary paramsieters is limited to only three.87) For a binary polar-non-polar system the modified form is identical to Eq.9915 I/I 0. vaunislming of time cubic terimi wisen Ilme number of components increases.0601 (1.(4.00194 0.723 18.160 4.(4. with the results given in Table A.9933 Expt.06(11 0.000402 0.9696 Cmnhend.4.87). since S~. by subdividing water in two identical components. Xp in Eq. lmcmmcc.090 I t).3216 0.000490 0.5243 *Cmnlculmmmed waier is the suurn of tIme aurmomunus un “water I” and “wmmncr 2” n19 0. Effect oh inmvuuriunmmcc comm(liti(snm (so predicted pimase equilibria of C —iI S—C0 —ll Q at 1 2 2 2 i’=3 11.3207 0. overally performed nmore reliably than others.26 MPa 1571. no puirtictular commsptmtumtionmnl nmemnory atscl space reqtuirements are imposed for uilmplicumliots of time proposed nnmodcl.3216 (1 ((. and for water m=0.(4. The authors.89) Catcid. Miximig Rides 161 aA = (4.t)lt)I (tot 13 0 1)113 ()(16() I 0. The detrimental effects of the invariance condition can be demonstrated clearly for a mixture shown in Table 4.0065 0. wimereS~= ~ ilcmmce.3. ‘Y=0. Wamcr~ I’eu’m. eliminmutemi lIme prohletmi 2 completely by substituting xp with S~.00198 0.9677 Calctd. 0. that is. instead of using the generalised correlation.1151)4 0. This also avoids time dilumtion problem occurring with the mixing rule in hq. .1)114 tIlt 114 0. 0 0. For mirixtures consisting of polar components only. - where for methanol m=0.1517 (1.0653 0.8197 0.00350 0.1527 0. The authors [57] applied the mixing rule to tine Valderransa mnnodification of Puitel-Teja EQS to model the phase behaviommr of reservoir fluids including water.3209 0. The predicted composition of the non-polar-rich phases are only very slightly affected by the invariance condition.86) I” anmd “water 2”. and the invariant version Eq. The binary interaction coefficients were expressed by.1 K. mind nmnctlnmumsoi which is commonly used as hydrates inlnibitor. time same binary interaction coefficients can be used for both forms. generally.86) has a nunsher of important advantages for application to reservoir lluids.3207 0.0602 (1. ‘l’he hltmron-Vidal mnmodel [611.8385 0. s’mmsd P=6.0082 0.86). as a(Tr)= (1 + m[I - t (Trf ’J j2 (4.0l62 0. diunx. ______________________________________ — (‘onsnpuuncnt “wmnucr 2” /“wancr I” Mcnluurne }lydr. and T is in K. aA = P (4. ‘fhe musing rumle ~rf Eq.0269 0. C’. Kmrumulscmm Ct uml. 0 1/9 3/7 0.0269 0.0503 (r. I ~ =10 ~—l~(T—273) (4.3213 (1.00326 0. the mimiximig rule amsd its corresponding invariant version lead to identical results. A maximum effect is observed at equuimmiolar annotmnts of “water 0.5248 0.5244 3/7 0. To furtlscr immnprove tine muccuummucy of pu’c(lictiouns of both the vapour pressure and the saturated volunmes of pure polar commmponemsts of water and methanol. . as additionuml smmnnmmmatiomrs of nsole fraction produmcts are only for polar components.0894 0. The above mixing rule. and the term aA becomes identical to aCwitlm polar-polar interaction coefficients equal to zero.76757. should not he affected uudversely by the immvmmriancc condition when applied to reservoir fluids. whereas the random mixing rule with foumr binary parameters failed. The above function will change sign at some high temperature values where it can be set equal to zero.mlcnd. Time prediction deteriorates puirlicumlarly for syslcmsns near the plait point. since 1mm this case tire terms in Eq.r a/Stale 4.(4.00326 0.000008 0. Carh. mv.1517 0.00151 0.8391 0.(4.5243 I/l 0.(4. Eq. 0.52084. I-Iere the subscript p refers to the index of polar consponcnls.67933.86) containing polar component nmole fraction products contribute negligibly. demnoted as “water I” and “water 2”.1530 0.09tu3 1)0903 0. C’mnlcnut. amrd is tine biurmury iustcruiction coefficient. Cmnk’ud.5028 0.6 in Appendix A.9823 1/7 0.=1.000402 0.0602 0. typicmmlly just a few. =x~. S~. 0.0114 0. ‘!‘=0.8383 l/t Expn. however.(23) were determmmined by regressing 5 pure compounds data.00052 0.8391 (1.00199 ‘fine local comnsposition miximmg rules relying on description of non-randonn forces by iimcreasing time order of concentration polynomials are more sumccessful in modeliimsg tine vumpcrur-liqumid eqtuilibrium than the liqumid-hiquid equilibria.39116 0. The binary interaction coefficient should be a decreasing fuimctiomm of temmnperatture as the asymmetric non-ideality reduces with temperature [431.000016 0. sulfi.8382 0.I 0.0284 0. Fqunasionn.82).8(r).86).00036 0. The three-phase equilibrium of the four component mixture has been predicted by VPT using two expressions for the asymmetric contribution.5t$uS Wamer-riclm liquid —— -t3uupn.1531 0.3. 1541 cvmmluated tIne capability of different leadimig mnmixing rules to describe time pimumse hehnaviouur of msnixtures eomstainmimng asymmstnetric commrpoummds by coniparing predictiomm with cxperiummcmmtal data. Commmpulation tiumne is short and is commsparable to that of the random mixing rules.00197 0.0894 0. mv. In mill other cunscs tire predicted composition of the water-rich liquid depends very strongly on tIne ratio of time identical water components.88) ‘fumble 4.(4.9696 1/9 0(100104 t).00)214 0. the constants in the correlation of a(T ). The binary interaction parameters and coefficients were obtained by forcing agreement of the mmsodel to binary data. based rum the principle of minimisation of excess Gibbs energy.

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D.. Part 1. 1993). Avlooitis. 3.6. G. Melhiemim. and Clumney. P. Fluid Phase Equilibria. SPE Res. Mansoori. 99-I 10(1991). OP. 300.c of State 4. 45. M. 37. J. P =2 and o~0and.H.S.. L. amnd 4. 82. Calculmute time vuuhue of criticuml compressibility faclor as predicted by PR. A.164 4. Turek.. 58. A: “Measurement and Computation of Near-Critical Phase Behaviour of a C h/nC24 Binary Mixture”. and Firoozahuuchi. 1986). J. and ~ in RK are equal to 0. A (sine litre cyliirdcr comstmmiurs 16(1.45-61(1995). Fluid Pisase Equmilibria. 1649-55 (Nov. hl.M: “A Modified Pemmg—Rohmnsomn Equation oh State”. 271(1992). 67.. with those of the generalised comsmpuessihilihy clrutrt sho. ML. and l’odd.43 g of nmethunnse at 373 K. 2nd ed. A. Eng. Sisow that tIne vuilumes of respectively.Eng. 35-56(1989). Dcv.S: “Binary Interaction Coefficients for Mixtures Containing lIne n-Alkanes”. Washington DC (1986). 189-237 (1989). Fluid Phase Equilibria. 6. Eds. Calculate time vapour pressumre of normal isexane at 477. Prentice-Hall Inc (1986). D. A. A. Eli.C: “New Mixing Rules for Cubic Equations of State for Iligimly Polar.571-582(1986). Vol. J. 23. 94. N. Lichtenthaler.6. Dumnesh. G. 105. Whitson. 259-278(1991). Des. Todd.R: “A New Generalised Alphimm Fnmnction for a Cubic Equation of State. Courspare tIme calculated values of Z at T =1. 13. 3 1-44 (1991). Todd.08664. and Prausnitz.. 61. Asymmsms’metric Mixtures”. Calculate its pressure uusimrg BWRS. 361-368 (1993). Depmmrtmncumt trf Petroleumusm Engineering. and Cunningham.4. A. 7 51. Sci. E. 10991113 (1967). 3.C: “lmsmproving Predictions of Equation of State by Modifying its Parameters for Super Critical Components of Ilydrocmmrhon Reservoir Fluids”. C. A.M.C: “Comparative Study of Cubic Equations of State for Predicting Phase Beimaviour aind Volumetric Properties of Injection Gas-Reservoir Oil Systenss”.A. R. A. 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References 165 36.P: “Vapour-Liquid Equilibria in Nonpolar/Weakly Polar Systems with Different Types of Mixing Rules . Chem. M. 44. 3. 1221-1233 (Nov. JPT.22. Peng-Robinson Equation”. Fluid Phumse Equilibrium. 40. I: “C . Report No: PVT/93/2 (July.E. Xu.5. 67. Matlrias. Kmmudsemm. B. Huron. T: “Revised Procedure for Phase Equilibrium Calculations with Soave Equation of State”. P. RN. J. Twu.R: “A New Generalised AIplm~rFunction for a Cubic Equation of State. Eng. Experimental Data and Improved Prediction Techniques”.. mnd. and Copeman.. Klotz. 54. J.. T. mumd Kuslemnummaciser. J. and Renon. Stryjek. 300. 11: “Equation of State: How to Reconcile Flexible Mixiusg Rules. 255-271 (1979). 4. Mictielsen.M. Fluid Phumse Equilibria.. R. D. (Sept. Prausnitz. 3. 3: “New Mixing Rules in Simimpie Equations of State for VapourLiquid Equilibria of Strongly Non-Ideuml Mixtures”. Stemrlmy. of 55th Ann. 57. Cimaracterisatioms”.Z. Voros.7. 3. and the “Michelsen-Kisteunmacher to Complex Mixtures: Evaluation of the Various Forms of time Local Comnposition Concept”. J. and Robinson. GA.vn in Fi~ure 2. ~uu 4. 4.. AICIrE.2. Coon.: “Pimase Behaviour of Syslemiss Comprising North Sea Reservoir Fluids and Injeclion Gases”. 39. and Cunningham. Metcalf.5 46. J. in “C . What are the predicted values of tire saturated vapoumr and liquid density? 4. D.. 1-29 (1985). 47. ACS Symnp. Varotsis.G. and Soreide. Teja. and Vidal. umnmd Fiedenslund.L: “A Modification of Martin Equation of State for Calculaling Vumpouir Syndronme” for Mnlticotsnpommemmt Systenns”.. J. 181-216(1994). N. J. 105.. JPT.L. J. and Daubert. 1. Fluid Phase Equilibria. Mathias. Fluid Pimase Equmilibrimu. Tehrani. 58.1. T. Xu. 91-108 (1983). Pu’ovc Eq. Vol. Suuinsm.W: “Extension of tine Peng-Robmnson Equuition of Stumle 52. R. J. J.H. Ser.(4. Twu. E. UK. P.A. Anderson. Proc. 79-97 (1982). 43. Final Research Report”. J. R. Conf. Clssrn.C. mind (‘ioodwitn. Calculation of Partial Molar Volume in Non-Polar Liquid Mixtures”. D. 33.E. and Todd. 3. ACS Symp. J.J. Panagiotopoumlos. 1980). EXERCISES 4.4.H. Stewart. “Reservoir Fluid Studies. 42. 53.. .A: “A Comtmprehmensive Comparison (if Miximmg Rules for Calculations of Phsase Equilibria in Complex Systens. Fluid Phase Equilibria.3. Chem. J. K.L. 1978).. 112. L.13). 38. Danmeshn. A. 38(11). and de Azevedo. Part 2. Eqiiation. 91.M: “Equation of State Mixing Rules for Mullicounmpomment Mixtures: the Problem of Invariance”.. Proc. A. Coon. Chueh. Fluid Pimase Equilibria. 743-748 (1985). umnd Reid. D.6 K using SRK. 49. 47. 59. J.. Fluid Phase Equuhmbrua. 49-59 (1995). 56. 13.. 4. Fluid Phase Equilibria. 60.. 48. 18).M: “Vuupour-Liquuid Equilibria utt lligls Pressumres. 55.11: “An Improved Equation of State”.. Liquid Equilibria”. Elliot. and Firoozabadi. Yarborough. Redlich-Kwong Equation”..s”. and Vera.(4. 609-610(1978).

1 10 Inirprove time predicted result by including the volume shift correctiomn.10.0 K and 12.07 MPa.33).u.C ~ mmnsd nC =3.30%. Iypicuml calcunluumiomns of cqtmilibriunnm conmdilions can be classified in Iwo categories. waxes and hydrates. SRK and VP1’. thre majority of phrase equnilibrium calculations are unruled ommly to two phases.(4. Predict the density of a single plsase mixture csninposcd of (‘~=59.8as calculated by the original and modified correlumlions by tine untutlnoms. a. time conrposiliomn and properties of the co-existing phases at a given set of temperature annul pressure are required. Imowever. Use PRIo estmnra(e tIne fugacmty coefficiennts. us PR for ilC. PR predicts the density of a nmixttnre of C -nC (50-50 mol %) equnuml ks 52(1 kg/urn’.8. The main interest inn dcumhimrg with solid-like phrases. Prove Eq.24% (nnolar) at 311. Isowever.(4. Malimennmmticmml mmrehhnods for calculating vapour-liquid equilibria can also be extemnded to ansy nunrber of phrases. The uniformity of fugacity of each comnnponent thsroughirnut all phases. 4. .c ofSioe 167 Derive an expression for the critical compressibility factor as predicted by SW in terms of the acentric factor. 4 Equuatwuu. and it can also form solid phases of Inydrunlcs mmh cerluninr conn(hihmons of presstnne mind tcmsuperature. mm order ho improve the accuracy of predicted gas soltnhmlmty. Derive the expression for fugacity coefficient of a componcmrt in mm mmmnxtunrc usimrg the random mixing rules and the generalised EOS. (Answer mn Appendmx B). that is. PHASE BEHAVIOUR c ~& L CU L AT!ON S l’hnasc cqtmiiibritunsr cunlcnnlmmtionms for pchr(slcummmi reservoir fluids irray in general involve the Imeatmunenh of a mmtmmnrhcr of flumid mund solnd plsases.9. given so ffieicnt ti nme.14. Ins sunclm cases the overall composition of fluid phases remains uuuuchrmunsgcd mmnrd tIme ImInuse u’qnnitihn inunnn calcnmlationms for fluid pimases can be performed generally imndcpenmdcmrh of lIre sirlith ImInumse. lur line second case. in advance.11. is the determination of tlreir fornmnuntiomn consdilions. The formation and deposition of solid-hike nuateriuml of asphaltic mmumttmre resultimmg from compositional changes in miscible displacemmrcnrt or vutriatiouls in pressure mmnd teusiperature are well docunnmented. using PR. 4. onne hydrocarbon rids and one CO rich. vapour-liquid equilibria.(Mcmmstured m 1 value=297 kg/m ).13. mmt T~=0. such as mnsphaltenes. can be in 2 eqtmihibriutum wills the vuupour phumse.15. Wisen displacing oil in a reservoir with CO at 2 low hcmnperatlnre two liquid phases. to detemmine equilibrium conditions regardless of the nunnnher of plmurses. Also. In Exercise 3. hccunuse the effect of water on the hydrocarbon phase hmeluuuvios’ur cams lie ureglecled ins inmost cmscs. 4. TIre mrinnmher and state of the phases at equilibrium may not he known. Compare the value of attractive term temperatunre coefficient. solids and fluids.166 4. This can be determined by minimising the Gibbs energy. Prove Eq. tIme saturation condition. or tensperature. 4. uunnd uulso by tire Twu correlation.12.69). as will be described. either temperature or pressure is seuurclmcd for a given commupositioms and pressunre. as the requirement for chemical cqumilibrmtnmmn cams be eusrployed. All co-existing fluids and solids in gemnermul should u ltimnruutcIy attains cqui Iurnitnmns. 4. TIne appearammce of two distinct liquid hydrocarbon phases formrred by retrograde condemssumtionm has also beets reported.5. 4. 4. Water in general is alwumys present in reservoirs as us separate phase. In the first cmmtcgory. the soluhility of etbnane and C02 in water was calculurted by uissunsning the gas fugacity coefficients equal to one.

(5. and the vunrimitiomis utre witlmims tIme experimental accuracy in collecting samples.9) (5. usiimg umumnequilibrium thermodynamics.= and z.6) redunces to. I (5.(5.q. ignorimig the heat flux due to the temperature gradient. The dew point is most semmsitive to tIme unixtrure heavy comnspomnents. = y /x into Eq._l)un” f(n”) = — (5.2 N (3.(5. The variation of fluid composition with depth may be estimated by applying tlmennodynamic concepts introduced in Chapter 3.11) provide the required 2N+2 independent equations to determine the 2N+2 umnkusowns of x .h-3). 1 K =y /x i=l. i.) = ~l+(K. become qumite significant for neuir critical fluids.(3.5. by comnhimming time above equations. TIme bubble point is nsost sensitive to time nsixture light components. which exhibit smssall K-values.3) hum delermimse the value of ms~ (or eu. the observed differences are due to imsiproper smtnsphitmg.43) y = K. llence Fq.=y /K =z /K. airy of tIre above two equmrliomrs cams be stmhshituted inn Eq.3) = where N is the total number ofcomponents in the systemn. whmichi exlsibit l. however.10) At umumy tcmnmperumlurc time bubble poimst pressure can he deternsined a.9). Vapour I.6) 5.ce Relman’mu. Eqs. the fugacity of any component. mm the misixture. I.1) ‘lire uubovc cqnmttionm yields a plsysicmilhy correct roust for mm’ hetweens 0 mind I.l) results in. and reservoir oils containing high concentrations of asphaltic nmaterials. a degree of compositional gradimmg should alwumys he expected. ‘ l+(Kn_l)nV (5. Moreover. however. i.6) reduces to.mrge K v. as. and solving for x amid y using 1 1 1 1 x.2 N (5. (5.(3. is generally the preferred form.43) 1 1 1 The material balance equations.(5. . Both approaches will be described in tins chapter.(5. lime mmiixlure is at its hobble poimnt when mm” approacines zero. mrs given by F. s’. ‘lime compositional gradient with depth is often negligible.huikuns 169 Fluid samples collected from various locations and depths within a reservoir ollen show somise discrepancies.2).ulues. or be tremrted uut slcmidy sImile comnditiomis with compositional grading controlled by the balammce of clmeirricutl mind tlncmimmal fonecs.4) x.7) with material balance for each component.iquid Equtiiihriunnm C’afru. N N z(K—l) 0 x. The lack of reservoir fluid maturity cumn also caumse conrpositiomnmul vmnriuntitsmms willrimn mu reservoir as mentioned in Section 1. z 1 = and x. and At equilibrium.uar (‘alemmhnlsunm. The number of variables can be reduced.8) where z . as its vairue nmomnotommically decreases with increasing n”.(5.(5. provided thuit.ntisfy Eq. Time reservoir could also be compartmental. Ilence Eq. The total material balance for the system is. K . ii).43)./K =I 1 amid (5.l teunperatuire T into mm~ immtrlcs of liquid aumd (5.c . uts tIne lemsuperatture mmmrd prcsstmue chrummige with depth in reservoir. liqunid anul vmnpour. Substituting the equilibrium ratio K 1 Eq. with limihed comnmumnicmmtiomms betweems uhiffereimt sections.(5.5) Simmmi lumr cqumuut i(rums cunni unlso he hcri vcd imr tcrmmms of is’ iussteumd of n”. kurown as the Raclsford-Rice LII equation.x.) An iterative msmelhmod is required to solve time resulting eqtmuution. and the equilibrium requircusscnt. y~. Eq.(5. K. .+nv.2) ~z /K > I (5. In some cases. The fluid column can be assunmed at equilihriunn. ~z. 1 and 0”.1 VAPOUR-LIQUID EQUILIBRIUM CALCULATIONS Let one mole of mixture be flashed at pressure P and nn. It can. The equality of fugacity can be expressed by the equilibrium ratio. xj and y are mole fractions of the component i. I n” moles of vapour. 1 1 respectively. Tire followimmg equation. n~approacises I. For kmmowtm values of Ki. in the vapour is equal to thmtt in the liquid. At time dew point.s the pressure at which K-values.12) 1 1 1 Time dew point prcssmnrc is thruit urt wlnicim K-vuniucs satisfy Eq.z y I + (K— l)nv (5..168 S I’Iua.1.nL +y n” 1 i=I. = ~ (5.

00l Connpomrenrm 2: nC ID Ttse convergence pressure at 377.64 0. (20.I0).2). The trivial solution sirounld non he mistaken as time critical point predicted by the equation of sturte.05 0.6 K (220 ‘F) is estinnnntcd from Figure 1)1 000 (Appendix D): PkS psia (34. Eq. z.5. usumng aim equihmon of state (EOS) or K-value correlations. when using K-charts. s=0. The above procedure.08 11.(5.13) 1. K =3. particularly in the critical region.895 MPa (1000 psia). uccordinrg to tIme Gibbs phrase rule. Eq.n.and K =0.K. (c) For mm himumury .89<1. 2 y.9980. P/ruse Be/..02 0. winds have a faster convergence rate than successive substitution methods.4-5) gmve Ihe Cofliposimi(rtn of equnihibrated phases as follows.3 K and 6..(l. psia.ur cohuhutuo. vunpoumr mole fraction: v liquid mole fraction: ~LØ543 0 0457 Eqs. Hence.(3.=0.6 K mmnrd 27.0! 2 ~z.8) should be satisfied.a.895 MPa. and the phase compositions. (b) < I..7504. is sclnemsnumtmcahly slnown in Figumre 5. The iterative calculations are complete when values of check ftnmmcnmons air all smnrmuller tlman certain pre-set tolerances.737.. tIne K-vmrlnucs are constann and independent of the overall comnqsm eon non. have been reported in the literature [3-81. (MPa) K 1 K 2 e.58 MPa (4000 psia): K=l . Various methods to imnprove the convergence rate.6) for the next round of iterumtnon. the solution is reached by iteration. (c) Equilibrium flash equations for a binary system can be solved anahynicmrthy. Isence. — I) (E5. (experimemmtal values K.6) can be used to identify the state of a fluid mixture at a given pressure and lenmmperature.8. Time solulioms of Eq(5. flaslr calculations are relatively simple. For an undersamurated vapour. such as promotion in equilibrium ratio updating. where the compositions of equilibrated phases are very close. ~z /K 1 1 Eq. at the separator conrditions. to be substituted in Eq.4+0.03 096 . (a) What is the shame of mire fluid at reservoir ctsumdimiomis? Use lIme (WA lK.6 K and 27. Eq.(5. 1-5).=l. yet reliable in most appticaiionis.2 umnid I).3. K =0. nnrmuy he tIne oniy mnmatlmeum’natical solution at conditions such as tine eqtuihihriuumim flash its single pinase region. Vapour Liquid Equilibrium calculations 171 Eq.02 1. I. y =O. lii general.1.2 mind I). Eqs. The equilibrium ratios of Ci and nCl0 are then read fronm Figures D. Ii is often a convenienl practice.l) 1 1 2 1 ‘lIne dcgn’ccs of [recdsunr Dir mm hi mary vmupour— Iiqmu id system an equil ibriu in conditions nrc misty two. x. 1 2 1 Eq. A sinnple sumccessive substitution iteration method has been used in time flow chart.(5. 13.(5. Sol.=4~0t)5. whneme the dependency of equilibriuns ratio on phase commnposition cams he msegiccted.00 . The K-values are read frons the charts at 377. or all inqumid. A ressonrable ininnumil guess for a reservoir oil in most cases could be the pressure at which (Kz)C. and calculate the gas mid hiqunid mole fractions. (23.68) 3400.(5.6) estimated from Raoult’s law. K-values vary with commrposihion. witlm an appropriate correlatiomm for lIne vapour pressure. (24.58 MI’a.(5.miio. 1 At low and nusderute pressures.sysncnru Eq. Note that ~zK~ strongly depenmds sn tire K-valmne of nmetlnane.rncdiatc scpmnrmmnor nt 344.=0. lruswever. A reservoir hydrocarbon fluid has been mvuodchled by a nnixnurc of (:1 nod nrClfl (60-40 msuoie%).7) and Eq.’ Component I: Ci (a) ihe experimenlal valtne is 23.(E5. lIme trivjmml soiutiomm. The unhove trivial solution is a major problem in phase equilibriumn calculatiomns when equations of state are used in deternnining the fugacity coefficients.66). The calcunlunted connpositions are then used to re-evaluate Ki’s.263.3 K amnd 6..K 1 3500. was found the mixture nrmay be consm(lcred to be eitbser all vapour. Using Figures T).chrmuris givcmm in Appendix I). an 377.2496. line calcumhatiomm damn hegimm by umsmtiahismng K-values in Eq.(5.(5.47 MPa). TIne use of cquurlionrs of sImile ho estimate hhe critical point is described in Section 5. e.2 using the Gibbs energy mninimisation metlnod. A more rigorous approachm to identify ttse slate of a mixture is given in Section 5.170 5.9) must he satisfied.5).6) yields the compositions of the two phnumses unsing Eqs. Derive the appropriate expression.0027 E49}). or the more widely used Wilson equalion.999. 13 (Appendix D). Example 5. experimental values).(5. Successive substitution methods may prove to be very slow in counvcrgnng to a soltutiusn. The nil is produced through a one stage inher.4) and (5. the fluid is a compressed (undersalurated) liquid. K =0. =0. (h) Calculate the bubble point pressure. due no its high volatility and concentration.4x0. I.50 MPa (3408 psia) [2]. Hence at a given tcnruperrlumre mmd presstnrc. This occtnrs often in tine critical regions. II slrouid he noted ttnan tIne soluntiomm of xj=yi=zi always satisfies the set of equilibrium flash equuuuhiomrs.( 1.6) redinces ho: nV =~z (K — K )/(l — K ) lI/(K. y=0. respectively. using EOS. Its replace mu reservoir fluid by a binary mixture in sinnulumnimng certain reservoir processes inn tIne huhorunnory. x =0. 13=0. The reservoir temperature and pressure are 377. The ushove idcnmlilmcuition is valid if reasonably accurate K-values are used.6xl . whereas for a nwo phase systemmi both At the bubble ponnn Eq. respectively.98 I 0’) 0.l) results inn.=0. If a physically unacceptable root of either n” >1 or n” <0.O020.6 K by iterating on pressure: P.(5.ms .44) 1.l3 1 (x=0.K 1 zK 2 2 (1.80 1. and the use of Newton type metlmods. y.98 0.06 0.4 Checking ~z. respectively. as K-values are known.60 3000.K.0029.g. at 344.

43) instead of solving material balance equationus.58 MPmm. The binary interaction parameter between unethamne and n-decmmmme is read from Table A.050)+ 0. Figure 5.21(5 l9(t. Note ttmat ly.27 inn ~ a 4.70423787x I 2 2. (3) The Wilsomm eqnnmntionr.4 tI. ic ~ Pc amccntric I 2 Mcmlruuiue n-lk’ummmnc i’emrg-Rtsbinnsonn 16.6 tI. 25 h = ~ x h =0. a. a 1 ~ I 2 0.43). Exanmple 5. = (2) A bubble poimmt isressure of 27. 173 The approach is sinnilar to that for flash calculations as shown in Figure 5. (I) l’he properties of Compommemnt I.7 4.25).4x(0. are calculated uisiumg the mixing rules.66).6x0. Vapommr Liquiinl Equilihriimnm Calcuulathnu. However.(mmm Ikgmmmusl) ‘line ii mnmml resu It slusnuId mon depennd on the initially selected value. respectively.043 142.6x0.=0. rcstm Ii ing iii 1 Y= .4.18935786 Tine liquid mixture paranneters. mind K =0.(s K: K =2.1.. Liqnmid Phase: Calculate the bubble point of the fluid inn Example 5.702753115 1.457. 17538971 x8.1.(4.~)= 5 0.oumr (‘a!culotio. Eq.07281059 . The liquid conmpo. 1 . CI.x (a.01923838 MPa.1 It) 0.4x0.74) and (4. the vapour comnmposimion can be calcuiaied fronr Eq. Flow chart of flash calculations using equation of state.m. nC It).4x0. ms )° 1 — l k. mind 377.0004684.70423787 xt).(4.249575l7 5. the pressure is not known inn bubble point calculuntions mmd nmust be estimsmated and iterated in converging to tIme solution. A=5. and Component 2.Rohiunsonm DOS.(4. are read from Table A. Eqs.0lX)l 1(74. amid y.4 x 0. Eq. ~ Fquamion x. Nnunnnt’.(4. Eqs. 17538971 x 1+ 0.6x(8.474.050)+0. I. mis in flasln calculations.18935786=0. The dimensionless values of DOS punrammiemers are calculated from Eqs.(3.0500.6x0.52284853 t).sition renmmains unchanged in bubble point calculations.39665578 0.8t)67.56 617.71576(176 0. is used to estinmsmmne the equilibrium ratios at 27.. (5) TIne Pemmg. usiimg the Penmg-Rohinssomn equation of state.4-6).2.x.27 calculated as follows.650l.c 5.02680134 0. Eq. /~gmot) 4.1.(5.l in Appendix A.4923 lIne EUS lsmnrmunmnetcrs for fluid conmpoimemmts at T377.(rn~ 4. 1 2 (4) The vumisonur cnrmriposimmum is cunlctulated nusilug Eq (3.599 2.4x8.cr Conumpt~ineni MW .~/!.172 5. Connp. is mmot equal to I wtmich only occurs mit time correct bubble poinrh pressure.(3.70423787)” x(i-0.6 K are h 4.0268013440.l7538971 8. y.= K. and 12 11 k=k =0.78). 17538971 )“~X(l-0.3 in Appendix A: k =k =0. Phone Re/nau.23 a MPa.3t)): .7-8).70423787 0.58 MPa (4000 psiuu) is assunnned as the initial guess.29 a.c Solution. anrd B=0. therefore.8!irol. is set-up for both phases.6 X 0.1)9182395 m’/kgrnol 11 5~ a = ~~x.0115 0. b and a. whicln results in the following cubic equmatiomm for (he liquid coummimressihiiity fmmc(or.

.4899 0.92877 K.. if tIne system is in the two-phase region. I.Yi.0426! 0.52 21187 20.=~1(Z_l)_In(Z_B)~ A b B(—2.13 211. (hue to umnreliahle K-values.. Convemstional flasls cumlcuulahiomn procedures.02295 0.(4.5548 1.08487Z-3.34tn8 for tIre vaposur phase.56/0. or complex msmixtures.22 4m 1. q~- .14575 I)uring the iteration of Eq.. be rejected as these will yield negative phase compositions.P 37.029834 (E5.474 1. Agrawmml et nil. fugacities. 1 = ~fL/~vp=(h/p)~fL/4sV 1 That is. 0.9289 0. suclr as tIme one described above.2991 11.MPa 2624 25.Ya. the mmcxl pressure is.92134 0. Applying the pressunre updating mehhod guvenn by Eq. isowever.a.58 0.0285 0.92 21.87 20.1)5 13 1. a series of conventional isolhrernmnal flasir cumlcsmlatitsns mit variosus hemmmpcratures can be conducted. MPa Equation I 27. followed by calculation of nIne systemrm entlnalpy.56 t~’y. it will provide only one rool for the molar volumsme. Alternatively. Eq. are for known tennpcrature and pressumre coirditions.. and concluded that the former approach was mrrore robust.. Hence.003345 0. Clearly the fugacity of conmponents are non equal in the Iwo phases al lIne mmtrove selected pressure. 24. with only one real root for its compressibility factor ctuhic eqsnatisns.. values of n” >1 or n” <0 maybe obtained at conditions where htsth phrases pbrysicalhy exist.9157 fi. 89802.6). ho find Ihe tctsmperature at wlmichm the system enthaipy is unchanged. usinng Eq.60000 2 27.861 MPa 1)113383 1103246 002989 0.. Km’s.02295=26. At a lcnmperahunrc unhove tIme psesudo critical temperature. Z’ = I .04628 0.8932 0. I 9332Z’-2. this advnsahle ho continue tine iheration witim the obtained values as realistic data will generally follow after a few iherations.c : . =(a.294 1 v 0. Comp.02225 The above equation has only one real root (Appemndix C). sunclm ms vaporisuttnon of oil or condensation of gas through wellbore or pipe restmnclnons. tIre systenmr enhlmurlpy nusuny he assumed.re Re/urn tort.082677 0. The values of 1 in”> (l-Kmrmin)’ and n” < (I-Knmrax)’ should.0369010. (ES . 2 3 14 29 tner. albeit slower. l’rcs. hn~. 4s~ 05. 05. instead of pressure-temperature.6292 1. steps (4) to (7) are repeated.98213 K. Both approaches are almost equally effective when optimally implemented [13].J2) a i ‘J —~ Z’ 1.10653 0. In such connditiomrs. (6) The fugacity of each component is calculated in both phmnses. 0.0661 mund B=0. and equilibrium runtios mire urs follows: x. where equilmbriumm’m ratios.3643 22. 0. At temperatures below Ilne pseudo critical temperature.6296 0. or tIne conmnpressihility faclor.04182 0.)” ‘(I-k. The negative flash approacir is mnost effective for high pressure conditions. This approach known as “negative flash” has been addressed by a number of authors li0J and investigated by Whitson and Michelsen [Ii].. P= 22.580-12 b hn(~~_—_~2)B) Z+(l+. y.(5. tlnree real roots for the molar volume at any pressure convergence rates have also been suggested 191.z..40000 . Other methods to iterate the pressure wilts faster Cuhuc equations of state (DOS) can he comnveniently solved by analytical or numerical methods.861 MPa 20.c 175 (8) Now wills the nrew pressure and equilibriunmn ratios...9l57m-0. Tire mathennatical hehaviounr of EOS for mrmultieomponent systems is the same as that for a pure comnrpoummmd. ft. Tlrc analytical solution of tIme geumeralised EOS. — f’ / fV)? = ID’ is far remote from the objective value of <It) (7) The pressure is adjusted for the nexm iteration as follows: At equilibrium. Zv=0. P. 0.3! . 1121 comsrpared tire uuhove approach with the method which solves material halanmce annd energy equations simultaneously. tiasIm cmnlctmlatiomms mul us given pressuire enthalpy.2) where a.97777 1 ~ ..2 1. The results of a few initial.9329 0.2’)..(E5.055569 ~mr 7. this camm disturb time convergence trend towards the solutiomi increasing the number of iterations required. 12). 2 3 14 29 ff.029834 MPa 0.(E4.91638 0. No. MPa $LXP fV MI’u. 1I~: ir) = /~‘ J Root Selection = p[~x~~i~.9774 ~.~. by invoking energy hmnlamrce equations arc requmired.).J2)l) MPa 21 86 21.~. depend on plrase composition and the iteration process can become quile extensive.051(29 0.004)1874 0. /‘lra.000186 0.055615 0.58 0. The resulting error value of ~( I “. ~yi fV =4~”y P. the pressure can be adjusted as.59 24.0985 Vaponur Phase: A procedure similar to that of hiqumid results in A=h . 1.174 Z’-O.. intermediate and final iterations are given in the following tables. CaIr’ulritro.5841 1. The common method is to reject Ilmcse values and constimsume tIre ileruitioun wihhm new physicumhly acceptable values.022228 fV 0.2’) where r is the iteration numnber. is given in Appendix C.97E-07 3.constant due to low heat loss.9828 . 2~xa. at a given pressure. Vapour 1_iquid Equilibrium Cenlculasion. [however.38239=0 5.2 0.03690 0. 1 The calculated values of fugacity coefficients.05E-02 4.24 MPa . K.43E-02 5.5).. Wlren Ihe phase change is due to a sudden or a steep pressure redunctmon.

as described in Chapter 4 for puire compounds. s.3 in Appendix A.04728482 1. The selection of the smmiahler root identifies the fluid as the liquid-hike. Eqs. The general behaviour of typical EOS has been detailed in [1 4j. 4 and substitutiing o =i+~. the intermediate root is ignored.249591 J~ In some cases it may not be straight forward to identify a fluid as vapour or liquid. “0.279 I 2728Z-0. respectively.(4.)” ‘=1.l8). hence the parameters of EOS.18)33 from Tumble A. (0.27).(4.2558l788 1 5 1~ NIPa.23. Is minrd mu.= (I-k. b.lO-ll). has three real roots. P/nate Behariour Calculations I . At pressures corresponding to the maximum and tire minimum niolurr voiummmrcs predicted by EOS. 74) mind (4.447h5879 and B=0. are not knowms in advance.30) results in the following cubic equation.50486716 0.86 MPa. Apply the mninimummm Gibbs energy 3 the proper root.(4.9742 kgmol/mnm’ Zh’-B B(&. i.064.( .2.027622=0 ihne mibirve cquuuutimumn Inns tlnrcc rcuul rtssts: 4=0.07243918 NIi aturd lsmurmunmietu’rs.’presemnns the stumble pimumse with a lower energy level. and the lower and the higher values of compressibility factor (or molar volume) are assigned to the liquid and vapour phases.5. and the fluid is vuilxrur-hikc. is selected. where compositions of vapour and liquid phases urt equsihihriumn are different. It is ohviouis that for multicomponent systems.M. with fugacities determined by EOS. concept to select Whnen at a selected temperuuture-pressure.27 I 0. otherwise.86 MPa: A=0. Wlscmr three roots are found for such systems.(3.394179 Z.5000 1. is regarded as the molar volume when time pressumre approaches infinity.13) RZn4~aBAZh~nB M=~x. Eq.176 5.e. or using the total fugacity coefficient givems by Eq. EOS gives one real root. and tine one which gives the lower Gibbs energy from the other two is selected.3759 mn’/kgmnuol MPa.s. (aP~ ~aV)T_T (a2P”~ I~av)TT — 0 (4. Example 5. The Peng-Robinson EOS is used to predict the density of a single phase equimotar C and nC~at 396 K and 3. only the root assigned to the phase whose commrposition has been used in determining EOS parameters. h = ~x. we obtain.95856673 0.585538 2 a = ~~x x a =l. a 4. —G. thumt root will be expected to be tIne Correct root for time phase under commsideration.6(12(11108 0. The imsitially estimated composition for a phase may provide a wrong single root.. mrs a a b Equations 4. 13) to obtain the expression for the Peng-Robinson 1 EOS.97553625 0. with k.5) Z+~ B 2 z+&iB Ilence..9) does not occur at the true critical point of the mixtuure. respectively.1.394 I 79x 0. will be of interest.)IRT =-0.78).= 0..29 4.a.=0. )(a.(4. ) ‘/a_bj/hI (E4 . Ihe calcunlated horizoustal immflectiomm point by Eq. The change of Gibbs energy can be calculated using Eqs.0I77t)302 0. — loll z~ +~iB)1Zh + p. The pseudo critical condition can be determined using the same criterion as that for the pure compound. That is. (.h. whereas that of the larger root indicates mm vunpour-hikc fluid. as shown sclnenrmaticaliy in Figure 5.(m’/kgmol)’ The above values result in the foihowing~ dimensiommless param~etersal 3. it is possible to obtain a molar volume smaller than tIre co-voluimme.14) and (3.57602453 0.ms Solution: The paranselers of DOS are deternmined for the equi-molar mixture of C.5001) I. Vapoumr LiquidEqailibriunn Caleulatio. (Component 177 may be obtained. =0. ‘fIns shotuld be rejected as the co-volume. With some EOS.109 p p~ kgmmrol/mol M=152.. Zh is time correct root. mire cmnlcun hummed musing time rmmiitloimi mmmising rules.23 a. 4 rn. t Z’-0.3. such as the Penmg-Rohinson EOS.27 4.0l kg/or’ If the above is positive. mm. at 396 K. temperature.86/(t).6704416 1. A b ~ (I ~ i=n N Rejecting the intcrnmednate root.=I’ItZRT)=3. It should be noted that. written in terms of compressibility factor (or molar volume). mixture of . For example.05631263 2 0.280758 Z.9) The above set of equations provide the same relation between the pseudo critical pressure. the intermediate root is ignored. and ~2=IEq.~ ) 1 (5. two of the roots will be equal. and the equation of state parameters.=5 1..07547i77 4 Substituting tIre rsarameters in Fq..4.‘ouuip. the systeimn mumolar Gibbs energy difference at the two roots Zh and Z is determined as. using the Peng-Robinson or Soave-Recliich-Kwong EOS with component fugacity coefficientsas.1.(m’/kgmol)’ a. When EOS.=a.(5.9245282Z +0. Figure 4. volume. Z. 1 (Gb —G )/ RT (Zh Zn)+ In(~~)— A 1 llme deumsity is cmrlcuu Imuted mrs. I) and nC~(Componnent 2).Ot)046 in ln4. Phase behaviour calculations using EOS is an iterative process as compositions of all or some of the phases.1)0831 44x 396)=2.

29). = [I + mnn. which Usmnmg the rmrfornnimut non gives: =397.onrc botnndary.. the correct rool cans he identified by comnlpulninrg Ilsenrr wills tire pseudo critical volsinre 116]. Interfering in the iterative process by adjushing roots.)° — l k. The fluid conditions in cads cell at each time step is detemnsnimred by equilibrium flash calculations. finite difference methods are commonly employed wisere the reservoir is described by many equilibrium cells. = If compuirison of time predicted volsmnrse witin Ilnat of psesudo crmlicunl vunlue mndncmnned time pmcsemnce of a wrong root for the phase under consideration.178 .95 K J’he corresponrdnmmg pseudo crinical pressure is.n. is not the crihical temperature of nine mnxture. Ilemnce.K.nms’Ikgmnrol. tIme nennmpcrumlumre at which the cubic EOS shows the inflection point is tIre mnaximsurn temperalure for nirree real roots. rT. and Imave suuggcsted emarpirical criteriomr ho mivoid sck’ctinng wromsg r.prcssurc. however.2. At temperatures below the pseudo critical teirrperatsnre.4).~ /1 ‘I 6 determnninned in Exummnple 5.a.s slmould pronmrole tine identification of that pirase by EOS as vapour or liquid.g. Z .Iucd line. .s.o77796R(.) us..(E5.iorur Calculations . m is detcrnn. uund clunninating tIme isseudo critical pressure results in. = 0. including the spuriouns (lerivatives nmeuur time predicted two-plnunse 7. Mumthenmatical naselhods and associated prohlenms in solving equilibrium flash equations have (recur extensively sttndicd 117.. Pmhimig et un. The calculated value. it is that of the liquid phase. As only one root is obtained. 4 far away from the correct value. at a constant temperature.0083 144 MPmi. results mr run eqnnuutuonr wnltn tIre psisudo reduced lemperatunre as the only unknown.. using compositional Example 5.mr (~olculatjo. as predicted by EOS.. it will be assigned to the vapour phase.( I ~~(T /-i )° ‘)l’ P unmsd.. rn..9). If time prcdicled root is less tisnuir tIme pseudo cut icmnl volrune.4) NoIc thunt mu.. For flash calcn.) 6~ (E5.0 43759 nmn’/kgnnrol.c 179 The pressure-volume relation.rl.uquirlEquilnhriu. for the correct conrposihiomr of a vapour phase. This can be obtained from Eq. Improper root selection due to inaccurate phase composition. ml. 1 3 where.um.. Solution. amid nC.. tIre estimniated vumlumes used inn cquilihriummmn calculations should he adjusted. 161... Vapour l. otherwise that of the vapour phase. I Rh. b.’ lire nratineunumtical behaviour of mm cubic DOS for a single phase mtmlticomponent mixture. I. What is the maximanum temperature at which the Peng-Robinson DOS provides three real roots for a single phase equimolar mistsnre of C.3 omn a. increasing or decreasing the concentration of light compomment. which is the highest of all.457235R ~‘ = 0.(4. BoIls roots mrnuny well be liquid-like or vapour-like which may correct themselves (luring fimrtlmer itcratioims. mm. 0. snrnuluur to that for a pure compound.. 1151 lsunvc mulso stnidicd tlse above problem. 3-8].9985 MPa Comprcssit’ilily factor Rapid Flash Calculations Figure 5. Punnticuilar considerations have been given to development of robust and efficient algorithms for applicationm in compositional reservoir simulation. lsave been addressed by several investigators e. hum it can be regarded as the DOS derived pseudo critical lenrrperuuunn re (~ ~ (~ ~ Setting tine unirove Iwtr deruvatuvcs eqummul to zero for the Peng-Rohinson DOS results in two eqnuuuninnuis simnmmlmur to t:ri (4. a. Ins the numerical simsrumlation of reservoir processes. is shown by the solid line in Figure 5.(4..27).5. where three real roots may exist. _1_J________ z4zt ___________ ~ _____ r’~’=3. N 4 Estimated Com~. Tine problems associated with improper roots during iterative phase helnaviotir cumlcnilnmtions.i~/~l’. Cheurrly the correct root for the vapour phase is Z . dume ho poorly assigned distribution of components between the phases. is unlso a fnmnnction of lcnnnperuntnmre: Tone Connp~msrlion ~~x x (us. R=0..1. however.2.. uund substihuting them in Eq.mhations mit a givcmm tcnrpcratnnre. as. = . mimuly have an adverse effect oms tlnc convergence [13.silion~. bm=0.4. 1mm the near critical region. is the same as that for a pure connmpounsd. Phase //elulr.) Connnisinnng tire twrr equannomns.1 7014’t46(ur. Time pressure-volumsre 3 relation for the vapour with an initially estimated compositions is shown by tIne dmo. The root is. often only a single root is found for cads plmase.5.. wlnere its conmnposihiomn rcnrains nunchamngcd.immcd Ironnn Eq. t5.

using a quasi-Newton method. a’. a’ I for a set of uu’v muumd h”.16) I If any of time above values is more than its selected tolerance. describing the fluid by a few pseudo conrponeflts.v a — and = in — nvhv a.ns 5.a’.3 equilibriums shows the variation ofof the CPU comntacted time vs. b” and ~V. v and L. where q . 1 Calculate K. winch is often required in the design and operation of fluid processing plants at tire surface. 1 (3) Evaluate check fuumnctiomss. (5. ~ ~ or.3). (5. then return to step (2). 1 Dstiunrumtc time vumltics oh’ um’v. Phase Relnoviour C’alcn. perform an iterative co~ctionof a”. 19-20) and evaluate ~ L and ~V from Eq. N N ‘ a ri —n v. The connmmnomi method of reducing the computational time is to group fluid commmponcmrts (Scctiom~9. The figure demonstrates that the CPU time required by the conventional fornnnniation.17) models and complex iteration procedures. tire imsipleummenmiatiomn of tine method using the Peng-Robinson EOS is as follows: With no binary interaction parameter. t 5 (2) Calculate aL and b . the random mixing rule for the attractive term Eq.14) where: = ~z. Note tinat tIne commiputmitional time decreases sharply for the conventional nniethod when the number of conmponents describimmg the fluid decreases. winch imsdepcndent variables a’V. For example.m. vapour and liquid phases respectively.(4. q~. +q b~ 2 (5. with little additional complexity. I). b” amnd n~’. reduces to. regardless of the nunsher of comniponenhs whmcmn inn hiuimmry intermictiomi parameter is used in the mixing rules (Section 4. = 4. where indices F. and x and yj from Eqs. . otherwise the solution has reached. I refer to tine feed. whereas the reduction for time Micimelsen nsetlnod is insignificant. the total mmtmmber of equilibrium flashes may exceed many hundred thousands. h.latio. is as follows: (5. is about two orders of magnitude Imigimer than time Micinelsen unsethod with no BIP when the mixture is described by 25 conspomsetuts. Vapour Liquid Eqnnilibrinnnnm C’alcm4latio. Si on larly for punranmeter.78). ‘I’he reduction in computational time by employing the .18) paraimmeters of the liquid plnase can be detemnitsed fromni. IS). Hence. as suggested by Michelsen. a~ Substituting the above in Eq. e~ = e 2 = ~(y.) Iv+(~+I)h1 L~’+(l_~h)bi .a’. the EOS Michelsen [18] has shown that the number of equmations to be solved in flaslm emmiculmmtions.(5. 1. a = ~~z z~(aa ) 1 j~i a’ 1 = ( I I — is” Tine computational procedunre.(5. TIme number of components describing the 25 component mixture has been reduced by groupimig them. h~= + Reservoir fluids are conmposed of msmany commmpoumnds. q2 depend on1y on the mixture properties. Figure 5.4) amrd (5. b. T and P as. and summing up for all the components. the number components for predicting conditions a computer blac~oil when with a richof gas at 373 K and 20. 0 q =‘—lnl 0 Ip(v_b)] I RT a’ ql~( 12~ . simulating the advancement of injected gas in a reservoir [19]. T atnd p~ Multiplying Eq. For a large reservoir. the fugacity coefficient can be expressed as.(5.5). b.79 MPa in fouur counsecutive stages.(E4.15) (I) At the given T amnd P. is determined conveniently using EOS at given values of a’.180 5.2).c 181 (5. _____ — x. 1 V umnd mv.(5. ammd a’.from Eqs. can be reduced to three for two parameter DOS. I I (I — ~ (5.20) N ~za~ i=t 1 ) = = (a’) 2 involves only tine three (5. resulting in expetusive compuntation.19) I lence. we ohlumi mm. we get. a~~=nVaV+(l_n~/)at The number of equations describing the equilibriums between tire pinases imscrcmmscs with tine number of components.~/4~.2) by a’i. evaluate a’~and h for emmch component and calesilate a’~’and h”. ln~ 1 = q 0 + qa’. v.) —h ~y. the reduction of computational time of flash calculations is an imniportant consideratiomm in compositional reservoirsimulation. using a cubic equation of state. TIme mmnaims drumw back of unix mmnctlsod is time loss of detailed compositional information on produced reservoir fluids. a’ - e~—-—-~—-—i 1 ( Pv ~ a’ q _~—1)4’~q 2 The molar volume.

nsnuist he known.li~.rul. mis slunswmn inn tIre rmhovc section. FIne rigor(ssis mmretluoh of delcrnnninnimrg tIme cqumilihriuuumm mit mm guven prrs. In stucir cases. Note tlrah dcpendiimg on the mixture composition. ihuis uuppromnclr simonnld ssnfficc for most fluish calculuutionns. at eqnmilihriuin. ( ‘.Stolr. umnrd prccilsilation (if unspinmultennes mmn(l waxes are commnnnon examples. at a given temperature and pressure. one can consider many cases wlncrc mrmore llrmnms two plnunses uunc present at eqnuilibriumnn. It us not generally difficult to idenlify mm reservoir fluid as a liquid-like or a vapour-like mixture froni its cousnposilions. as (~JG)~. tIre sysleos can formsr ommc.8) 00 1(0 Mi.4.fl..9) (3. it is advisable to estimate a~-. ‘. and pressure. hlemmce. (3. cams he illtnstruuted gcoumietrically by exannining tine Gibbs energy surface for binary systemsns 1211.22) The cireck functions in Step (3) sirould also be chanrged accordingly. at eqtnihihriuum conditions leads to the umniformity of lIme clmcmmsicunl potential. and to avoid false snsltmnionns. The proposed method of estimating the parameters of the vapour phase to initimnlisc cmnlculations.r >0 (3...u.r ~r !?c/. aV= aF_(l~~nV)aI (5.nhipnaius. xF.(5. the satuuration pressure cult he cmilcunluuieul rut mu givemm Icnnnlrenuntune.182 . with the exceptiomm of near critical flunids.15) Ilcnnce. g = x p. as shown ims Figtmre 5. 1 . and Liquid L2. Comrsider a himmutry systeurn wmtls lIme conrspositionn-pressure diagraisi.hetscn Cnnvcnrional -. Then the valumes for the vapour will he calculated fornn equurtionrs eqtnivmulemnt to Eqs. two.~ =0. Else clnemmnicurl polcmrh imnI of emucir consup(nnnemrt wutinimmmi phase is defined mis. or three pimases of vunpoumr V. tire prcscmmcc of waler mit low tennrpcrunlsmre csnditions can lead to fommation of a trsnmmmbcr of solid plnunscs of Imydrates mnund ice. Liquid LI.21) ilne umnimnimimisurtion of (iihhs cnmcrgy to delcnnsine tIme equnilihriunm conditions. tire use 2 of binary interaction between non hydrocarbon-hydrocarbon is required. mind (~‘~~)n’. Ilowever. of each component throughout all co-exishimng plnases. clsses nust imnrposc mnny pruuclicuml limitation omn the number of possible phases. Comparison of computatiomnal time between the cooventionuil uund Micliehscnn metisods. in real reservoir fluids.. The implementation of zero binary imrteraction paratmletcr for isydrocarhomr-hrydmocarhon compounds of reservoir fluids is quite reasonable. Wmuher is alurnost umlwurys present no ecervusirs as a liqumid phase sepmlrurte fronn line hydrocarbon ricim liqtmid plrutsc. described in Step (I) above. Tine imumber of phunses at equmhihriumm. as they mure Comnrpose(l of nrranny consrpomnents. g. at constant temperature.2 s’I’ARILJ’rv ANALYSIS lIne rcqsuiremsment of minninrnsnmrn Gibbs eneugy. suds as C0 . -.. similar to those given iii tIne above section for vapour-liquid equilibria. - a . therefore. /‘/r. The above mnodification innproves the rohustnmess of tire Michrclsen mnnetlrod for gas condensate fluids 1201. below its satsmrumtion pressure. 19-20) as follows.rr’. I lowever.rv ~ 2 . discussed in Section 1. Hence.nii.2. In tm flasln calculation of vapour-like fluids.n of plna. to be minimal in such cases. unifornrnity of tine fugacity.niuln~ 01 183 Michelseum method depcnmds also on the matisematical methods used to solve tIne set of eqtuatiouis. The occurrence of three pimase systcmuus in riclu ~ fitmids. (~G I ~mr )nt’.cure and temperature is to find the conditions ut whuicir tIne Gibbs energy of tine system is at its global minimum for all possible co. = and by = hr _(l_nv)bI (5.3. of cmuclr phuumsc cans be calculated from the above definition as. as described in Clnapter 3. for any non-hydrocarbon component two additional equations will be included wInch must he solved simultaneously with the three equations. The inmproveunent could be less striking wills mnretimods more efficienst tirmrmn tIne omme tused ins tire above cxunnmple. A set of nnmaterial balance equations and equmaiity of fumgacity. is the mole fruuctnon. are in general undequahe ho dehemmine equilibrium conditions in tniost petroleum engineering problems.se.3. except br lcann gums nnmixl tires. for fluids with significant concentrations of non-hydrocarbon compomsemrts. b insleundl of tlnsse for vapour. Irowever. as pointed out ~nSection 4..rl. tIre nroluur Gibbs energy.j 60 40 20 5 tO 15 Number of Conrrprrnenus 20 25 Figsirc S. nnay head to lack of convergence for gas comidensunle systcnmss.c and component dislrthulion. P. The fluid is conmsiu Ieru’d ltu turin u t svo Inhmurses. The advantage of the simplified method is expected. TIre Gibbs phase rule. x . This was expressed mnuallrenmnuthically inn Clnuuptcr 3.23) wlmere. 5. the nmtuinmher of pirases mnmmuy not alwusys he known in advance. Imence. 1 + s n 2~ 2 (5.5. mmd cvuuluualed for the liquid parameters.

u. nun(x~5— x~)= nm2(x~— x~) (5. we get.5.1 that during vapour-liquid equilibrium calculations. G = ~gF = ~ttgR + 0 9 n g (5. 5 I Figure 5.30) X~’) mnmn(x~— SQ U x~ )= (5. U U (5. the mixture Gibbs energy will be reduced to the value at F’.5. Schematic pressure-composition diagram of a binary mixtuire at constant temperature. Sen hilit A.r (‘aleudatio.29) Since the mixture F emits attuuin a lower level of emnergy by splitting into two phases of B and D. B and 1).27) and (3. phases with negative mole numbers may appear tennporarily during iterations prior to converging to the final solution witim all of tlmemim positive. The above observation can he used to eliminate non-existing phases in flash calculations. in Eq.24) Substituting tine ctmemmsicah potential by its equivalent.4. lowering its energy level to mlmat at A’. can be calculated by thermodynamic relations.malvsia 5 185 n /n 1 (5. mind the vapour phase V at point D. a line tangent to the Gibbs energy curve. are at equilibrium.23). Composition.(3.31). Eqs.4. using an appropriate DOS. x (àg/~x ) 2 2 (5.25) and p~ =g—x (r~g/ax.(5.26) Thmut is. If it splits into two equilibrated phases of B and D. relative to a reference value.184 = 5. time hiqsuid phase LI at point B.= I) at a valume eqsnal to tIme cheimsical potential of component i at the point of tangency. its Gibbs energy is equal to gFas shown in Figure 5. an ultinnate convergence to a solution with a negative phase mole imndicates tlrat the system is an under saturated single phase at the given . at pressure P1. II was indicated in Section 5. however. Composition. a physical impossibility. = where n is the total number of moles in each phase.4.5. we ohtaium. that is the derivative of Gibbs energy.2. tinat is gF~.31) 02 The mixture A. is a stable sinrgle phase because it cannot split into the two phases of B and D. it nmunst be unstable as a single phase.27) and (5. as illustrated in Figsire 5.c 5. intersects the Gibbs energy axis (erected at x. due to the material balance restriction.5 by ~ and ~ I lemmcc. calculated by EOS. I’or tine litre Imningeunt to mire Gibbs energy surface mit two points. If the mixture remains a homogeneous single phrase. Now. conmsider a imsixture at point F ins Figure 5. and g = G / n g — The chemical potential of each component. Phase Relnauiou. is conceptually shown in Figure 5.) 1 (5.32) 0 which cans only be satisfied if the mole number of one of the phases is negative. as a hypothetical single phase fluid. Figure 5. Imowever. for exaumiple at point A. xi Figure 5.28) Tlnat is. Variations of calculated Gibbs free energy with composition at pressure P1. The molar Gibbs energy of the binary system. 4 mm’’ = mm is(n — (5. ‘l’he nunsber of moles of each phase at equmilibrium can he determined by immaterial balance (lever nile).

will also lead to the same overall Gibbs energy level of gF . As the previously determined phases share tIne smurne tangemnt plunnne.iuur Cale. L2. X. For example. The above conclusion. C gr gi ma TIme hcternsination of tIme Gibbs energy surface and all tine associatedtangent points is relatively mm simple task for himiary mnnixtunrcs. Figure 5. therefore. and flash cumlcumlatiomrs are sumhsequenhly pcrfornmed. only tIre ptruiscs mut K uurd Q.2. witls nhuc nmnixtsmrc cnrcrgy at its lowest possiislc vmuluc of g~. Stability Analysi. the above steps are rcpemmned until all tIme phmuses are fosmmrd to be stable.ul 0 0 I.5 that the tangent line intersects the (. is to be stable. Amirongst all the tangent points which suntisfy nruunlerial balance equuitiorns.. Amy mixture with a composition between those of E and N will split into the llrree equilibrated phases with the amount of each phase determined by material halansce. i’/. been umsed by many investigators to develop nummmerical imirptcmnscnhuutuusnn of stumhihihy analysis[22—24]. .6. A single line can be drawn tuungemnt to tIme energy curve unt points E. reached by examining a binary mixture. at pressuire P2 (Figure 5. The calculated molar Gibbs energy of the binary mixture. thence. is tIme distance between the two parallel planes tangent to the Gibbs surface at the two pirases of y. and x. as a snniqume solution. Note that a wrong assumption of two-phase equilibrium for the F rnixtumre. When iterating on the vapour mole fraction. fixed by the selected temperature. would he innpracticuml. was found to be above the first one. hut trot a practical propositmomn for multicomponemrt systems. 2. only tlnose by the tangent which identifies the lowest energy level mit tIne mixture compositioru correspond to the true solution. as Gmhhs energy curve becomes a hyper sunrface with tangent hyper planes.ase lleha. tluc mnxture nsnay split into equilibrated phases indicated by tIme points os tIme Gibbs energy curve with a connunon tangent. by formninrg tlmree co-cxistiurg phrases. M and N indicating the Three equilibrated phases of LI. mmd iemut Inrg I .0 . A feed witim composihion F can split imrlo two different two-phase systems at equilibrium. must be non-negative for mull possible comnmposilions of nnixture y. All tire above example. Figure 5. Tine mnnctimod developed by Michnelsems 1221 cain be successfuulIy applied to various multiphase cqsuilihriun prohlenms. however.c lead to this consclusion tinat a mixtunre rcnniuuimms a slmnhle sinrglc pInuise when tIre Gibbs energy surface is concave upwuird at all connceotruilionss. satisfy material halansce mind equality of cisemical potential requirements. tIre mixture F will lower its Gibbs energy from gF to gt~. or FN. A plamre is drawn hangenrt to tIme Gibbs energy surface at tine feed composition. X.ms 5. the degree of freedoun is one. as shown by the Iwo tangenrt lines drawns to the Gibbs ensergy curve. Otlnerwise. The (hislunnmce hctweenn tIne two parallel tmmngent lines. 187 temperature and pressure. ssnchi as E-M.I ml mn(I I . Ilcncc tIne Gibbs energy minimisation cannot identify the nunmiber of phases mm thus cuisc. represent tIne tnme solutions. is equal to the diileremnce between tIne clrenmnical polcnntials of each consponent at the points of tangency. so >~ so 1. a negative value indicates an under saturated gas.4) for different conspositions. The same conclusion is valid for nuulticonnponent nnixtures.6. line hammgcmmt plamne criterion has. that is determination of the second tansgent plamne. the original nnixture is stable.7. For a bimrary sysncnru witln mInce equilibrated phases. A so LI) . Its compositiomn is so determined that the tangent plane mIt tlmat point nm tIme Gibbs surfuice becomes parallel to tine first plane. is equally valid nnulhiconrponent systems.33) Composition. If tire second plaume. Variations of calcunlated Gibbs free energy with composition at pressure P2. otlscrwisc it is considered to split into two phases. Both ideotified two-phase systemns. a value higher than one indicates an under satunrumled liquid. and V respectively. that is. Variations of 2 calculated Gibbs free energy with composition at P3.n!atio. analysis indicates that tine tangent plane criterion is a necessary and sufficieumt conditnsn equihihritunir.2 N (5. n’s’. 5~ A p Figure 5. Neverhlselcss. The geometrical illustration. the three plnumse cquihiirritunrn will occur only at P1.186 5.4) is shown in Figure 5. Although in hotim cases the nmsixlurc energy is reduced relative to tIre lrypotinct ical xi ogle phrase cond it ions. line tmnetlsod is sclncnrnumhicahly as follows: :~t. the value of X. For omme of tIne plmases ohtaiured by equilibrium flumsh calculations.2 I uqsu md pluuuses.0 C 5-) a Cn.mrrNrsituon. If the nrixture x. i=l. A seconmd phase is assumed to be present. 4.7 shows tine mixture molar energy as a hypothetical single plnase at presstmrc P3 (Figure 5. Note thrat tIne difference is tiue sanume for both conmponeumts mis the lines are parallel. 3. ‘time crucial clemsmemrt in time above procedure is the second step. It was dcnnonnstrmuted in Figure 5. lIre snurhilily ununmilysis should yield identical results irrespective of the selected phrmise. Irowever. for time tire for wlrere. assummed single phase.ilmhs eurcrgy mixis unt a vuiltue equmil to the clrcmnnncal potcmntial of that component at the point of tuunugency. for all possible compositions.

both estimates should he considered. is at its saturation conditions in equilibrium with an infinitely small amount of phase. A similar behaviour can be eurvisaged by startimmg with a siungle plmase vapour and compressing it to a volume lower than that at B.(3.2 N (5. The method of solution of Eq. mis. as it can be presented by. ‘I’lue umbovc alrpromuch of stabihihy uumruulysis winch starts withm a single phase may become quite tune cinmrsulmnniung whucmr minute thmuimn two islnmmscs mire expected to exist at a given pressure and teunrpcruim tire. avoiding fluid agitation. An alternative uipprouncln 1261. saturated liquid.36). An additional benefit of applying time above procedure is that when the hack of stability is verified by converging to a solutioum with > 1. Examples can be found where suuch initial guesses nmay nniss a possible solution. a saturated vapour. for liquid-like and vapour-like mixtures. but for liquid-liquid. respectively.66) can be used to estimate K values for vapour-liquid equilibrium. fornming a stable two-phase system at equilibrium with liquid. Eq.8 shows tIme variultioru of total volume with pressure for a pure fluid at temperatummes below its critical point. (5. as it Tine fonnation of a new phase is generally preceded by some degree of supersaturation. Furtlmer informatioms on tIme selection of initial estimates and associated numerical nmethods of solving Eq. An equihibriumns stumuly of Ilsis problems umccessitmutcs time existence of at least four phases in typical pipeline conditions. are the compositions of the searched mixture.38) It is not.x 1 (5.37) are given by Miciselsen [25].40) 0. y.(5. This provision could help equilibrium calculations near the critical point where close estimation of initial equilibrium ratios becomes essential.~below its bumhble point value can be inhibited to a large extent by expammdimmg the liquid gruidually.8. however. RT[hn(Py 4~’)_ln(Px 4~)J=X 1 1 i=l. and defining a new variable. that is.2. the composition of the new phase tsnuuy be estimated from. resulting to further expansion of the liquid as a metastmnhle phase.34) mixtures. x./RT) 1 where. I or e suumn ilile. i. the reduction of pressure results in a stable expansioum of the undersaturated fluid down to A. however. where y. and the two tangent planes are identical. suds mrs at time semi bed lcmnnperatumre in offshore production. with fugacity coefficients 4~’~ and n~X.37) is similar to the conventional two-phase equilibrium flash.27) and (3..(5. The Wilson equation.35) (5. For near critical fluids wisere the nature of fluid cannot be clearly identified. and ensuring the lack of umsinumte gas pockets inn the liqunid prior to the expansioun. Note that Y is not the mole 1 as described by fraction. For a two-phase vapour-liquid analysis.. but can be interpreted as a measure of the mole number in phase. hnY +ln4u~’—Inx. and x. 4 Expanding the above equation.(3. as discussed in the negative flash approach. Eq.37) requires a global search. or solid phases otherestimates are required. .Y/~Y we get. y. X=0. Phase Fk/mausuuir (‘a!cunluutiunus 5. The formation of tine vapour pinase at point A mmnay.3(n) i=l.respectively. wax mrumd musphmahtenc phunses mime a strotig possibility.e. uit lemust llmrcc ptruuses of vmulmounr.(5. Y . yl ~‘.37) Stability Limit I at all solutions of the above equation. Figure 5. and then search for the non-existing plmases using materiumi humlance restrictions. Al low tcmmnpcmumtumre conditions. the mixture.seimt. iii I ranspoitmitmuir of iumm~miocessed well stream fluids through a pipchimmc. in time above. Michelsen [251 suggests that the initial estimate of the new phase composition is not crucial. = K. based on the tangent plane criterion. restricted by material balance equations. and water are generally pre.(5. At Ienrperature TI.188 5.2 N (5. lime formnnalmum of lmydruute. x.. ‘nm 1. 1 Y~ =y exp(—~. sinown by time (lotted line in Figure 5.. iS to assume a reasonable mnuiximnsum nummnher of plnases at equilibriums.28). Stability limnmit for mu punre fluid. Such systems are metastable with an energy level which will be redunced by fornming a new phase. The bubble nucleation in a liquid at a pressnr. the converged K values may provide 1 appropriate initial estimates for suhsequment flash calculations. and pure phases only composed of the lightest or the heaviest components can be selected for hydrocarbon Vohnmune > Figmure 5. Y /x =~/u~= K 1 1 1 (5. y. Eqs. as one could converge to the trivial solution of y=x. amrd tlre feed. Further expansion should result in gemnermution of an additional phase B. Stability Analysis 189 Substituting for chemical potential.—ln4~’=O 1 The mixture x is stable provided that indicates a non-negative ~. At ~ = .39) A or Y 1 = x /K 1 1 (5. Imydrocarhon liquid. Locating all the solutions to Eq. be inmhihited or delayed.8.

They are all equivalent to describing the tlnermrrodynmummnic stability limit as the bound outside which entropy will decrease in real processes. wmntn vunrnuuhlcs ot tenssperuuutnre unnd voiuumnre. The above criterion cans be expressed in ternsms of other energy [saruumrncters. -.0 . Ann increase of x will force 1 the mixtunre further into the metastable region till it reaches poinst N. amid (5.1229661 v’. Whereas in the latter. at poimits D and F respectively. 5 u Figure 5. see Section 3.120877 5t)7. winch will not plnysically occtnr except at the critical point. This behaviour is also predicted by a cubic equation of state. that the hinodal curve and tIre phrase envelope meet at the critical point.190 5.spnooc/al comes. A similar argument is valid for compression of thue vapour passed E. a 2.O. Iat.i-0. we obtaiur. when time phase change is neglected. are called tine .t .683527 h 4. sumuin mis lIne Iheimhohlz or the internal energy.Stab.1. .938436 a .e.5l70t2 4. it can remain as a mnelastable simmgle phase.sic stability as timey indicate thue houundary for ml urnetuu. For a punre comnipound at coimshaunn tempcratunre lIne above reduces to. Note nlmunh tIne gmup between the upper and lower imntrinsic stmnhiIity limits decreases witln temoperuittume unnrd vuimnishnes attire critical point. .ns 5.9). dA~i’shV I Figure 5.26205757v’. we ohtminn. urn tcrimns of mIsc Helmholtx emmergy. Intrinsic stability limit of a binary mixtuure al constanl pressure and lemperatn.(3. A nnmuin applications of determining tIme inntritssic stability limmnit is inn determuuinmulnonn of tine criticuul point by an equations of state. 120877 nsn’/kgmrsol. tine slunhilily hinnit nod lIne phnunse houmnmdmiry coinrcide mrt tIre critic-md point. a violation of the second law of thermodynamics.0 K. respectnvely. a a.1. It was noted in Figure 5. The condition of intritssic stability is a suhcase of the tangent plane condition. This feature has been used succcssfumlly to detcrimninse time critical point of nsulti connponent systemns. whereas the tinird and fourth roots represent the volume limits Conrposilion.So/mution: Dcxc ruhunug nine snmntrnlnuy tm. a global searcin is requuired. - m’~ m ~1I’~.= 0. The expaumsnonm of tine liquid phase passed D should result in increase of pressure which is not nncchuusicmulhy feasible.23 t.55 1) x 5 v=-0.0 K as follows: Tc l~rluiatnOn Pc on . line curves formnncd by the two limits at various temnnpermntumres below tine criticurl temperatumre.(3. Tine detemninmation of intrimnsic stability hinnnit provides immformation on time limsnit of supcn’satunratiour of a reservoir fluid in a depletion process. where.hiy Ana/v.22 0.9 shows the stability limit for a binary system on lIne Gibbs energy plot mit crsmmstamnt pressure and temperature. tIne fornnier cutn be identified simply by evaluating the ‘g’ surface at the feed conditions.8. (IA at which the reduction of Gibbs energy isjust to be violated.8). Tlnese points nrc reIcrred to as the hunnits of intri..(~.1. on the isotherm as described by FOS.( 3. . mmmd rigorously calculated using thermodynamic relations.nsut cm uncruonn. That will he the hiusmit of intrinsic stability. Ilcnrce. The muhove descriphion of mnecinanical sturhility for ml pure sumhslanrce is mm spc’c’imnl curse nsf tIne general criteriotr for shuut)ilihy mrs givemn by Fq. using uhe Soavc-Redtich-Kwoing FOS (SRK). one negative and the other smaller than h=0. 4 v +(2Ir — 2uu/Rl’)v 1 2 + (h + 3mnh/ RT)v’ — ah tm /RT = 0 lIne FOS p~nrunnrmdlcrsbr nucsnnnn.6. tlmat is.2. umsing SRK. as showmm in Figure 4.OOl 20518=0 wittr the roots as: ~ LI A . sinsilar to those inn Eqs.066I55 Snnbstittmlinrg nIne vmulues sf a mnnrch h inn the above equation results in.crs 191 Assuming a continuous transition from one phase to another.6 3. 2 2 (d A/~V )~ = ‘_~ (t)P/t)v)~ =0 mm ‘I Iran us. mmd hIre nsmixtcmrc nnuumst split into two phases of B and A. 2 tI G = 0 (5. —4 22 2. whncre mm iimtlcctksms point on the g curve exists.(m~’ ~mnno~)~_. Note that while the nnixlure F mmiush form two phmurscs of B uunsd A at eqtnihihrium to be stable. Eq. I’hase Be/nanwur Caleunlatio.25 0. Prove tlnat 11w unccinanicat stability hinsrit for a pinre compound.79623 no’/kgmnmol 4 TIne firsl two roots are non acceptable..41). as both the hinodunl cuurvc and tine plnmusc envelope camm be expressed by energy terms.8.41) = —Suh’l’ l’dV + ~~t~Inn. i.n.nre.uI lucxmmne are cuilcumlated at 473. v’.1)25 1)2659 4. will be expected.30412 mmm’/kgnnmol v = 0. ntuc stuuhilnny humus for the vunpoumr aurd lidiniud phases of a pure compound lie at lIre nrrmnxnnmiumnm and nmnnnnmruumnl pressunre values.9. as shown in Figumrc 5. line immnrinrxic stuulsitmty liuuuil .stuulmle simrglc tluase fluid. I 2). a minimum and a maximum pressure. Indeed.06014 v~=(>08275 nn’/kgmol nmrVkgnmol v. Find the stability hinrit of normal inexumnne al 473.4 I). as described in Figure 58 cair he derived by tine genreruil energy concept. Calcunlatimng lime derivative of pressunre with respect to volume at constant temperature. is tIne cunuditiomn Exanmple 5.

against experimentud datum. Mixing rules. A 0 =0 (5.14). Therefore. they fail the whole purpose of tire exercise.(3. have also been suggested [28] to predict critical properties.4 I).192 S.l2).l48 MPum 5.. X . (~. incorporating experimentally determined interaction coefficients.33% and 1. Practical examples are miscible gas displacement fluids (Chapter 7).42) 01 A . immstead of time Gibbs energy.(l. is deIimmc~as. Estiunsurted critical properties of these siunple mixtures are useful in designing mixture compositions amid test conditions.3). however. A — (a2A ~ I ~Jms. is any pseudo critical property. Tine approach is not only more reliable than using empirical correlations [29). pressure. Later Miclrcisen mmmd Iheidensumnits [32] proposed a more commnputuitmonally efficient procedure to solve tine above equnurtioums pam’ticumlarly when all binary interaction coefficients are set equal to zero. but it can he quite useful in studying the belnaviouir of nncar critical volatile oil and gas condensate systems. The most common approach is mnolmmr mixing (Kumy’s rule). [27] used a modified Wilson equation successfully to describe the excess properties. 1 5 P =0. in comparison with the experimental data. The critical temperature is particularly valuable in designing tests to simnuhurte liquid-like. /‘lna. The metinod requires the evaluation of third derivatives of the Gibbs energy with respect to concentrations of components. hence. The main disadvmuntage of all the empirical methods is that the predicted critical properties may not be consistent witir the fluid phase envelope as predicted by EOS.(5.Eq.. oflen binary systems. however. Model fltukhs. The method was evaluated by predicting the critical pressure and temperature of 32 multicomponent mixtures.14) I-Ieidcnmrmrmmn mmmd Kimahil 1311 proposed applying tine criticumi point criteria as stated by variations of I Iehirnlnoltz ennergy. or volume.s 5. are unique and can be ktcnmtilied relatively reliably both experimentally and also by variotus predictions rnuetlmxls. or so-called tuned (see Section 9. The Gibbs criteria for the critical point lead to the semrrch for a stumble point wlnicin lies omi time stability limit as schematically shown in Figure 5. 1 (1. and O~ is the critical property of component i.‘uIs(’al!‘oi.. J (5. using EOS.nt Cah-uilatioums 193 for liquid and vapour phases. studs as temperature. respectively. using EOS.3 CRITICAL POINT CALCULATIONS Variations of fluid compositions in a reservoir mmny result in tIme critical stumte. . ~ mu’e time second chcrivmntivcs of tine total Elelnnmholtz energy with respect to moles at constunmnt teurtperatumre mmtnd total volume.ce flu’/nai’nonj.. The critical pressure mmmd temperature of a mixture with fixed composition. The definition of the lleltsihoitz energy is given in .?.3 1%. computationally quite demanding. which fornn elements of a number of high order determinants. hut also provides consistent data with the phase envelope predicted by time same EOS. Peng and Robinson [301 applied the method by calculating the Gibbs energy derivatives using the Peng- T.4.46) Robinson EOS.me critical temperatture is to use the Li’s mixing rule (33): where z~is the mole fraction. can be applied to predict the critical point. ~0. ~O. = ~XT (5. Determination of the lrue critical point of a reservoir fluid mmrmmy nol be of mnntnciu imntcru’st to ml practising engineer. The concept of excess critical property. and it can he calcunlated. becumuse it leads to less comnplex equatiomss when pressure explicit cubic EOS are used: A A L= A 21 A . or vapour-like behaviour. particularly if the equation of state describing both phases is to be calibrated. defined as the difference between the actual value and the calculated value by the ideal mixing rule of Eq.43) 55 where.44) ‘l’inumt is. A 00 A A A M= 0 = 0 (5. Rigorous thermodynamic methods.8. Calculations of vapour-liqtuid equilibria for these flumids neuur the saturation pressure is difficult. are frequently tested in laboratories to investigate fluid hehuiviour. =~z O. There exist numerous conshinations of mixture comnslitunents wlnicin pi’oduice crimicmmh tiuids mit mmmsy given set of pressure-temperature in multicomnnpomment systems. Tine true critical properties are. (‘a/s’nu/atiønu. 0 . respectively. A sinniple nnethod to estimate tire trn. has been used to predict criticurl properties. Simple empirical correlations arc adequate in most curses. The pseudo critical properties of a nnixture are conveniently calculated by mniixing the critical properties of its constituents. A kumowledge of the critical point can be used to identify problenn areas and avoid unnecessary numunnerical complications. simnilar to the Gibbs energy. different from the pseudo values. The associated pressures umt lIne stmmhihity limits can simply be determined from SRK by substituting tine values of vnnlumne ammd temperature. 1 . and flumid colummmmns ins reservoirs exhibiting severe compositional grading with depth. which resulted to the average absolute deviations of 2. which will he discussed imm Scctiomm 5. 1 (5. Tine comnputurtionah effort in determining the critical point by EOS is comparable to that of an equilibrium flash [13). and expressed by Eq.. Teja et al.45) ‘time cifcclivc cotmecnmtrunl ionr.6995 MPa P =2.

‘Ilserefore.3377 0. lise prcsstum’e also clnaunges according to tIre hydrostatic head for fimmids mnn rest. I simows tIme lluuid comunposilion of a Nom’th Sea reservoir at dnfferent depths [37].12 or Figtnne 1)1. for such syshemmns. Tumble 5.872 0.49 318 2.2585 rn’/kgumroh result inn an unacceptumble value of P.88 1.61) (168 207 (1. Sucin ur nsajor clsange of cotmipositioun cannot be ignored as it strongly affects tine estimation of n’eserve. comrupositionrmnl vunrialiomms witlnins u~reservoir. Fluid t)epnlr (owner sutssea) Nilriigen (mnilniir t)ioxidc I). when the thermal mnmnd unmeehanicumi eqtuilihu’iimtn mmre esnurislishned. I 2 clearly demnonstrates such conrplexity as the mmnixtrmre critical presssum’e is mnnosnly Iniginer thrmmmu those of tIme conrnprising connmposundls.1)8 9.27 0.48 B.1)8 399. and even mumch luighier ins cxtrenssc cunscs. Phase Fleluii iou.74 0.18 151 0. Welt 2 3 I 56 059 2. Fusr a single plmase fluid.32 4. It wmus ~ si msted omit IInuit lateruil ammch vertical cotnnpositmonral varimutions witlsin a reservoir are expected dumring tine early reservoir life.7. Note Ilnmrt tire nniethmmmne cusnmccntration iuas decreumsed from 72. respectnvely.1. the above mmssumphion leads to the uniformity of tunguneihy of curds counnpurnrennt I Irronmgirsmmt all co-cs ntinng plsases mrs the requmreutrent f(sr the chnenmnicmil eqtnihihriunnnn (Section 3.25 55.04 0.96 2. Mixtures containing methane were not inclunded in the cvmiltnmntiotr.ics Itepumines (k’nauies N on mu lies )ecajnes I .4 COMPOSITIONAL GRAI)ING I)~ =~ + (5.s 195 where z and v are the nmohe fraction and critical molar volume of component i.m. 290 0.sa. tIne mniixturc is expected to get niclmer in ineavier compoumnds. Tmuhlc 5.33 1.18 5.0597 0.261 t 1)0995 (3.194 5.6622 l~utraiuc tbnspa ire n. that is. A simplified correlation of Kreglcwski and Kay 1351 can be used to cstinnumutc tlne criticurl pressure as follows: Snnhstilnunirng tIre above values ins Eq.93o)[~~ 1 — I]] (5.02—0.48) Esmumate the crntncal properties of a mixture of ethane-normal heptane (6))~4()nniole%). hecurumse of lIne lmrck of reliability of the correhatnon. 1 1~ TIne method was tested for 135 binary hydrocarbon mixttnres. t0444 0.nn’/kgmnm~ 5 305. Vmrriations of fluid c~. cunn be used for rough estinualiotn of line eniticuul pressure of mmnixlurcs commtmninnimsg usnellnmuine. I). tine umnifommity of fugacity is eq iiivurlcnmt to tIne munmi fornnn ity of Cource mutrunt ions.nme cmulcmnlumted by Eq.8768 . Whemm tIre reservoir is comnsidered mahuire. Oume mmiight expect time reservoir fluids to have attained equilihriunii nut nsatlmrity due to molecular diffusions and mnixing over geological times.0 [36). stmilar to other available correhuitions. (‘ith’ulatjsou.12 8. In gencrurl.22 MPa which is in reasonable umgrecmsment witin the reported vunlue of about 7.3 bar [29].L~ 0.75 . The lennpcrmuhuumc inucreumses wills deptlr wills mu gradiemmt of umbotit 0. itowever. Figure I .03 K/meter.ane T./P. t 398 0. line locus of critical points of binary mixtunres as shown inn Figure 1.6000 0.n.1 260 0. tIme dhiffUsive mnmixing may requnire many tens of million years to eliminnate cornspositi(snal heterogenumities.4000 0.79 4.62 61.tS etim~ne n.74 2.923 t . whereas the pseudo value of 399 K does non.096 4.27202 0. whereas the gas condensate dew p(nimnt imucreumses wihin inrcrcasing Iremlvy fractionms. with depth .47).w. uunnd lIne critical volume of 0.Jv. luswevcr. 5.x. The oil saturation pressure generally decreurses witlu dccrcumsimrg mnretluumne coumcentration. The pseudo critical pressure of 4(12 MPmi is nrnumrkedly deviated. 540. The simple molar averaging of critical compressibility factors of flunid componmcnls gcnrcruilly provides reasonable estmmates for hydrocarbon mixtures.808 + 4.46 A.47) wimere p~c and p c uure the mixture pseodlo crinucuml pressure anrd tcnrupcrurhn.It ulanc in-13 ninmmne n-t’cnnmrnc 54.=4.30 nnole% to 54.03 MPa.K 72. it is often assumed nlsunt fluids ase at equilibrium.(5. temperature and pressure can be used to predict the nsixtumre critical voltnmrme.53 2.11 357. Welt I ‘1136 v~ =Z. The pressure umnh lcnumpcrunltmnc. 183.09 11)9 t.22 The calculated critical temperature of 461 K agrees wilts the reported value of 460 K Sicitectitmir Wenghin th~asiicsiaj..MPmnv . sumch as methane.8625 59.83 1)61 1 79 (1 75 086 113 1)92 054 3 28 5 49 33. t 712 0.94 m 24 2. respectively.RT. Solution: The properties of pure conmiponenls are reund from Table A. 103. Applyimrg Pr=Z.92 mole% over a depth imrtervuml of only 81 mnmetcrs. and using the nruolumr unvdragl’ comrnpressihility faclor of 0.80 MPa [36).428 xT.0873 0. irncreasiumg to IlK for mulhicommnponetml systems [34) Empnrtcal correlahions generally fail to predict the criticuil presstmre of multicommiponemrt syslenrns as its relation with the concentruution of fluid components is highmly non-hioemur.tccmines Plus 2.03 1.RT. Example 5. I in Alslsemndix A.019 x. Welt 2 31)11 0.85 5. At tnnnifortni hcmsmperatuure anmd pressure. we get P~=8. and (I) us Use nnsoluur avcruuge acenntnic factor. particularly those with a tall eoltu munnr oil fbi id shromn Id he expected.14).c 5 1 (‘iou-al Point (‘aleu!atio.14 2. containing less of light components.19 216. The estininated critical com’uspressibilily factor. (5. using the critical properties of pure constituenhs and reasonable unixing rules.02 6.4 285 0.50 0.47 1. umre not tmnniform tlmroughmout a reservoir. ansd production planning.2585 Sum I tc.87 2.18 8.30 8.1455 0.3495 0.8722 etinane n-heptane Pc.6 267 0.66 2.( 1.2793 -.1995 0. The variations of composition and temperature of fltuid wihh deplim resumlt in clmmmngcs of smutinrmnliomm presstnrc with depth. Well 2 3217 0.8480 64.2720. mumnil average values are calculated as follows: x I) (iS 2 56 C.91 6 00 43. Appcmrdix I).16758 0.71 3.6(1 2.76 460.44 Mcntummnre cornponerutT.l~pi.U~nsmtLoms with deptis iii a reservoir.2 ~I 2. with aim average deviuution of less than 4 K. The correlurtion estimateh the critical pressure of 967 mixtures with ats averurge error of 1.92 9.hamjsJn~osLucs Motceutar Weigtrn Specific graviny 10.

due to the hydrostatic head. respectively.10. MPa Saturation Point t).10. M is time nnohecular weigint. by going through a local critical point. Fluid Deptir(meuersubsea) Measured Reservoir Pressure.0 1.2.2 [.4 I 380. m /m’ Tank Ott Specific Gravity 397. MPa Separauor Temperature. The variations of properties of the reservoir fluid. 71 ~t~’ = —(Mgim”’ — Mgh’ ) — (5.0 0.8254 which reduces to Eq. the cmnergy cqtnat mum.4 33. Pressure. however. The uniformity of cheusnicuml potential oleumcln conspoTment througlnout the system. wills deptis are given Table 5.8 MPa at 25 meter urhove that poiumt. Eq.2 N (5.(3. will he replaced by.8 53t).8 185 The variation of composition with depth in a reservoir can he predicted by assuming equilibrium within the reservoir.2 400.35 382.7 37.3 MPa at a deptin of 3181 meter subsea. kg/rn’ Saturation Pressure. hut witln mmmi additional energy lerns due to time gravity.50) wlnere. Furthermore.o . the gas oil contact is expected to appear at that point.rilional (. equality of fugacity. + 1t Mgh ’ = ~t~’ + M. Ikncc for two points along the flunid colunsn. The estimation of compositional grading insight help evaluating the reliability of fluid samples taken at different depths. as slmown in Figure 5.rlcnt equnrtiouis. kg/rn’ Separator Pressure. or tIme prcscnscc rf mm mmummmbcr ol’ isolated reservoirs mistaken as a single reservoir can also be invcsligmmlcd. no gas-oil contact exists in the reservoir.unmn Asstmnniphion Assignsiung null avcrumge lenupenuil Lime t(5 tIme Iluid coiuuuumnn murder comssidcmuut ion.gh’° = i. I~quilehr. Pressure.(3. however. fiO = f2l~~p[~5~__— = Table 5. that is. Well 2 39.22). A more rigorous approach. is tire nmsunss of tinc humid element nut tIre height h. \ \ A Gas t’miuti. 2 RI’ Inn) f’’ I f’ ’ I or.2 1. due to time developed density variationms within eacis fluid column. Furthermore dispersion emma stromigly affect the (ruinslen processes in these reservoirs. and g.(3. The fumgacities can be calculated by Eq.4 6. The reservoir pressure was above the saturation pressure at all depths.4 C. W(nemn tIne composition of a fluid. RT 1. with compositional grading in both phases.5 285. when the two points are at the same 290. can becourme the dominant factors in controlling tIme conspositional variations in cotnparison witln tlnose itmmposing therniodynamic equnilibrium. and no gas-oil contact was observed in that reservoir. described in Table 5. tine pressure and temperature gradients depend on flumid flow characteristics and cannot be expressed by static gradients.(3.0 Dew Point Densimy at Sat.8 Dew Pu. It shroimld be emphasised that tine ummetinods are applicable to static amid non-depleted reservoirs. and reversible thermodynamic relations are mixed to nrccount for the effect of level. MPa Measured ReservoirTemperature. hence. I’oimrt 546.2.)) 573.9 390. Phase variations in reservoirs with compositional graditmg.89 379.3 Dub. time fugacities of all its components are known at a point witinin the reservoir.49) “ where on. the fluid composition and properties at hifferent depths can be predicted when this inforniation is availmible only within mm limimited depth imrtcrvmml. In this approach the coupling of thermal and compositionurl gradient is ignored. The fluid can.jnnt 503. ~VcII 2 217 45. I 611. ~ ‘~.4. In producing reservoirs. Point 540.9 304.)) 0. WetI 2 3I8t 44.8 37. will result in equiv. Note that the hydrocarbon mixture has a bubble point of 37.24). and the superscripts refer to various heighls with a total number of selected points designated by t. the forced ammd natumral convections. Both approaches are addressed in this book. If the saturation pressuure at any point becomes equal to the reservoir pressure.1. I).4 1005.15).0 0. time shift parameter should be .93 384.t~° + Mghi°> (5. for a fluid nut dE= dU + d(mgh) umccclenuitksn. Applying thernnodyumummrmic relations.52) Im~1 iwl .1. is the graviturtional Pressure Pressurc Figure 5.9 557.53) Rub. we oblmiin.mdung 197 The pressure in reservoirs increases with depth. Eq.)) —Mghln’’ — In’’ I (5.7)177 3156 44. If the saturation pressure remains below fine reservoir pressure at all depths.7 3m t). whereas it shows a dew point of 37. similar to the mmpproach used us Section 3. I’hase ite/nar’innmr Cnlcuulation. 5 ‘C Separator GOR.(3. the comnposition at any depth coumld be determined by using time above equation. K Density at Res.i’.25) using EOS. (5.0 - A.6 308.2. behave oil-like and gas-like at the low and high sections of time reservoir. Properties of fluids at different deptIns ins lIme Nortlr Sea reservoir.1. Well I 3136 44.0 0.5. (‘onnpo. pressure change. is to relax the assumsuption of equilibriuumrn and apply irreversible thermodynamic concepts by considering the coupling of heat and mass diffusion.196 5.8 170 0. In reservoirs depleted below the saluration pressure.ici ~ (lit ‘ I Oil nest reduces to. ‘line possibility of existence of an oil column under mm gas reservoir. on the equality of chemical potential as the criterion of chemical equilibrium. When using a two-parameter EOS witin the volume shift. we get.51) Expressing tIne (lifferensce un chuenumical potential witlu tinat in hermsms of fsmgacity mis given by l’AI. Section 4.

They attributed part of the deviuution to the deficiency of EOS to nsnohcl tIre plrumse hclnunviour. Non—Equilibrium Fluids ‘lire equilibrium criteria. curclr comnuposcd (If mummy connrpouimds.’h nut cmxli gniruill. tire umet flux of each component. N = ~ k-I +L. and that of meat flux due to concentruition gradient (Dufour effect).J 1 (5. Eq. tIne hiux of courmponent i.4.ia! G.33).~= wInch is relerred to us thtc Omrsuugcr rccipnocuml rehumtiomn.I 98 .X~ (5. can be determined by combining continuity equatnoims nsass. = ~ N (5. Conn . As the reservoir temperature increases with depth. The heavy ends umre genrenally reported mrs pscunuo-counpouncnnts on groups.l j=t. amnd heat q.k(Xk k~i +Q~X ) =1) 5 (5.acioi~r(a/tu/atj.. are given by the plrenonnnenological equuuutions as. I hcnmcc N J. is different at the two levels.asuio.2 E. As Ihe hluid cousnpositioui remniumimns mnnchmmnged with time. The trsain problem witin applying time above nmetlrod to tlncsc flui. = ~LJ~X~ i. Ircnce. producing Inca) flux. wlmere assigning a mmnnfonm average temnlpcnmrturc lu tIne winole fluid colunrunr will not be justifmahle. I’.jk wills jk express the cross or interference phenomena. stmcls as (Imose of lncmmt umtnsl nnuass.53) suggests that compositional graditng hecousmes unore sigtnifieant wlnens tIne mnnixtinnc is cotsmposed of inolecuhes with widely different molecular weigluls. suclm as tennupcnmntune annd concentration gradients. 3.56) unmud N 3..ig 1 199 (5. hence meat of tia1n. respectively.’. I.s/roi-L Conmsbitning the mmhovc equati(rmms for thne fluxes of meat and mass. Omssagcr lras presented a theory for time systemurhic innvestigation of irreversible processcsl39l. (5. cumcln mit uunn uuvcmunge tennmpcrumnnmre mocreursnng downward.~mis lIne Imuck of mudeqummule fluid charactenisation.i.1. ennergy. When consnpositionurl grmuding occuurs. For such systems. suds as that of mass flux due to thennrnuil gradienmt (Soret effect). Section 3.) (559) wiscre Q is cmmlled tIne /1(01 of trwm. Making proper choices of fluxes and forces. it can be assumed that the equilihniummn exjsts locally. N = ~Q.(4.60) ‘TIsmul mx. The above statement can he expressed by tIre gencruil phenomenohogicah rclmution as. [‘hose Fle/.~jjcan be the heat conductivity amid tIne diffumsions coefficient for the meat flux and tIme mass flux. tIme matrix of phenomenological coefficients becomes synnmetnicmul. This is required. can cause fluxes of different nnatures. compared to tIne repontcd vumhmne of 17 mohe%. = sectioum. X~-+ I - X (5.55) included in calculating the fugacities.. it can be shown that at the isollrcmral condition. unnnd lire unse of a fixed value of nnrobeculumr wenglml reduces lIne reliurbil ily urt tine prehicncd results. tIre saunme thermodynamic functions relating state properties of equmihihriunr systenus will he valid. According to his theory. witln mon unvermnge nrrolccnulan wenghun unssignsu. prolnibit tIme existence of any gradient or flux wunlmnn a fluid system at equilibrium. Thre dnivnng forces for tnmass.1. the assumption of equihihrnmmm for a flmuih colunrnnr is not valid. J~.. k—i ~t~(X~ N +Q~X. Monleh mind (‘noucl [38) used the Peng-Rohinson EOS to eslinsnuute lIme eonnmpositionnuih gruudinmg ut tine hiund column reported in Table 5. all shriving forces wilhin a syslemms. TIns is of purnticuluur significance in oil systems with large comncentrumtiouus of hemnvy comnipomremnts suncln us ursplnmmllennes. Xk is the driving force k. ~ ns the total number of driving forces. the coefficients l. In tall columns.produnction anmd momentum.57) 1 I )cinnnnnng.58) we ohlaimn.62) Xq = —(gradT)/T (5.s.. Any force can give rise to any flux. and employing tinermodynamic relations to (lcteninnnne for the nale of emntropy describing irreversible processes [391. The estmmated clsanmge inn nnnchluuimne comncennnmmmtiomn (lute to the gravity over the ahove deptin was only 6 mole%.54) ~L. Tlme connpositioumal gradttng cumin tiren he cvmilunmntcch for cuuclr secliomm wutlr calculaled composition an nhe bottom of emrch section used mis thud of lIne lop in tine uud~mrcemnn lower l. lIne reservoir cmmmm he divided mnlo segnruents. mnunmsn Ire iero.adi.j is the flux j. I towever. Xq.61) where i. TIne coefficients l. if chcviatioums from equilibrium locally are not very large.sport. mm in d -- Tgrad~m~ ITs (5. Eq. Qi tine nmnummc is tine huemut lruutnsporncd by ouse umoit qunantity (ummass or tsiole) of component i. lIre conccmmlrmmtiomn of connupinunmds wilhninr eurchm pseudo— cooupomrcnst chmunges. For mu nnnixhure wills N commnpotrenls. as the fugacity coefficient nmiultiplier duue to the shift. irreversible tlnermodynamic concepts nmay be applied to analyse coniupositionunl variations. Xk. ~ I .s . wlmnch is the curse un pctrolemmirr reservoirs.63) . and heat. For example. and L k 1 is called the phenomenological coefficient.(5. as suggested by Onsager.1.

The density. and g. critical point of (he flumid reported in Table 5. and. Neglecting the thermal gradient. =In~ —h~ (5.69) . Usimmg a value of 333 kJ/kg for the heat of transport of methane 146) and a thennal 2 (5.T.. indeed at all the points on term and a non-equilibrium contribution. respectively 138). tire following ‘There us very lilt he inn fonmmrmrtionm omn IIme Incat of tramnsporl in unulti—coumiponent syslemnms.64) commdensuute sy. it lnmiy he applied to describe tlne heat of transport in oil aund gums (a1. Appendix C.slemnns. ‘l’lmercforc.~= ~v~x~/x . v~ ~ (M~—pv~)g (5..(5.65) I. Eq.. gradP + ~ / ~)x ~p. Eq. Appendix C.t is the chensical potential.I~= (~1k I aT)~. Hence. Eq.62-64).(5.. were 293 K & 40 MPa. The information on the heat of transport. refers to tIme pseudo componemnt composed of all componeurts except k. Broadly. and 363 K & 40 MPa. are the partial molar volumes of connponents I mind 2. gradx.(5.65) shows that the effect of gravity and temperature gradient is nsore sigmmificant when (~ktk /ax )i.65) relates the compositional gradient to the temperature gradiemnt at any direction.44]. Oosl et al. the expression for Q* is as follows..67) ‘line partial heat of vaponisation mrmnd minolar volumes can be cahcunlated by any relimible equation of state.(5. the lack of adequate information to evaluate time heat of transport has resulted ins ignoring the thermal effect in most studies. un the mnuixture amal in the ideal gums state. to dense gases witlm mehiumblc resumhis. Figure 5. Q. approaching the critical value. respectively.onur (‘alciula:ion. reservoirs.(5.~.71) (M~ — PVk )g — Q (gradT/T) (5. Heat of Transport Transfer parameters ~an generally be estimated by nmethods usiung concepts of statistical mechanics.68) will be as.68) 2 where v~. 1411 applied the urbove expression. and v2. 140) proposed a method lo estirmsmmte the heat of Irmunsport for hiusuiry liquid systems. Compositional Gradiing 201 where F is the body force acting on unit mass. as it does not include the energy transferred by the mass. the pure heat of transport was presented mis tine sum of an equnihibrium some degree of conmpositknnal grading dune to non~equilibriumis expected in all 1 lIne stability limit curve.72) where. which was developed for liquids. respectively. A simple uupptounchm is to reduce nmnulti—comnmpoumemmt umnixtunres to pseudo—biumary systems. Phase Re!mau.k defined as. where appropriate expressions were developed for each term.4.73) 2v ~ vi. = ~ Q where vk. Neglecting the non-equilibrium term and assuming the liquid as a regular solution. however.66) n~k 0 (5.r. and the variation of chemical potential with composition. Hence. where the vertical variations are only of signifmcance and interest. temperature. Significance Although which will reduce to Eq. Clmmrhmmck [45) conmparcd the effect of thermal gradient to that of the gravity for an equi. partial mnmolar volumes. ls~ are tine partial eusthalpies of the consrponent i.52) when applied to two points along the fluid cohn. particularly for nearcritical fluids. Bearman et al. expressed by the entinuilpy term.. Applying thermodynamic relations to evahunate vutriuutions ofchenmmicuul potenmtiurl witlm teurmpcnmrtmure and pressure. and taking gravity as the only body force actimng on the fluid. L. Q’/x 2v~v Vu ‘Fine mumea.nmolar mixture of nmmelhnuumne mind normal butane’ at a typicunl reservoir condition of 378 K and 10.70) (5.I ~P)1. and v is the mixture molar volume. v.xjj is small. as equation is derived by combining Eqs.200 5. . is sparse. The chemical potential is a function of fluid pressure.uimmn.u grurdx . At the critical point.gradT + where Ii. is the partial molar enthalpy. can all be determined using an equation of state. Eq. The compositional grading.snnred mmmd piedicled.65) reduces to time conventional equationn expressing the compositional gradient due to gravity effect.43. (5.=Qk—hk t (5. xi. is the partial molar volume of tIme conunponent k. using EOS. mind is i -i. p is tIne mnnixmure dcnmsity. (5.34 MPa. Eq. Q is called the pure meat of transport. and composition.4I).r 5. L is the heat of vaporisation. . hk. = I —1 1 = (5. Although the coupling of compositional and thermal gradients Imave been nrcknowledged by most of the authors. I at time deptin of 3i56 umieter subsea. Note that as the mixture temperature increases. wlsere tIne subscript mm. ~~(~I1k /aX )~ .(5. the determinant of the above derivafives is equal to xero and profound commmpositionah grmndimrg shounld occur [42).(5. have been strAdicd by a nunmber of investigators(38. the compositkmal grading with depth becomes more significant. gradl.11 connpares the predicted variation of C of the above fluid with depth at various 11~ tennperammres when only the grading due to gravity has been considered.

The Ineat of transport. reported Table 5.11.1. Petrol.. 12. CaIu-uulaiion. at various tensperature grmmdients. withn tIne imeavies more concentrated with depth.mal (.mitio. Hence.lO 6— 5~70 5 5 5 7 2 5 2 3 h. it is conceivable that a fluid nununy nnnutnmntuniun Ilne suttmmc counsposition with deptis. 1952).OOy nCt4 3200 3250 De mti Subsea.. The predicted compositional grading of methane. using equations of state.. Aromatics.13. Vurrnuntmotrs of unretlrummne concentration witim depth due to combined gravity and thrermnsal effects. hence.. as observed by Shulte. such an assunmption will exaggerate tIne counposiliomnunl grading for aromatics..trexmmne n(. I. 0525 -~ 0520 o s. Note a significant increase of methane grading with depth by gravity due to the additional aromatic content..n.~- 4 3731 - 5l 75 C 405! a 13 (‘5 nC’S C) no I I I S S 5150 — ~ ~ithIhum. 19.02 K/m..lc% Arorn. at 0. Tine ligintest mind tine iremrviest counlpomments of a Inonrohogue group tend to grade more significammtly than intermmnediate ounes.3 shows the composition of two oil samples with (hifferent aromatic contents.12 149]. As tlmc thiermmnah urmsd gnavitatiousal effects gemnerunlly operate at opposite directions.i. meici Fngumrc 5. Table 5.02 K/m. 10.3.i.i nC6 hen. increasing the concentration of light components at the top. hi~h. Comparing two reservoir fluid mixtures which were only different in tIme ummount of aromatic contents.c ¶ 4 (‘ompo. Ruicltford. F’/iase Re/i. with and without the thermal effect. N2 5 5 C02 5 5 Cl 52 52 C2 8 8 C3 5 5 iC’4 It) no nC4 4 4 gradient of 0. -. tIne d’omnnpositionmal grading in tIne above higlr aromatic oil is nmrsignificaumt. the tinermal effect.(5. he showed the tendency of these connpounds to concenlrmntc witim depth. The three parameter Peng-Robinson eqummtion of state. (‘ompiincnn Iliglu Low nni. 5. mrimh Rice. at 361 K and 34. Sec.. the grading decreases and the difference between the two fluid becomes inmsigmmificamst. for lIme two fluids is shrown in Figure 5. Variations of C 1 tenmperatures. and the heat of branrsport given by Eq... Aronnn. Eq. particularly dune to their highm density as discussed above. and operating at the opposite direction. IioIt et al. due to strong bonding.. when the opposing th~ninal effect is included... nnetliane concentration may even increase with depth.67) shows that the compositiomnal grading due to gravmty is nsore pronnounced for mixtures with components of vastly different sizes.5 REFERENCES I. .utimsg Flursh Vaporisatiots I tydrocarboun Equilibriunn”. amnd onuly gravity effect for low aund high aromatic fluid samples. Is Teiuper. 2. Technol.. As hIre thcnntmal amnd giunvnlationunl effects gemnerally oppose each other..na. Figumre 5.73) have been used to evaluate the conunpositional grurding. due to combined gravity and Figure 5. At Iniglmer thnernrmrl gradieusts. Shulte [47) conducted a sensntivnty analysis of cotnipositional grading due to gravity.202 5.025 K/urn. in Vmu-immtions of nsictlrunne concentration with depth. Note timat at a timermal gradient (ml muromnund 0. .radiiig 203 Tumble 5.o Fngumc 5.iiioii. Sec. witln heptln at vmmnious llnerniuuul effects.(5.13 shows the predicted cotrcemrirmrtuon of tnnetlnanc wulln dcptls al various lemnperature gradients. mmeglecting thse tlscnnuil effect for arommiatics is a umrtncls more sever assumimption tlman that for paraffins. 1+ of Fluid C. and conclunded that aromatics play a major role.. 3 (Oct.s : 0 2’o iiopuli RO. m 0 2 2 5 5 25 50 75 100 Oepih Reiow Refrmnsce Poinn.~h . Counposition of Inigli mmmd low aromatic oil sarmuphes. As aromatic compounds are relatively much deunser than paraffins and naphthenes with similar molecdmlar weights and volatility.6!.. depends on tine latent meat of vaponisation.. The reason appears to be due to neglecting the themnal effect by Shulle.o~~iy p. hill. the thermal compositionaF~gradientwas estinmnmrted to he abotul Irutlf of thnat due to the gravity. very similar to those studied by Shulte[47].i h. [48] studied the compositional grading by considering both the gravitational and tisermal effects and reported similar behaviour for aromatic and paraffin oil systenns cotntrary to the SInulte~sconclusion.cne ni(’7 iiituucune cym cyc.flii~ K — ______________________ ~0i 3798 388i . ID: “Procedure for Use of Electronic Digital Computers in Calcunl. have higher values of latent ireat tiran paraflins with similar molecular weights.5 MPa.. Flowever. such a conclusion should be expected.

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Fluid Phase Equilibria.L: “An Iterative Sequence for Phase Equilibria Calculations Incorporating the Redlich-Kwong Equation of State”.P. Des.1. Gozalpoimr.A: “Application of the Tangent Plane Criteriomm to Saturmrtiotr Pressure mind Temunperature Computatiomms”. aund Luks. A: “Tiserniodynmrrtmics of Petrolesim Mixtures Containing Heavy Hydrocarbonns. JCPT. 769-778 (1980). 5. Phase Split Calculation”. amsd Ileidennanum. PD: “A Critical Review of (‘orrelatiomis for tIne Criticmrl Propenlies of Defined Mixtures”.M: “Vapour-Liquid Equilibria at High Pressures: Calculation of Critical Tenniperatures. R. Phase Rehuni-ionsr (. 709-710. 184-188 (1986). Fluid Phase Equilibria. Poling. Lacey....C. W. D.. 1978). Y. P. (1949). 1983). Eng. Proc. 112.. 672-676 (1983).Ensg’ng. ACS Symposiums Sermes 300.S.C. Pierce. 51-64 (1986). Whitson.c 205 Sage. K. Equations of State Tlseories and Applications.‘a!cudations 5. Avoiding Trivial Roots and Spurious Derivatives”.M: “Thermnodynmmnmic Properties from a Cubic Equation of State. 19. and Todd. Xu. 5/6. Sl’E J. I & EC Proc. 53. 590-596 (Aug. SPE RES. amid Prausnitz. 3 Efficient Flash Calcmulurtion Procedures Using time SRK-Equation of State”. 9. 72. Nghiem. AS. CF. SPE 11198. 9. Fluid Plrase Equmilibria. Stability”. R. 29. Tejui. and Heidemann. and Nghiem. Aziz. J. and Vidal. 20. R. SPE J.. Reid.L: “Simplified Flash Calculations for Cubic Equatiomus of State”. Chem. A. J. and Kahitventeff. 34.E.H. 1524.A. A.mlti-Plsase MultiComponent Isenthalpic Flash Calculations with a Cubic Equation of State”. 17.5. No. A. 0. R. R.. Gulf Publishing Co. A.K. 31. 24.C: “Applied Hydrocarbon Tlmernnodynannics”. 3. 21. 1-19 (1982).D: “Gibbs Energy Analysis of Phase Equilibria”. Dcv. Rijkers.

Kreglewski. 49. Calculate tIre (hew point of a guus uunixhtnre connsposcd of 90 mol% methane and 10% normal decuumie urt 377.s 207 35. Los. Prove that the extension of amny tuongent line to conslmumnt redince terniperature curves sirould not cross the Z axis at a negative vurlue. ummrd reduced pressunre. Tehran University. 62. 239-244 (1991). Derive an expuession to select tine proper root of generahised EOS for a fluid. 1 39.ENG. Kirkwood. (Sept. Find the ophinnnuurm separalor pressure 10 ohtmnun tIre mnnaxinnumn (nil volume at the stock lank conditions (0.1 0. SPE RES. 157 (Feb. AICIiE.7. Chem. to Gravity”. 1988). Journal of Faculty of Engng. 36. McGrurw-Ilihl Book Comiupatsy (1959). Conf. SPE 15856. A. Bearmumn Ri. W... Advuunuces inn Clncmmmicmml Physics. mmsmnrg tIne cruticuil properties of pmmrc consstituents and reunsonable nnixing rules.36 10. (Sept. J.1 assmnmtninsg urns average lcnnrperurlure of 377.6 K for the fluid colunrmn. AM: “Cormmpositiomnal Variations within a Hydrocarbons Colummn Dune SPE 9235. D. Z. Katz. SPE RES. mmd surface processes can he simulated by a series of cqimilihrmumin IhasIr cuulctmluutmons. (March.6 EXERCISES 5. 10. T. M: “Slurlistical-Meclrumnnicuul Theory of Transport Processes.. 5.. R. Nurutln --I un I:uurd Pimlrhishninig (‘a. 1980).46 4. and Roof.. 44. 59-68 (1997). H. Danesh. Lira-Galeana. 5.!) N:)) Si’)’) The oul is flurslned mit 3 MPur aund 32S() K. A fluid mixture consists of methane (30 % mol) and normal heptane (70 % mol) at 338 K and 6. Whreaton.B: “ The Critical Constants of Conformuml Mixtures”.. Slmulte. T.Cunlcinlumte (Inc reservoir connrpositionr urt 500 nnmetcr below that given in Example 5. 40-60 mole %. JO: “Calcmmlahionn of Thcrnnruml 1)iffmnsiomr Factors for the Mctlmumne-n-Butamie systems in tire Critical and Liqmuid Regions”. Proc. as stmowmi inn figure 2.. 73. 5. Whnat us the.ENG.22. 45.. and van Dale. Auunsncrdumnnm (1959) 40. 43. 8-94 (Jan. 1k ( root. Write ann algoritiunmm to simulate a constant volume depletion test tusing FOS. and Ratkje. Lindeberg. Rutherford. No. 48.J: “Treatment of Variations of Compositioun witln Depthr in Gums-Condensate Reservoirs”. TIne comrspmcssihnhity fmmctor. A.L: “Prediction of Comnspositionnuml (‘unuudiurg inn mu Reservoir Fhtmid Cohninirun’’. K: “An lnvestigumtionn on Compositional Gradient with Depth in Petroleum Reservoirs”..21)). J. (‘omit..G. Oost. I’hasr !.72 MPa). Montcl. mnmmxmmrnmmns pressure at which tIre Peng-Robinson EOS provides three real roots for an equinniolar fluid comrnposcd of C -nC at 380 K.. TIne oml in Exercise 2 ms to be stahihised by one internrediate separator at 325 K.3. paper 11761. C: “Discussion of Treatment of Vmuiations of Connpositionn witlm Depth in Gas-Condensate Reservoirs”.. and Saktlnikuniar. Cump~jnok% Ct C 2 C. et al: “handbook of Natural Gas Engineering”. 1992). I.5 K. 30-I.M. W: “Thcrmnmurl I)iffmusion in Moderately Dense Gas Mixtures and the Pair-Correluition Fumnctiomr”. 5. Physicun. JPT.uincui’. 5. Proc. F and Couch. A: “Role of Asplsaltenes in Compositional (irmsdinrg of a Reservoir’s Fluid Column”.9. Exereise..J: “Discussion of Treatmrsent of Variations of Cominposition willr Depth in GasCondensate Reservoirs”.K: “The Effect of Gravity aund ‘Temperature Gradients on Methane Distribution on Oil Reservoirs”. SPE umussohic.73 77 7 77 11)1 38. tmsinrg SRK (nircasmnred value P =33.inc’ M .. 46. 47. and Movaghar Nezhad. W. J.56 7u (tiuii. 1969).5. Phys.1 MPuu mimic! 288 K). 5.khaiioiir (‘aleulations 56.1. Use the Stmnrmding nmetlnod to estimate the equilihriumn runtuos umnnd cuilcu mute tlsc conmmposu t noun umnid nurolc fruich four of equ ilibrunted gas and Ii qmnid plmascs. Ilmrscberg.’’. J.5 MPa.93 856 . 4 5. AR. 5 4 5. Most reservoir.. 3359-3366 (Oct. 1986).. 5. 42. Chaback. 158 (1992). London. Cauwenbergh..4. SPE 14410. E. 841 (1963). Neveux. 5.2. is consnnmnommly plotted as a function of tIre reduced nemnmperurmtnre. and Kay. based on tIne nsmimsimmrummn Gibbs ennergy. 409-426 (1972). WA. ol fiOtIn Aumur.. S.206 5. (Oct. What is the state of the flunid 7 . Holt.ENG. 1983). 1’. SR ‘‘hlnerumrodynummmuics (ml Irmeversible l’rocessei. 37. svellhore. t3stimmnuute tIme crinicuml pnopernucs of us mnnixtmure of methane ammd n-decane. S: “Dehimucation and Evaluations of a Nortln Scum Reservoir Conlumining Near Crilical Fluids”.8.6. P. SPE RES. Proc. 985). 1-13 (1958).. iC’ 4 nC4 ir(6 27. ttne Heat of ‘Irurmrsport in h3nmsany Liquid Solmmtiouns”. amid Fixuisan. 38. of SPE Emropean Petroleunns Conference. TIme coniposulnon of an oil sannmple is given in tine following table. 41. of 55th Ann.

though developed using experimental data of pumre compounds. within time C 6 to C groups. l’isc distilled hydrocmrrhomm groumps are clmaracterised by measuring some of tlseir properties such as (lie average boiling poimmt tennmperatumre. counld he composed of thousands of cotsnponents which pose two rmnajor restrietiotns: (I) A full descriptiorn of tIre fluid by idcçtifying mill its constituents nmiay not be possible. sucir mis. . hcnzenc. These properties are used in generahised correlations to estimate other properties. however. the required data need to be estimnmated by othser methods. 11 S and hydrocarbon groups for 6 2 2 2 Ineavier fractions. (2) Pimurse hchiaviouur curlcuulatmoums for systenus defummed by a large number of comnsponenmts are timmre connsumnming aumd particularly immnpractical in compositional reservoir simulation. The 9Imydrocarhon groups are gemmerally determined according to their boiling poimrts by (listihlation aumd. nmay also be identified. Real m’eservoir fluids. are sttccessfully applied to predict phrase behaviour and volumetric properties of multiconmipomment systenss by emmmploying mixing rules. cyclolmexamues and xylemse. gas chirournatograplny. such as the critical properties and the acentric factor. In some cases an extended distillusnion of heavy fractions may Irave not been conducted. or. A reservoir oil or cousdensate is commonly described by discrete hydrocarbon components up to C and the non hydrocarbon gases. hence. toluene. molecular weight and density. Tine concentration of certain major uron-paraffin constituents.209 6 FLUID CHARACTERISATION Seunmi-empirical cumbic equations of state (EOS). C0 . as described in Chapter 4. wliicin are required for EOS application. such as N .

‘Tire puruty of SCN grounps camu further be improved by using a more efficient distillation apparumtuns. may he estimumted from the 29 correlations given in Sections 6. for different sets of uunits is given ins ‘lable A. TIre latter mrseasuures hIre lneriixl of oscillation of mm tumbe tilled with tIne fluid. TIre tnse of a 90 theoretical equmihibniuni plate unit. such as using empirical correlations 1 4]. R. mmd will he left in the po mis the residue. TIre density of each cunt is mrseasumred by either weighing a known volume of the liquid.3) where P is the gas density at the atmospheric pressure P~and tIre standard tenmiperalure T . such mis t aspinaltenes. There are.1. Figuure 6.001 g/clms .3 0 The value in Appendix A. or calcuihated. C3))~ wiren tIme hasn drop of distillate is collected at the boiling poinrl of nnC . wlrcre each cut hegmnms uuumd ends mit lIme boiling point of mrormal C~. 5-30% of the C~fraction could be lighter than the unormsrurh (in. can he analysed by liquid chronrratogrmrpliy techniques 131. As reservoir hydrocarbon liquids generally contain very heavy comsipounds.I [5]. pycnonrietery. as will be described in Section 6.7 °C.210 6. Incncc. above the normal alkane boiling poitnts. to detennmine the critical properties and tIme acentric factors.30.nired. Pg =(PaMg)/(RT ) 0 (1. each within a temperature band at the column top. Fractions are commonly collected witlrin tIre temperature range of two consecutive nominal alkanes. and thmc resunlts mire given as tIme percentage volume distilled versus the normal boiling point.h. True bonhiung point (IBt’) distillation curve of a North Sea condensate sample. The fractions are called. by ~veugInmnng a knownn guns volumnne. Each cml is elnaracterised by its uiroheculmrr weight. As light compounnds vaporise. Each collected fraction comsspriscs mm large nuniber of comuiponents with close boiling points. a certain amount of the loaded saniple will not boil-off. and is mclemued to by line cuirhroun urunmurher mm. Itence.unlermrct time hiqinid Isold-up in tire apparatus for imnproved purity.1 EXPERIMENTAL METHODS Samples of reservoir hydrocarbon mixtimres. in firrmmr of discrete comnponents. as shown in Figunre 6.2. but tine cohunnn pressure is lowered stage-wise to vaporise heavier compounds to avoid higls temnrpcrmutures which can cause hydrocarbon cracking. . The distillate lenmperuuluure is converted to the normal boiling point. hence. depending our time distillation unit and the fraction. pumrticutlarly for gums condensate fluids. vuiponising its cotnponents accordiung to tlmeir boiling points. or by tire more rapi(I. as shown in Figure 6. The boiled-off fractions mire collected as distillates. Fluid C/. Sectuomr 6. Ia 6. TIne urvemage hoilnurg poimrt of the residue. tine reported C fraction.. are generally flashed at laboratory conditions atsd the conmnpositionrs umn(l properties of tire separated gas and liqunid phases are mneasuured. wisich fornmrs tIne residue in distillation. The errors inn cousnpositioural anumlysis of high pressunrc reservoir fluids associated with the flumstnimrg hcclruniqcue.1. that is. 5 of universal gas constant. the midvohuuunre temperature is about the satire as the arithnnetic average of the boiling poiurts of the two nonmnmrl paraffuns at the boundaries. Distillation The liquid phase is generally charactenised by fractional distillation and nrieasturing the properties of the collected fractions. 9 comnrprises all time counrl)ounds collected as distillate. withini the temperature range of normal octamne and normal nonnane boiling poinls. mIs ulenrsity.~ z ~ t .araeteri. curn be cuulctnlumtcd try lIre nnuuihuur ummiximig rule. nonancs. however. The l)oihing pounrt is taken mit its mid-vurlumune. are discussed in Section 2. t and normal C~. the temperature is gradually increased. % Fmgumre (n. collected mit bottom lsole or sepmmrmrlor conditions. siurgle cmmm’hon number (SCN) groumps. compositional changes. The standard niethod is fully described inn ASTM 2892-84 ]2]. is gainiung popimlarity. or nnnorc comnnonly by distillation [2] and reported as liquid fractiomss. density and normal boiling point. TIre comnsposmtionral anmurlysis durhum of tIne separated phases are tinen nummerically recomrmbincd in (Inc surface proportiomus of gums uuurd Iiqmid to detennine the composition of the original reservoir fluid. For cxmmumnple.med nunit slsould provide density data with an accuracy of better than 3 ±0. A pot is loaded with the liquid and heated up. A cuuhihrr. M=~y~M~ (6. The measured properties are used in some generalised eorrclumtuonns. increasing the concentrurlion of heavier fractions in the liquid. The nesudunc is reported mrs Cnm+ e. yet rehiumble.1) 0 600 C 0~ 0 0 . lsennce. 20 4)) 60 80 tOO Cunurutuumive Dim/lIed Volume.’nmental Met/nods 211 . approximately from the ideal gums law (by missumnnimsg Z= I).. The nnixhunre average misohecular wciglnt. In practice the boundaries are selected about 0.2. if reqn. have been stnggested to extrapolate the TBP curve to 100% distillate.3.2. The gas density at laboratory c(nnditions cuin he nnieasunred. nnaunrly to c(.(ation 6. As tine boiling points of the neighbouring normal alkanes are chose and tlne distillate recovery is almost linear over a SCN range. 1. The oil composition can be determined by gas chromatogrunplmy. The distillation begins at the atmospheric pressuire. Exper. Methods. The heaviest frmrclion.1. instead of the standard ASTM 15 plale unnut. Tine distillation is commonly conducted using a column with IS theoretical equihibriunm stages at a reflimx ratio of 5 and is known as the true boiling point (TBP) distillation. at the atmospheric pressure. M. which depends on its mass. The gas composition is determined by gas chromatograplry (GC) ]lj.respectively. more reliable unrethods In describe tIne residue by a number of fractions for phase behaviour modelling.g. oscillating tube densitometer. (~ 1 400 where Yn is the mole fraction of component i in the gas mixtuure. i’lse liquid phrase courhaimns mriununy comnuponnennts witlm properties varying in smmrll increments. time frmnctnommaliomr of hiqumid into pumre compounds is unfeasible. Even then.

5< K~ 11.909 0.14 12.888 0.5 < C4m C42 (‘43 C44 - K~ 13.1.2 shows the variation of SCN group density in different samples. ‘lime cuulcmmlumted critical properties of generahised SCN groups.87 11. (121 huive mmlscs reported average SCN group properties for North Sea oil and condensmile sanriples. dens.2 in Appendix A. is expected to increase with increasing carbon number.0 213 The average molecular weight of each cut is often deermmiined by trremistmring tire depression freezing point of a solvent.nd Cluarauleri. specific gravity. known as tire generalisecl siurgle emtrhon numnmsber ulatmu.07 12. Experimental Met/nods 11. Iin. Katz and Firoozabadi [7] extended the data of Bergman et al.02 (‘21 (‘22 C23 C24 C25 C26 C27 C28 (‘29 659 671 681 0.0< K~ 12.866 1)871 0876 t). using the specific gravity and molecular weight of each fraction. Osjord et al. winds differ somewhat from those given in Table 6. e.1. The PNA analysis of SCN groups is not generally required for modelling of vapour-liquid equilibria using equations of state. imowever.2 shows the paraffins.09 12.11 1213 12.931 0.861 0. by dissolving oil at a concemntrmmtion (ml about 0. may be used to estimate the concentration and properties of SCN groups 161. 18] our the average boiling point.82 1185 1186 11. mmmc giveum inn l’umble A. However.04 C30 C3t C32 C33 728 737 745 753 760 768 774 782 404 415 426 437 445 456 464 475 (2. for example. I.920 (1.5 Paraffins C45 826 0. to improve consistency in the reported unrrlecular weight. Table 6. All the hsydrocmmihon commrpoumsds witinin eumchn SCN gromip do nnot lmuuvc tire sumunue mrtuummlwr 9 ofcarbons.13 12.2)~ (‘39 C40 788 796 81)1 807 813 821 0. For pure hydrocarbons the above definition of chiaracterisation factor results inn: 12. The plot clearly demonstrates that the density of a SCN group can be lower than its preceding neighbour.836 0. revised by Whitson [9].938 484 495 502 512 521 531 12. all time properties of SCN groups should not necessarily follow the same trend.96 11. Figure 6. The properties of paraffins. Note 6time9 putrmrffinr group that. Methods.91) 263 275 291 300 312 1193 1193 It . K~.843 0851 1)856 0. benzene. Indeed aromatics with the samnne caubon ntmmsnber as puiruiflins will uulmpeumr inn tIme next higher SCN group due to their lower boiling points. Fact. respectively.95 11. is commnronly described by tire Watson or UOP (Universal Oil Products) characterisation factor.99 12..89 11. A deviation of about 2 units of molecumlar weiglnt cumn typically be expected in a carefully conducted test. SCN - Boiling Pin/nt Spccifmc Gravity molecular weight and density of SCN groups of a large nunsber of reservoir flumids.5 8. detailed infornmatinn ors the content of each SCN group may be required in special cases. ~(l.9(12 0.01) 1201) 12.g. when two hydrocarbon liquid phases or liquidsolid hydrocarbons are formed.91)5 0.212 6. The mmnolecuhar weiglrt.933 1)934 0936 0.ruutio.n d)f I 6.912 (i. The overall characteristic of hydrocarbon fractions.2.925 0.. In such cases. 7 8 9 Due to an uneven distribution of hydrocarbon Imomnologumes in SCN groumps. A measured detailed mrnalysis would be more appropriatein such cases instead of estimating them from the correlations. unaterial balance methods.929 0. 13] to estiniate the PNA content. For exanisple bemrzemrc. am 288K 0690 Molecular We~Iu kg/kgmol 84 96 1117 121 Watsinn Char.07 1208 12. using correlations described un Scctiomn 6.1.782 CII C12 Cl3 461 482 51)1 0793 t). napinthenes and aronsatics (PNA) content of a North Sea stabilised crude oil and their properties over the C -C range. [III and Ronningsen ct mrl. C and C groups.8Tb)~/S K (‘6 (‘7 (‘8 C9 C II) 337 366 391) rel.917 0. using the density and molecular weight of the whole distillate and the TBP distillation curve.S))4 1)815 1)826 I 34 147 161 175 190 1227 It 97 1187 1182 II . The properties. Table 6.88I 206 222 237 251 1184 11. have been proposed [4.14 where Tb is the boiling point in K and S is the specific gravity. If the distillate is accumulated in a receiver.927 382 394 1203 12. (6.11 12. ____ 0727 0749 4ft 439 1)768 0. present in each SCN group are different. the properties of each SCN varies according to the relative eonmcentration of the comprising homologues.87 11.84 Ct4 Ct5 C16 (‘17 (‘18 (‘19 C20 520 539 557 573 586 598 612 624 637 648 0. naphthenes and aromatics.9)5 0.95 11. uniohecular weight and Watson characterisation factor of single carbon nunmber groups [9]. instead of collected as isolated fractions. Avermmge normal boiling point. the properties of each SCN group cannot directly be determined. Naphtimenes Aronnatics Tire cisaracterisation factors of generahised SCN groups are given in Table 6. e.892 324 337 349 691 7(11 0.1. mire umsed when the measured data on a specific fluid is not avaihmubhe. relying on material balance and empirical correlations.85 11. IS mole per kg of solvent. Hence.896 0899 360 372 709 719 0.09 C34 C35 C36 (‘37 C38 .81(5 (1.g. toluenc and xylenes are counted as C . Haaland [10]. are given ins Table 6. Their data. as follows: K.940 539 .922 t).04 1205 1205 1207 12.. the density of naphthene group in C is higher thumn tliurt of 6 in C .

052 0. comiunmionly available for petroleum fractions.3.1 128 5 22)) 11)6.2. General purpose columns partition conrponenhs mostly umccording to thucir boiling pOints. therefore. TIne iuntcumxrediurlc ununh lrcuuvy lrurctionns arc ehrmtcd. htrdivtchunmnl peaks msnay be idenstified by comparing their retention timires iunsi(hc tine coltinnnmn wills those of kunowus compounds previously analysed at the satire GC comnditiomss.1 0750 ___________ not.214 6 1/mid ( jlariiite. -. FIne variations nih K~ ns ueIuutivchy smnmmmll lou dnfferenrt fractions.as Chromatography Tine guns comnrposimionr is determmnimned. Tire resulls.4).3) lIre Iwo most conrinsnounly umsed detectoms are lhc flunnure ionisation detector (FID) and the thermal connduichivihy clclector (TCD). particularly for Incmmvy fractions in 5 It cann Ire nssnnnnnd I.836 862 t)663 HexaneGroupNaplrthenes 0. t’uuckech colunnimurs. ‘ilmis is very simiunlar to the fractionation behaviour in a distillation mnnit and lreated simmuilumrly. Ihummt is.713 0930 0355 0870 1. not widely used.4. 1(1) is ofnems umsed for urnmnlysis of gaseous mixtures tlrat contairs non2 2 Iiy(lr(rcarh(nmr connupouncurts. as slmown in Figure 6.140” 1. referred to as the plus fraction.. it can he related to the mnolecuhar weight (M) and specific gravity (S) [9]. The GC operating conditions may be adjusted ]h6]. . Tirese data are (6.4) TIne above relatiomn is particularly useful for the last fraction.787 2. ho siustunlale the 15 tray TBP distillation. especially for complex fluids.435 261(1 1416 13i1 1)889 1)34 0343 11)54 I 556 0941 1)877 1)699 (122 11)0. are nIne unuost versmrtile unund frequenrtly imsed devices.886 0. and transported by a carrier gas. Recent mmdvatmces ins gas chromnialograplny have enabled laboratories to extend the nnethod to oil analysis with a conrpuirahle mrccuuracy. TIne elunted conrpoumnds are carried.90 0. by the carrier gas.cUtjo.88 0. cannot detect non—hydrocarbons such as N uuusd CO . by gas clmromnmatography (GC). TIre FID respourse is almost proportional to tIme mass comscentrmrtioum of tIne ionnisech connupounnnd. may he obtained by including a third physical property. In. may appear as naphtinemse evalunated by its K~. using the Riazi-Daubert correlation.185 0. . Tinese columns are capable of base line sepmmrumtiomr of gaseirtus comsnpirnumnds. vaporised. witlu ann efficiency ruungimrg fronnn lemns to hundreds of eqmmilihrium stages. lhucrc’Iusre. Tine smiusiplc is injected iuilo mu Ircumted inure.86 en C 084 082 0. (. nuuisst cases. A mixture of arornmntics and paraffins. Paraffins.. it is a useful single factor describing the characteristics of pelrolcuurs factions. mm conmstuntrl for lreumvy frmuclions to evurhmmmute tIne 1042 2464 1)872 inuterunuil coursislenscy ut uuiemusuircil (lanun. however. hensce. ilowever.5.2. however. Huthmig-Fachnveriage Copyright.s ineunvy mis (‘5)) 115! inn ui urumnller of Isomurs using only a smunll fluid sample.s 6.059 70.682 1. The percemntage area under the FID response curve luas been tmikeun to he eqimivaleurt to time percentage volumne distilled [17]. Other characterisation factors. are quite comparable to tlmose generated by tine TI3P nneihnod [2]. Fugnunc 6. 5579M° °‘~s 84571 (6. The characterisahion factor for a mixture can be estimated by time weighted average mnnixing rule. all tIre counponents detected by GC between the two ureighrhouring trormrral paraffimrs are comrimonhy grouped together. rcsuluinrg ins partitioning of tIne inn jected sample eonstituuents.?nrei:fa/Ales/rods 215 Table 6. TIre above equation becomes less reliable at M>300.912 3. Densities of SCN groups of Carbon fluid samniples Number fronn vuurious Northu Sea reservoirs. Eq (6. Ilnc Wumtsorn cismrrumcterismnlion factor cuimn he related to properties otlser than the boiling point and specific gravity. its efficicuicy lowered. or no estinmruute nmnissing iunfnrunatinn. A more reliable characterisation factor. known as lire simmiuluiled distillation. K. Component Wcngtn(% . however. measured and reported as mm SCN eqnnunl to llral of the IrigIser noniral paraffin. have also been proposed 1141.2 87. naphihenes and aromatics content of single carbon nutriber grommps of C6 to C9 of a typical North Sea oil [III. gas chromatography cams identify components u. ‘l’hmmt is.j.1 781 1142 11)26 92. such as the viscosity or the refractive index.958 0739 0646 1. into a detector wlscre tIne conmnpomsent coniceumtratiour is relurted to tire area under tire detector response-time curve as shownr inn Figtnre 6.2 1)686 1)769 0884 1)7(17 1)772 1)871 1)721 )) 4. as a continuous stream of oven Imnppimrg comnrpouuirds. gui’ Hexane Group Paraffmns 0647 1. using correlmmtiomms given in Section 6. Wtnilst urn extended oil analysis by distillation takes many days miund requires relmslivchy mm lunrgc vohiuumse of sample. ~ where w~ is the weiglnt fraction.80 078 076 0 74 beliumxn. Reproduced fronir [Ill wills pernsnission. K = Heptane Group Paraftins Ilepiane Group Naphihcnes Hepuane Group Aromanics Ociane Group Paraffmns Ocnane Group Naphthenes Ocuane Group Aromatics Nonane Group Paraflins Nonanc Group Naphitncncs Nonane Group Arornatics 0.‘ f~efm’r. as will be described nun Seclinsin (r3. For example. usually 0.Motc% Votumric% MoIW liens.2. Imence comsipounds are eluted in a similar order mis in distillations. dchcrnnining their concentrations as discrete courspolnn(ls. into a columnun packed or iurtenmally coated with a stationary liquid or solid phase. llennce. innvuirimuhly. where its boiling poinrt is trot known.404 0. Figumre 6.

4. umsing a pumcked colunnum. relies on certain hiunitimig asstumrmptions nC 9 nCuo winds nmnuy lead to large deviatiomrs in measured concentration of non-eluted fractions [5(. known a. preferably not present in tIre oil. 0 (‘I A rplicustiomm of mm eomrtimmtmotms fumnction to describe tIme componeunt distribution (see Section 6. l’ire molecular weight and density of components ideustifued in each single carbon group can be used to estinrate the properties of that group. Hensce. using gas chrounatography.5) . by the following material balance equuations: Time > Figure 6. so C 01 0 600 0• OS 0• 0 0 0 I .n nd? uu~ mine Renenuson Time > 301) 20 Figure 6. TIne nirethod. Comparison of TBI’ distillation curve amnd simulated distillation restult.3 presents the components as identified by the peak nunsbers in Figure 6. are added to the oil at a knsown mass ratio [161. winere one or a few fully detectable compounds. Time comnson umietlsod of estimating the non-eluted fraction is to unse an internal standard.6. the unse of typical SCN groups. Molecular weight data are needed.u 6.3. used for oil analysis. Gas chromatogram of a North Sea oil sample. gives an indication of tine ansmount of noms-eluted fractions. as showmn in Figure 6.3) 1 extemnding tine mrrcursumred comrcenntrationn of eluted fractiomss to uleterumsine time non-eluited puurt is mimrd mrlso an option [5]. Table 6. Tine lack of molecular weight data is quite limitinmg as the response of FID. known as (he response factor. 4) C 0 0~ 4. is proportional to the mass concentration. ci.nn4ni. in preparing standards appears to be more mupproprimmie. 0 8 C 0 a 0 nC4 0 a nCS 501) z 404) 0S 0 0 C’. Erpe. However. tisey canmmot be detected by GC.C Sinrniaied m)isn. the concentration of tine plus fraction (last reported group) determined by GC. to convert the mass fraction to molar basis required for conrpositionai studies. M = (~w~))/~(w fM) 1 (6. The comparison of nnass ratio as detected by GC wittm tinat of graviusretricahly prepared mixture. The accuracy in compositional analysis can he improved by cahibruiting GC.6 for a North Sea condensate. inence. to improve separation and peak recognition.216 cm 6 Flair! (‘/n(una(gerjc..s spiking. Time effect. however. 1. of aim oil sarirple. that is. highs tensmperature columns [IS] are capable of almost connnplete elumtion of light conndensate fluids. using a packed coluumsnn. It is known that the response of detectors to paraffins and aromatics are different. is minimal [5] in most cases. Normal alkanes are often used to represent SCN groups. sinould always be treated with caution. 40 60 Cuunnulauive Volume. on the identified SCN groups. Capillmrry columns.:fjo.iinerusal Metluod. The courmimmon mnetirod is to ammurlyse a gravimetricaily prepared mixture of componeists witis known concentrations. equmivalent to many thousands of theoretical equuilibriunm stages. Gas chromatogram of a gas sample.5.c 217 800 Ce ci A C 0 701) . Time very high hoilimmg constittmemrts of a reservoir oil sample cannot be eluted. % 80 Figuure 6. can be used in preference to packed columns. therefore. determining the detector response relative to the concentrmrtionm of emmch counpoument mit tire operating conditions. instead of normal alkanes. as time staindard. A nrajor drawback of GC analysis is time lack of information. such &s the molecular weigist and density. molecular weight and density. aird tineir concentration.

NJ a 4.~.4 a’) 0’ ~ L.9LaM’. 4.’.4 sosososo.Ssososotso50.3.c ‘~ so Cc so-~ ~ ‘ 00 LaL4.. ~ a~-~r~ ‘ NJ ~) ..j C ———.9.9—JLJ~soLaC..9 0’ ‘. NJ — NJ ‘4..0 3’ C’ —4 . C .j a S S S so 3.0— —‘0 ‘04.. ~4.0000’ 0’ 4.9 ‘9.9.0 — -4 -.395~ 00 so so La 033999399©990099 B La003CNJ-J — .44. Reproduced from [11] with permission.0 0 . ~ ~ ~ 1.. .0 NJ.. ~“ 0 ~ o ‘~ ~) 7’.L. Peak numbers correspond Huthig-Fachveriage Copyright.d~-4 NJ.J—499—so—r..4.aJ~.9 ‘-4 ‘0 0’ -4 ‘4.4 -4 -.9 ~ ..4 .J’ a 0 0.2: ~ ~_~JJ ‘. .9-43 93099 33~39933 ..NJNJ 999999993393 —a099—---a.9 90’ NJ La — .9 ‘flNJ3.~. C) . ‘4. ~.~9 4.).4-.4.~ ~ 2.4 C C) C) 0) ‘0 20 30 40 50 04 Time.J~a ~ 9 ‘~ ‘~ 0 .’03N..9 9 .4 — NJ C’ NJ.a —at’. ..— so RC’0C9’0_4so —— — — — — ... soOc-soso--JOC C-C’0’0’30’ 0’ ‘..NJ. La NJ’0 0’ 0’ La 0’ 4.J0’ so so -J NJ ‘4.soSJ.) NJ’4NJsoso0. ‘0 a ~o — 5 3 .~r —3= . .0. La ~ 4.4.—3soL.soNJC-400 3-’3’O39~39~3.< r em 3 Co 02 ‘1.NJNJ39 3333399!2.0 NJ’.0 NJ NJ NJ NJ — NJ 9 .4’< N.4004.4 0’ NJ a ‘T3 0’ (5 .tLa so ‘ 9993NJ——33C3033333 — 00 0’ 0..‘~ -I La La -~ (‘)u~-° co~ ~ .0 so -4 0’ 4.0 C...~‘...6. so ‘... a 4/’~NJn1’~ . ‘t 0’0’’. — so -J 0’ 5~ 9 . to components in Table 6.. —~ —— 07.4 ‘4 NJ 0’—40’soNJ. H ~ 3 0 -‘ ~ ‘..a.9 ~: ~.. Minutes Figure 6.4 to a NJ 99993~ 0%0’ 0’—J0’--4so-0’-J so 00 La La a .9.. so -4 0’0’0’0’-40’ La i.9 0’ 0..) ~.9 9 0 (5 0 B ~0” (5 ‘M ‘~‘0’~NJ~~ 00 C em ~< 99~~333393*39~9_ ~.J 3 tO ....) ‘r~ La ~ ~ — QQ~ ~ ~ a ~) .) La 9. 5 .J 993993393 — ~4. NJ ‘.i .9 —~ NJ —9 so -..9 . 3’ 0 0% 8’ 0) C 3. —‘0— NJNJNJ.) —0..4-4. ‘4 0... .’4.‘~ -.J.4...4 “.J0’-4..0— 9 0’ 0’ C. 00 .33333333 3e~ so NJ 0.4.NJt4.1-40% 0’ 0—-) = a -4 -4 .9939~.0 . ~ 0. ~‘4.. ~ NJ NJ NJ 9 .LaLaa.~ ~-Jnrir~ aa’~L. = .9 N) .0.9—.J .0 — — NJ -J’C ‘0 c~ La NJ NJ — .. .499—0.. Gas chromatogram of a condensate sample using a capillary column. C0’C0’La. 09” .a La a.) 7’. a—NJ33 0. 9333999T0 NJ’.GJ..N4NJNJI.4NJNJaaaJosoNJso NJCJNJDJN. NJ?4———r. NJ4~————~..C — .C ~ .9 so 0’0’0%0’O’NJt’JNJ0%.9.9 — -.0 0% 0’ NJ NJ NJ so —4 0’ La — .9i = 4.LflJ.0 NJ * 3 ~4 ‘0 NJ 0999— NJ~~J__ .:~ ~.. — 0..9O’N4NNJNJ — — so NJ C a .JNJNJNJ—N.4 Laa —.90’ so 9. = 0.~ Za~—— a 7”) “ 1% -~~‘u9~~ — ‘~< ‘~ a n %j~ 4..)—t.0 C .‘r NJ — ~ r~ 0’ .. La 9 NJ — S so ~LflsoNJONJ0~3~4.a’°’a ~ ~ 0’ 0’ 0’ (‘) ~ 0 .a4.* 939939 999 S -4 5 a’ 0 .0so 3 .a -4 9 .CN.4.0 NJ-) 0’ 05— -.4——NJ— 9 = so so 00 = so 3 0’ Ct 0’ CCCJ.Jl() —. I’~i .4.a a a a t. 00 ‘... -. cm..4—NJ. It NJ ~ ~ ~ ~:. —4-J.4 La 3 -J ..

P~.1)83 0.259 Dens.244 3.237 1(12 779 9 2.216 112.086 0.4505 + 9. M. 0.7791 0.243 28. 15302 is1) x I (Y6T~—(2.1)93 0.2 CRITICAL PROPER1’IES Time critical temperature.trans-2-DM.526 UnspecifuedC8 0.523 3..352 2. ~ens~ -.7700 0. compressibility factor.034 44 1.259 0. pressuire.7900 0.tX)6 3.t)54 1.004 Tumble 6. The combination of results from polar and conventional columns are then used to determine PNA [8].886 65 621 0.4.259 126.034 0.7995 Several nnet.3864— 0.539 116 793 2.2.106 0.407 112 t41 163 It 12 13 14 IS 16 17 18 19 81)1 803 51 52 53 54 68 55 56 57 58 58 58 59 60 61 62 63 2.091 3.598 116.013 0(107 0.033 0.259 128.uuoO 126 243 128.7) humP.t)54 0.7200 175 190 21)5 215 237 251 262 426 836 843 849 863 844 846 857 885 - 3.163 0. ‘lime correlations in threir original forms use Field Umnits.243 126.243 126.642 306 Unspecified naphtlrene 2.M.277 0.846 2.7192 0.fiS-1-(O. 63 64 Unspecified naphuheune nC9 UnspecifiedC9 Nonanes total 2.000 89 754 11 2.Cy.241 2.9099/Sn) x I 0’’°T~ (6.216 114.114 0.TM’Cy-C6 Unspecified naphthenc 0.sylenc 4-M-C8 2-M-C8 Unspecified naphthene Unspecified naphthene Unspecifuednaphthene Ortho-xylene 3-M-C8 I.199 0.105 1)1)51 0. or pronmising methods.551 0.772 3.7799 0.243 126. tIre correlations urre presented wills SI units.006 0.6.7000 0. W. 6. boiling point.792 63 597 6 0. Ve.471 0.3 (Cont.7900 0. S.094 0. The differences are of the same magnitude as typical deviations in measuring the properties.R+450.3-E. without any need for flashing the fluid into gas and liquid samples for GC application [18].124 3.182 / S +t).DM-C7 Ethylbenzene . also known as the megabore column.436394-4.916 2.023 0.7144 0.7065 0.270 0. Tc.054 0.l l = 5 l.4. Conrmparison of single carhomr nuumrher group properties measured by distillation and capillary (ic analysis.479 1.437 2.3. 7 3 3.l44l — 189.106 162 175 3.801)3 0.190 0.0566/S_(0.037 0.034 0. can be used successfully in compositional analysis of live fluids.8000 0.427 5.105 Octanes total 46 47 48 49 50 .045 0.020 t).DM-C7 2.024 0.5.168 126.429 116 799 #0+ 10 90.011 0.007 0.7242 0. g/cnn’ 0.2.Tine most widely used. W.232 101.020 0.687 0.168 128.230 0.Cy’C6 0.1)5 I 0. The column which provides the versatility of packed columns.7900 0.and tIre acenrtuic fuuctor. 1. either in graphical forms or as equationns.220 Table 6. of single carbon groups.2l343/S )x lO” T +(o.191 31)0 134 148 868 2.009 0. Peak No.4244-4-0.599 0.259 126. whilst maintaining a high resolution capability.014 0.79(8) ().t)64 0.148 128.697 0.281 0. Tire majority of these correlations are reported in L h9~.667 3. F! mild Cluaracierisatio.232 114. siusnilar to tirose of discrete components.259 106.383 4.1)26 t).243 126. K amsd nm’/kgnnol.E-Cy-C6 Unspeciluednaphthenc 0.722 2.003 28.954 0.018 0. A highly useful column for hydrocarbon reservoir fluid analysis is the wide bore capillary column. Disnillation — GC Weigtnu % Mol.089 1)008 0.(u34 4.8844 0.231 0. hun ilsis section.112 0.DM-Cy-~6 E-Cy-C6#t.8714 (1.078 0.47579 + 1. and are given as such in Appendix B.cis-2.024 0.Cy-C6 0.7900 0.7242 0.7208 0.l. Individual components identified by peak numbers in Figure 6.130 422 ________________________ 6. The preference of direct sampling and analysis of high pressure live samples relative to the conventional blow down method is discussed in Section 2. Experio’nenla! Methods 221 Mol.).168 0.523 190 205 218 235 250 261 812 827 840 845 851 842 845 854 888 20+ 61. Time metinods have mostly used measured critical properties of pure compoumsds to develop correlations.017 0.4.135 3.7262 869 798 803 107 90. Tb.201 3.017 0.0069S)x l0 /T 5 5 (6.545 0.027 0.hsods to calcunlmtte tire critical properties of petroleum fractions are available.978 126.047 0.027 0.923 0.010 0. are required for phase behaviour modelling using EOS.057 59.018 0.volume. Component Weight % Mole % Votumnne% 43 DM.21] 74 S)Th +(o.~ Wdgta% ~ Den /mn’~ 5 0.4.7214 0.01)7 0(8)4 0.79(8) 3.243 28. The units of P.l2h6/S+ 0. or the molecular weight.020 0.649 0.004 0.259 128 259 112.098 45 nC8 0.7918) 1)8683 Unspecified naphthcne m-+p.DM-C7 I.559 0.124 0.790() 0.089 0.243 0.069 0.216 I t8. [20.825 103 778 3. The aromatic content ofan oil may also be determined by gas chromatography using a column containing a strongly polar stationary phase column which elutes the components according to their boiling points. of siungle carbon number groups and thç last (plus) fraction of reservoir fluids.259 128.155 0.737 82 695 0. Lee-Kesler Correlations so A comparison ofthe calculated properties of single carbon groups using GC data and the above method.7173 0.039 0.C6 I-M.082 0.031 0. 112. Z~.699 85 669 7 2. T and v are MPa.047 7.243 106.029 0.243 126243 11)6.7900 0.371 91 751 2.068 0. w.957 0.8) .m 6.984 3. respectively.7900 0. These properties are determined from generirlised correlations in terms of the specific gravity.5-DM-C7 2. are reviewed in this section.434 0.223 0. with those determined by 90 equilibrium tray distillation on a condensate is shown in Table 6.009 0.

04 0. e.000t)E+00 l.9). Nor.8).89698r~t + 3.8 1 +c0 2 +d0105)}0~0 (6. (6. i’~.007465K~~ + 8.6I97(InM~i . —7. Iiq.00546W + 8. and 01 and 02 cams be any two parameters characterising molecular forces and molecular sizes of a component. I 54 8 6 W + 2. exp[(s. M) or (Tb. i~he critical volume can be calculated from.14) v.52117 .03 - 0.359Th for T .65848(I0 ‘°)i’~ + 0. M = — +(l . +2.92714 + 6.318317 + 0. mit wlmuch time nsom’mmmal hom lmnmg pounil . ‘I’he estimmsatcd acentric factors by tIne above two corrclaliomms at l’~.1478b. It) I 3 Mt un. The acentric factor correlation.=0. ‘lIme correlations developed by Twum 1261.4. Eq.= [0. 15) for T~.9) is simply a re-aiTangeunneunt of lInc Lee-Kesher vapour pressure correlation.252912-03 - 1. Properties stuch as tIre mrnolecular wemght.l(. (‘.1. given in Appendix B.i.290l—0.3 t4OF-04 I .765912÷1%) 9.2).Iry~J~ i 286 4 2 W 3.03 2.16) (6.71 Sr 0.( I .533272 ±1)343831(11) )i’. The above methods do not provide immformation on the critical volume or compressibility factor. / I 0O)°J )2 0.(6.9) 0=a [exp(h9 (15.2641)4 0.601212. ~O. Eq.00001ij38) e I 0. P~.099334t~ + 2.. = 140. The correlations of Cavett [22].2.cal Propet lu’s 223 5.6875/T+. a to 1.0.2518—l5.0555 4. .286590(tn M~) 2 — 39. w={~[log(~/P )]4(1y’rb)_ l]}_t 4 (6.81)14 . tIme uronrial boilimmg point at 0.0879tma (6.1) C 2 I 11+03 3.(6.caiiom 6. Eq.~.18) (6. and then cxtemmd these e(srmelatioums t(r pclroletmmmm fractions. Tt. The Edmister0 correlation 1231 for time acentric factor is commonly used with tlse Cavctt correlatnon. refractive index. wlmo nised lIne difference bctweeir Ilme specific gravity of time Irydrocarhon fraction umimd tlmat of tine mmom’ummal P~’ a ff1us wit lu I Ire same I uoi Iinsg poinil mrs I Ire coru elating l)aruumeter arc as follows. 1 () c ‘t~ P~ P~ (vcfM) (vc/M) M 1)~ 01 lb M l~. P v =Z RT 0 0 0 0 with the critical conmpressibility factor estiusmated from the Pitzer correlation.3036 6.17) (6.1)846 1.71579 lnnM~— 0. 0..5.775412-04 3. Z 0 so ‘flie properties of rmornmmal paraffins are correlated wills tine normal boiling point temperature.9990I3. >0.)/Th.10).14 .58262 (71) < M <3(11) 3(111< ‘I’~ <61)) K) Perturbation Expansion Correlations Tlnese nsretlsods imnitiumlly correlate lIme properties of rrormal paraffins as time reference.0l063K.533114 - d 6.4721 lnT~+0.21)3711 0.()(. density.36159w’ — fl 7495111 wlsere tIre stmhscript p refers to propcrtmes of normnal paraffins and.122488/(ln M~rJ (6.657012-03 9.+ 1. Any pair sucin as (Tb.19) Riazi-Daubert Correlations Riazi and Daubert [24] developed a simple two parameter equatmors for predicting physical properties of hydrocarbon mixtures. munsd tire definition of acentric factor.526167(10 1 7 )T~ (6.51274 2.10) where Phr=PbIPC. The authors later [25] improved the correlation as.9.7490l~.7506 2.523312+00 3 1510011+02 C 1)5102+114 - - 3.97t0E-03 0. ‘Fable 6.31184 .984036 t. mu memustmred.g.2028 - 5. I —Tb/TCP ‘The ummolecnshunr weight of paraffins is givemr by the following inmplicit relation. critical properties.4791E.97476 0.(1.05 - ‘I’~~S M S 1 h S M S 7 5211812-04 I .5 Constants in E2c .rTt/rc.(I.21) —13.15) wlmcre.53691 1.408 0.6015 .43S77T 0.0460774 1(1’.(6..2998 .4 I . l69347T~)/ — (6.4844 0. S) may be used for 01 and 02.1352K — 13.11) ~2 S S S S I) C 9.ul /‘araJ]rns 5 where 13 is time atnunosplmcric pressure.20) where 0 is the property to be determined.843593 —0.03 4.222 o =(ln ~hr — 6.M and Tb.811)67 0.7512 InM~ + l9. lOt 3 MPa (1 urtrirosphcre) unnid K~us tIme Wunlson -Imuirmn&’Icrismut ions factor.401673 1..09648/T÷.12) — I.8544/(1nM~)—0.774)12-03 0544.651 ~ (6.. Time correluni ion is derived by crmbiisiumg tIne vapour pn’esstun’e relmul imruu.) 6 0-19012.82055 + (1.8063 0. Oa Oh n 0< 2 (6.28862 lflTbr —0. v~.8078E-03 2.904 + 0.04 85oS(it~l0 I .03 0. 1264(1 + 2. = (6.0. 0.mlerj.8 5 1~ ) forTh.21 266v~+ l — 34 Il.13) 2 P~= (0..I~ duller umbomit 2%. Eq. for T~ and P arc also often used in phase behaviour modelling of hydrocarbon systems. Fluid (ha. arc comnstumunls for cads properly as givems in Table 6. Ph is tIre pressure uut which “h is measured. heat of vaporisation urnd llremnal conductivity were successfully correlated by the above equation 124].642212.

= exp [0. Riazi and Daubert [25] compared predictions of their correlation.0 123420— 0.2 so exp[5(S~ S)] — I Critical Volume: = V 0~ [(l + 2f )/(l — 2f )1 2 Tine saturation pressure and density. 1.7.1 0. 0 0 (6. is not recommended.1) Maximum 13. TIme correlations are for single carbon number group properties.9 4. M~= Tb/(5. Eq.. i’he results clearly demmnomrstrate the major immmpact of the correlation used to cumlculuoe time critical properties on predicted results by EOS.-t). such as c +. predicted by tine Soave-Redlich-Kwong EOS 127] for a process where metlsane was imncreunentally added to an oil. ~M exp[5(S~—S)] — . — S)] — 1 to 0.002301931’b)+(_I m (625) +t)..ce Abs.22) generalised SCN groups.6 ((.2 03 0. Average 11. 1 40 = ex~4(S~ . Vutriurtiouns of bubble point pressure predicted by Soave~Redhich-Kwong EOS usimmg difi’crent correlurtiomms to estimate SCN group properties.8. The properties of any petroleum fraction are estimated by adjusting the calculated properties of the normal paraffin with the same boiling point as follows: Critical Temperature: T~ = T~p[(l + 2fT)/(I — 2fT)1 2 ‘ Table 6. or by a continuous function as described in the next sectiomm.2 ~ Abs.S2)] -1 35 ~::: Da~e4 Critical Pressure: = .l43979/Tb)ASMI 1 ‘1’ = 0. 182421 + 2. EnsMfrl’I+(_0. Comparison of several niethods for prediction of critical properties. with others for i38 pure compounds.244541 /Tn.. These fritlons should be 7 characterised initially as SCN groups. because of its reliability. and their application to very wide boiling range fractions. ‘Time Irropertics of time oil heavy fractiomrs were delermiuseci by various issetlmods for pimase bclsavmour curlculations.7 3. Critical Properties 225 The above method.15) using Tb and S.Crniicaimrmu ~ (6.2.2 2.24890/T~)As.26) Figure 6.5 31.224 which can be solved iteratively using the following initial guess. respectively.4277+l87. are shown in Figures 6.(6. with the results given in Table A.7 and (r.800—0.6. Average 2.0 0.cation 6.2 16.7 ~ ~ .4 3.4 0. Mole Ranto (lflMP)[(l+2fM)/(1_ 2fM)1 2 (6.0052Tb) Petroleum Fractions 6. N~cmlm~s~ —%Dev.347776/T~+ (_o.5 Aided Me(iiane(Oil.934/’l’~ us EnS ~.0175691+0.()0414963’Fh)ASP] ~—~_ — — = I. with the results given in Table 6.24) f so AS40. Fluid (imaracteri.~ Maximum 2..5 12 4 = AST[~270159hT~00398285_0706691~)~T] ~uvcui 5.5 11.432l IT~ .53262_34. has been used to calculate the critical properties of (6.6..23) Riazi-Dumubert l’wnj KestcrI.-‘~ — — ~ AS~[(2. 5(S Molecular Weight: mM — ~.2 in Appendix A. using the reported boiling point and specific gravity in Table 6.

16 t-T /1’. it is more advantageotus to limit the continuous description to the heavy fractmomms.1. along with the above calculated T. Althougln complex funnctiomss mnmay be found to describe the concentration distribution in the whole mnixlure.2 itt’ (‘~. 0. 520 K and 190 kg/kgmol. The specific gravity.MPa 6. F/uio! (‘/timrui’lerj. P~. Variations of saturated liquid density predicted by Soave-Redlnch-Kwong EOS using different correlations to estimate SCN group properties. S 11.(6.004386 1. as the concentration 7 C fraction is getmerally mime highest amongst tine SCN groups.536 065 l’hc cuilculaled values for single cusrhotm nummiher groups. Table 6. as the most readily available dmmtn. I.. wlnere relatively sinmple functions would suffice. -0.953 . 0 ‘lIme resunlts u if bittIn mnpproaclmcs. Figure 6.9) of the LeeKesler method is used to calcnmlate the acentrnc factor. which describes light comsiponents by discrete compounds and heavy fractions by a mathematical function. K 5 Table A. or M-S data of C.7635 Next. Mote Rali.20 P. .’ 6. Eq. TIne conrtimsuous description of um flumid is commonly used for compounds heavier than nC . (h) ‘the commtimsuomis dislribuliois functious nnay be umscd directly in pisase behaviour models.727 -0. munstead of d iscuele colmipouseust datun.7635. are read as 11. unsung liq (6. Figure 6. .826.25 0.. K 6.003812 0 I..226 6.. which results in. and 1’. AST I~ T.8 0. they can be more thoroughly expressed by courtitnuous descriptions.c(j(iopm 6.1. are initially calculated as follows: T . (u)=O. ‘lime conlimnumous dcscriplion of a flund mmnixture has two major applications: (un) II can be used to iursprove amid cxtemmd fluid clmaraclerisation through describing the plus fr:mction by mm usmmmnmher of siusgle unmsd mmrunltiple carbon numsnher grotups. I 5). the above calculated normal alkane properties are adjusled. volume amid tIre acentric factor for C~awith properties as reported in the generalised property table. i’lme conncemslrurlions of SCN groups in a North Sea oil sample is. pressure.S 1. A compound iisay be represented by its carbon number.8. umrc exaumrples of such conlimnuily.23 708 AS Equation . The Cg+ could he a ummore appropriate choice hr most cases.2. are ctrnmmnmnorm Iy mm sed lo esi unumute tIme criticunl properties.19 521) 686. ntn’/kguummii 060’ I’. K ‘l’~. 0 44 are given in Table A. and that of the normal alkane calculated above.1.55 00 01 02 03 0.3276 . and the gas chromatograuns. s 711) 711 v.ee-Kesler for the acemitric factor) and Riazi-1)aubert (l1dnrmsler for lime acentric factor).shown in Figures 6.734.4. mure given in Ihe following tumble. respectively. (m)000 . boiling point and molecular weigist of C. that is Equation T. Critical Properties 227 Ow As the reduced boiling point temperature is equal to 520/708=0. m~... MPa ‘t~.9. is somrnetimes referred to as semi-continuous description.826. 11q.. S Riazi-l)auhert Correlations lime critical properties cumum he estinrated by eiiher using measured T -S. C -C . Ilcirmg tIme i2dmislcr correlatioum.. S 1.9112 M.t>3073 0. particularly in the absence of cx pcriimmcnmtuml dumla. Solution.K 6.8135 0.18 S~ 6. Figure 6.1135 0.2 in Appendix A..1. results in.001399 m’fkgniol AS~ f~.4 1) t)aiasnsi’it Added Meiliane / Oil. bussed on the difference between ihe C~specific gravity.24 6.6348 0.S 1)75(1 M. 0.I I).2429 1. Tlnis approach. fronn Table 6. simple decay functions 11 can adequately describe time fluid.3 DESCRIPTION OF FLUII) HEAVY END Although numturuilly occurrimmg reservoir Imydrocarhons are commonly described by a nunsber of discrele components amid comnpomscnt groups.17 v 01 6. uniung tIne nmrellsods of Tsvu (I. 1 0 6.S M. Twu Corretalioums ‘Itne properties of lime norumsal alkanne witls lIme smmmnnc bonlnmmg t°”~~ mis that 521) K.0268l 0. MPa 1 6.~.(6. Example 6. hence. using the above method.75 I ‘[lie unmeunsunred values mmf spccituc grmmvnly and hoiliumg point. Tire TI3P cuirve.~.4 116 Calculate the critical temperature. that 6 of us for C +. v.

mixtures with component distribution vastly different from the normal trend.3.exp(—0. Reprinted wiih permission 1121. however. Pedersen et al. boiling point.27) where z~is the mole fraction of single carbon number group C~.28) where A and B are constants for each fluid. lix) en It Waxy 0/i ~O C3 - CS •‘ 111nC4 C 62 tIJ. that of Katz 1281 for the C7~frurclion of commdensumte systenns. Distribution of SCN groups in a Nortls Sea oil. A linear relation between the SCN and logaritlnm of concentration is generally adequate to describe heavy fractions of most reservoir fluids. approach is to use a functions to describe the comncentration of SCN groups. Description ofFluid Heavy E. Biodegradation generally reduces the alkanes and. Naphienic Biixieg.aded 0~i so I . Figum’e 6. Fluids Normal Parall’inic Oil containing high concentration of aromatics and naphthenes often point to bacterial activity in the reservoir. The above simple expression was capable of representing the measured data so well that the authors did not see any advantage in having measured compositional analysis beyond C ÷ in preference to calculated data from Eq. Figure 6.(6. Gas chromsratograms of four different types of oil sannples showing line distribulion of varioums components. to a lesser extent. 10. Single Carbon Number Function A simple. and evaluated it for a large number of North Sea reservoir fluids with measured compositional analysis to Cgo÷. Flutid Characterization 6. Various functional forms have been suggesled and applied 128-301. The concentration can be expressed in terms ofmole.9.nd 229 molecular weight.9 is typical of most reservoir hydrocarbon liquids.lt ~ . with reursonahie success. There are. Clearly the distribution of SCN groups in non-comnventional summmmplcs cuunnnot be represented by simple distribution functions.38205z~. or other properties. The simplest of all is.~ ..228 6. 1311 proposed tlnc above equation. Copyright (1989) American Cltcunical Sticieny. the aromatics. but very useful.28).J - 6 Single Carbon Number 29 Aroiltumnic It itxlegraried (lit Figure 6. weight or volume fractions. Inz~ =A+Bn (6. 20 . as expressed mathematically [191 by.25903n) (6. The distribution of SCN groups shown in Figure 6.10 compares different types of North Sea oil saumuples.

47 (1. Table E6.843 0.4 I 12.769 1)785 0.1)082 (1111164 0(1(147 (((11)39 (1(11)31 ((.56 1. SCN (‘7 (‘8 C’) molecular weight data of SCN groups. can equurlly be written iii lerimss of tIme molecular weight instead of the carbon number. Extend the analysis to C3O+ by SCN groumps. E.. M~ = 14n —4 (6.1)1 86 11.2586 9.8% 11. The two parameters of A and B of Eq.82)) 0(143 (1.9880 26. Description of Fluid 1/eat’s’ Eumd 231 In phase behaviour calculations the carbon number is umot directly used. 1 4 Mçl nö ‘ (6. S .04 2. it nmtmst be TIre mnmolecular weiglst is oftemr relaled to tire carbon Its x~ = 0.4200) 1)341 I 0.0104 (1.0717 0.31) .0243 11.1237 3. TIne unmolecuulunr weight amid specific gravity of SCN fronmr C .806 0.0568 ((.11 9. A value of ~=4 is mm rcuisonumhhe approximation in most cases [30].Suhstituting time molecular weights inn I Ire mnhmive relmml tin rennurns tIme results as given in the following table.4665 — 0.30) U a L .2586 2.05 2.17 5.4 117 126 40 153 16.1)8 0.1467 1.22 5. (‘~ ‘ C 9 C 1 C 12 C 11 211.68 427 3. is reasonable for this fluid.111124 (1. Relation of unmolmmr coutcennration wnilt umiolccular weight for SCN groups.188)9 (1.n Fmgure E6.83 3.7 (1.888 1)80)2 11.11012 0.844 1)843 (1(1St (1. lmenmce.7781 16. resulting in..909 222 237 251 263 275 21)1 300 Soluaio.6860 6..881 II (4(15 (1.(6.89 3.28).0923 11.3546 1. Eq.856 ((.l. CtO CII Ct2 CII (‘14 C IS C tO C17 (18 (‘19 C21) (‘2 I (‘22 (‘25 (‘24 (‘25 C26 (‘27 (‘28 (‘29 ~ C. Note thimt the uusxumtmstntion of a hinucuir relunliont heiween tine logarithm of mole fraction and the molecular weight.(6.899 0.9701 9.730 0.6062 2.rample 6.5 81) 07 209 The total concentration of C7+ fraciion of a gas condemnsale is 3. to C . . M .23 7. Wlsen partial analysis of the C + is available. which are not avurilable for very iscavy frmmctiouns. the constants in the two equations have different values.1211 0. suggests that Eq. are assurnrcd to be the 1 2 sammme mis those mm tic geusermutised table properties. ‘I’ahlc 6. Fluid (‘luaracterisatiopu ‘ 6.730 ((. The advanntage of weiglmt basis is tine lack of need for lIme 220 Molecular Weight Figure E6.785 1)799 11.866 0. (6.902 x xM.861 0. 6.844 0. nunnber by.111119 18.9220 10.3 I).0) 80 • 100 120 140 160 180 200 The above exponential function is also as valid when the concentrurtion is expressed in terms of weight fraction instead of mole fraction. 312 324 337 349 3611 372 382 S 0.0497 33.020056M .33 1.2.45 C C 14 0 94 11 7 126 140 153 t65 180 197 209 374 0.02 4..43 4.754 11.230 replaced by some physical properties.1’ V The abo~’ecorrelation.18115 0.1)427 11(13(15 (1.37 7.73 11.29) where ö depends on tire chemical nature of the SCN group.2. sM/S 1)2(121) Ii 2141 0.806 ((.111)85 5.04 t .933 0ft236 1)51)76 (1.(6.46 3.87 I 1)876 ((.3.2.57 (1.63 9. the constants cams he determined by regression.1111(18 (1. The expression in weiglmt basis mury eveur be nsore appropriate for some fluids.84 12.92 niote%’ with the analysis as follows. Composition and properties of C7+ fraction. 7 mininsising the sum of squared differences between the cumictulated mnmnd mmremmsumm’ed comsceurtrumlion of known SCN groups.2867 131.71) 0.2)) 21 .3720 7.0137 0.13 6.88 Tmtnat 0.38 (1.31) cars be determimmed by tine least squuare fit (excluding C.49 2.2 shows the relation between the nroiar concemmirumlioum nnd nimolectular weiglml of SCN groups in this example.769 0.0787 4.01 25.820 0. S lflZç=A+BM~ Obviously.1(159 1)9532 11.).7645 I .754 0.99 .32 166.799 0.

+XcsoMe..satio.fraction of a gas condensate sanmple are 0. C.(i36. and C as the tmeaviest fraction present in the mixture. (I — ~ ~e~~t(n (‘ ~ )I 7 (E6.. example by the mass and volume balance for the 1 fraction. C.067 (b) The C .)Mc..= 0. ~ j ~ =~exp(A+BMe.32) I I Z~ Mc .slrmutes tlrat lIne slope of the SCM group dislribution line..O. tine two constants cain be 7 determined by solving the following two material balance equatiours: Cn C~. by simiftimng tIme line up or downs in Figure E6. results in. by making Zt. molecular weight and specific gravity of the C7.. is deterimniimcd ilS. 2 M~. C .~. (‘~ UN =eft~~Mc. ISO.940 35 The molecular weight and specific gravity of C . c.MC.1. Me. Hence the molecular weight of C. Hence2 a similar approach to that of imrolccuuiar wcigimt cmmmm inc used t~ calculate the C.. as the contribution of very heavy fractiorns.. C so 9 ~zC. resmmlts ~ C.81 5 The volume balance for C . Solution: Xe~. Eq. ‘I’he mole fraction. . in mine nnixturc.8 15.MU. is minimal for practical purposes.33).87 S~ .. /S~ =166. jusl the ummolecular weight of C . 7 Sç. (6.3) dernmonm. 2~XcMc ISe. The puurmmnremer A affecls only the mole frurction of 1 (‘7. has very little effect on predicted results by EOS in most cases..(E6. respectively. =l65.4=~x(. whereas larger nrolecules with higher carbon numbers are generally present in oil and gas condensate systems.0392. . due to tiseir low concentrurtions.. Sunurularly for Eq.232 6. 7 7 (6. C. depends onmly out the irmoiccuilar weight of C .. so ~Z(’~ C. = M~. Values of 50 1321 to 80 [311.M(. im~stcmud of time C.. so~exp(A+BMc)=ze.013141 8.= 503 (c) The volume of C .067 (‘~ M~. could huuve been cmmlctilaled itm tins 5 C . + xU. r1_~xc. ~M(. C.3’) Norumnumhising tire di~tributionnof SCN groups mm time C .. timat is.933=0. Table 6. however. 11 l3~0. Fluid (‘Iuarncter.. the fluid is c. .mole fraction is calculated as. M~. A so Inn. 165 and 0. — ~‘‘ ~eBMtn c. .(6..= ~XC.. = eA~e~0 C.99+0. . fraction. fraction only..86w l65.31). 1 C ..=202.3) resunlts in.2. 1 I lermce. Description of Fluid heavy End 233 (a) The C~..M(.7+0.m 6. fraction can be considered equal to the surma of voluuummes of mmli its components. 7 I Assumimming SCN groups wills nrolecular weights equal to those in the geuserahised table. is available. we obtain... 2 Example 6.~. /S~ .33) A so irs z . I of its coulmprisiung SCN groumps.(6. fraction molecular weight and specufic gravity shotuld renmimin the suuumme when 7 described to C.3. The choice of the cut-off carbon nurmber. we obtaium.~.. C. C 7 ‘l’Immul is.3.. C~ Rewriting Eq.s. I I ~ C 7 ~ soO (E6.ci~t~ c )/(~enm~tn 5 \ j 202. fractions is suufficiermt to describe the distritaution CN is the heaviest carbon nunnber assunned to be present in the mixture.specific gravity.=l. so 131. have been suggested as the cut-off carbon number.. C.3) i3q.4/S(.067Ix503xM~. =~ /c.. Describe the C7+ fraction by SCN groups extended to C20+. =1-0. When little or no compositional analysis of tire C ...etu0mcn (‘~ ~ C 7 /S~. /S~. B.

0082 C43 ((0024 C24 0...0818 CI’) 0.. F(l). fractioun properties. mole fracniouus.. suds that.11043 C39 0.0125 C32 0. (6. I Ic m5c’c .3209 Ct 2 (1.0484 CIt 0.0178 0..MC .01)13 C41 (1. ZC .35) ~ /S~. can be determined simply by integratimrg the distrihutioum function between (n-h) and n. it describes line relative concentration within tine conml tusumouns purt .527 (1.(6.0243 (1..4 between nC and nC is taken as fine 9 10 comsccnrlralion (If ~ grotip.0082 0.2020 0.0936 C20+ Continuous Description The above approach of describing the concentration of SCN groups by a function.. C8 C9 CI)) CIt (‘I 2 Ct 3 C 14 P. is often expressed try nnolmur dislrihtnluomm.0568 0.36) In lIne nsmorc pruiclical setuni-coumtiunuious description.calio. The finnctiomi describes the heavy part by a number of SCN groups.1478 C 16 0.0(119 C26 0. II shsould be umoled tlmal the conlinstuouns distrihulioun is valid at all the values of I. SCN Group Mole % SCN Group C28 01)167 (‘29 0.l and C .0923 11. cars also be used to describe the concentration.=0.4074%. can be the carbon number or any property. is aimed.0030 C42 0. instead of carbon groups. only the heavy part (say > C. —C.4516 C 0 0. ‘l’hre musteumsity chislrihumliotn. Ibmurl is.0983 C27 0.4)1)71 C44 0.0313 (:34 (1. respectively.2670 C’ I 3 ((.0110 C22 0.0377 0.0717 0.le % 0.1604) 0.. SCN Cl J F(l)dl = I (6.roup Mole ‘S initegral between Cui. but it is basically a discrete representation.6. C .2221 (‘I 4 I).892 The normmrahised mole fractions of SCM groumps iii the C ..6.068 t (1)1567 (1.’n tues vmim ymung so gu udumally himmut (10 mnol allow (lnstilmclive iulennt i ficumi i) iti lime contitruorns dislrihutiomr of comrponnenls can he expressed by a function.0146 C30 0.0226 (:36 0.1)1 86 C17 C18 CI’) 0. within the idenlnfued range of commnponeurts. IS . then.0137 0.. such as the urnolecumlar weigist or tIme boiling point. urn lime seitmi—conl i nuotis uupprourcls the calculated Concerslration of tine comnttunuloums coussl ituiemsls slmouuld be inntultiplied by zI) to mm(srunalise it in the total mixture.(6. or lIre prohmnhihity of occurrence in statistical terms.~. contrary to the SCN group function which is valid only at tIre discrete carbon numbers.0104 0. Ilme area umuuder time curve in Figuure 6. for a fluid with the sanme C. fractious cmulcuilaled in this 7 tbnose calculated in Exmumusple example are given in the following table for comparison with 6. nsay appear as a continuous description of tIre fluid.0264 (‘35 (((((1(94 (‘45 11.0026 M. 51 210 5 = 5 F(I)dl=z (6. within the integral boundaries. where tIme distribution of all its conslitueusts. aind so used ins hhnis hook.0095 C38 0.0699 C20 0.u 6 1 /)ese.0306 0.37) svliere ~t) is line cormceuntraliomm of Ibte lseumvy frurcliour of tIme fluid described by the continuous ulcscm iptuour.6273 C8 0.. the specific gravity of C .. is deternniumed siunnilar to that in Example 6. with priifs.2.81)1)8671 Eq. tIne funchions provides lIme value of concentration 235 Substituting time B vmmhumc in Eq.0597 C2I 0. llmmrt is. If all tIne coinrporrcnts of a fluid is described by the continuous description.. F(l).’d tumble.234 6 F/tool ( ‘l.0195 C37 C18 0. i. represented by I.0305 5 F(l)dl = (6. A more appropriate approurch is time continuous description of the fluid.0430 (‘23 ((((367 CII 0.(E6..2 0. 5 so C7 0.a..=0. 11124 (‘I 5 ((. ‘l’lrc distrihmmtroun ftuuicliomu is generally selected sucln that the value of integral in Fq..0819 0. The insole fraction of SCN group n.1152 0.0209 0.0055 where i refers to all tIre commmponenls counrprisiumg thue SCN grotup n.37) becoimmes eqmimil to I. M~ 51 so ~XC.. iption of Fluid End cummbomm ntnrnmhcrs. wlrcrc z is time totuml councemntration of all line connpouscnts. Indeed the carbon groups reported by lmrhoramories mire deten’tnrined by integration of corsipotunds comprising the groups. trm hleam’u’ ntmurtlncnraticuml terms. 2 =i3”~ Assnuusning tbmat SCM groups have tine samsne specific gravity as those in the genmi’rmmhism.5.1211 (1.34) SCN Group Mote % C17 0. ‘time mass or voltuirme distributiomr. uss obtumined in gas cisrousrustograpisy or distillation.5429 C’) 0.31 ) is then used to calculate the mole fracliomm of SCN groups as given in tIne folhowiisg table. ‘the connhituunnini~uiu’sci jIlt ilium nctl(’(’Is 11w trure nmmuluin’e of reservoir firuids hinal urre corssposed of nummiuty ctimiiliiummmds.002! C25 ((.0465 E. atsd is only valid at the discrete F(l)dI so (6.1385 0. characuerisiumg the compounds comprising the fluid.with 0 tue unolccumlmrr weighst dcteruusinied mis: (:4.2141 0. fraction is determined by sumniming up C.0.a~’term. S.3’). CtS (‘tO (1.1(139 0. 21 C.005(1 The C. Tire variable I.) is described by line contimstmous fumrctuorm. For exmnmmnple.38) ..0251 0.2.1198 id/. time valnuc of A is deterussimned equal to .0038 C40 0. SCN (.3807 CII ().0971 0.MC..3 0.

ranging approxiumnately between 0. or less tiran. 1 A 1 A 2 A 3 A 4 = -0. parameters delermmrined by regression mnmatch used tine available SCN group experimental using 7 Eqs.3.482199394 6 A so -0. TIme function so developed can tisen be used to exteind tire fluid descruptmon to heavier compounds. Fluid C/uaracterisaiio.(6.45) Similarly.42) wlmere MD is the average molecular weiglmt of tlre continuous part. as a luning 6 parannreter 7 un tlse regressiorr. (6. and M . When the molecular weight of each component. the above equation becomes.40). . demonstrates tIne mole fraction of a pseudo component comm’uprised of all compounds with molecular weights between M .988205891 0. (6. Distribution of commnponents represented by the ganmrma probability function with different values of y.41) where r’(’y)..40) The most widely used distribution function is the gurummmsra probability fumnclioun.l Fleas”. Figuire 6. F(M)dM zc (6.11.43) Figure 6. r(y)so1+~A(y—1)’ Iy 2 where A represents the parameters in the approximate polynomial.39). and M . l)e. based on the defiumition of C .. M. It can be treated.193527818 7 A = 0.577191652 so so 0.respectively.918206857 44 so -0. fractious witim MC7 =20() ammd t=92. that is I M . F(M) = — t)~i exp[—(M — t)113]I/[IYF(y)I (6. conlrois the distribution skewness. The valune oft should ire between 86 and 100. identified by the sinaded area in Figure 6..897056937 A = -0.’ Enrol I) = . is determimimmed by. irowever. 51 5 The value of ‘p I. — c)iy 1 (6.47) . the mole fraction ofany carbon group. and ‘y and ~ determine the shunpe of the distribution fumsctioms with lime mean and the 1~32 variance equal to (~3+t)and ‘y .. t is the mininnumsi molecular weigint included in the distribution. Reproduced from 191 with permission.5 for typical reservoir fluuids. tlme molecular weiglnls of nC and nC . witlm itsdata. can he determined by incorporating the appropriate boundaries in the above integral.. ‘lime peak will smut towards Iseavier fractions by increasing the ‘y value. respectively. using the nsolecular weigint as the chumnmcterisatiomr variable.44) As described by Eq. F(M)={exp[_(M —t)i~3]}/I3 winds is a sinmple expourential distribution. reduces tire gannma distribution futmction to. 100 (6.(6. is the gamma function. 51 5 rime duslrui’uuutnon fimnctnomr us to getnerutlly to describe tIme C + fraction.39) which is the area under the curve of F(M) between M .035868343 8 ). so F(M) (M .5 to 2. the fraction of area under the curve between two molecular weights. winereurs valucs more than orre demmmonstrmnte a mmmaxiunsurms in concermtratiomn. tire vuulume of’y.seription ofFliii.u 6.46) 200 300 Molecular Weight 400 500 r(y) so which can be estimated from the following expressions [331. Values of yequal to. tire recurrence fon’ummunlum rsnumy he used to evaluate For y values otutside tIme range in Eq. JF(M)MdM = M~z~ (6. courmprised of compounds with molecular weights beginning fromsn ‘r and exlemiding to imsuinity. or pseudo component. Hence. The gamma function is. one represent 7 5 mmmixttmrcs wilh cotstimstnotrs decliume in commceumtratioum. — —i cM. the gamma function. mrs proposed by Whitson [9]. 237 (6. l2(M)=~i~_Li~exp(_M/I3) (6.236 6.(6.11 shows typical distributions with different values of ‘y kr a C . is used to represent it ins llue distrihutiomm function. or assumed eqtmurl to the 7 mid-value of 90 in line absence of unmeasured SCN group data.756704078 5 A = 0.39) and (6.11. . SPE Copyrighl. The molecular weight of SCN group n.

mire C..M —’t} j M —t 0 0 I ( [ 1 (6.(6.50).(6. — M .3 I). mhe distribution 47 function of time C.50) is the highest molecular weight present in tire SCN group and M~.—t) wtnicim results un. group of this example Immus.(6. ‘I’herefore.uiar weight compound present.tatnoruunaliscdnmole_fractions 0 1)858 0.52) I. we obtain. ‘lIme rmmohe frmrciion. ‘I’Imc rmmolcculmur weiglut houmundaries cumn he determined by solving Eq. F(M)= 0.. that is the fraction collected between two coissecmntive norrnrmul mulkarme hoihimig points. . and compared with the generalised vmnhrues.42) after seIecling the lowest molecumlar weight present in C.49) for lire geunerahised SCN groups.(6. mind nntegralimng it.inn Eq. The simm of nsole fructuous hecouuses equnal to i. ‘lime cormtrnhuulion of very huc’mnvy connpoumnds to the total mole fraction. Deccriprionm of Fluid F/e. / 79)=0. Assuming tlnat M.. Mote that the valuues are cquuaI willmin the accunracy of measurement. however. =(M~. due to lack of partial analysis of the C.0376 exp(-Mfl9) tum phase hehmaviomur calcumlatioums.mmok’cnnhmnr we ig ImI ..(6.2 702 842 - Ti. which results in ~3=79.(6.(6.. M. it results to carbon groups wills average nmolecumlar weights sigumificantly different fromir Itnose of generalised values.3l) us the molecular weight of SCN group.(6. time properties of identified SCM groups must he known. =l4.. that is. 1mm order to cimmuraclerise the C.49) —— ________ (l4n+2)—t M~ —t 1 = 7 z~. [ ( 14 ~) lnz~ =lnlexpi I—I [ ~M.(6.)/2+M .u. ilensce. with the values of A and B as follows: A= In expl 14 ~M~. and the values of group molecular weight calcumlated by hq. The simplest approach is to select the normal alkane molecular weights as tIne SCM group boundaries. Note that M. _~eXP(t/~)ft~~ + IJexP(_M.3 by mm countmnnuours function run lerms of the molecular weight.. t=86.49) are given un Table P6.SCN groups can be determined from Eq.48) The mole fraclions of . so _exp(t/~)texp(_M.. = where M.M. The calculated results will not typncmrlly deviate rnmore tinmun OliC unit from tire values determined by simple linear unveruigiung. arid uuse it to estimate tine mole fraciton of SCM groumps comprising the C7+ fraction.49). Solution: The value of y is assumed equal to one. Eq. arid M. Hence.. The given ununlecuular weigini boundaries are germeral and earn he riced for other fluids in the absence of numeunsuired .(E6. a nmolecurlar weight of 625. and M. cxp(—0.(6. the unse of SCN group properties for the above characterisation is not justified.0392xexp(-0. The molecular weight of SCN groups is determined by stubstituntiung line distrmhumlion function mu Eq. fraction in terms of the mnrolecular weight.hcr 30 41) 50 61) [. 1 lnz . calcunlated by Eq. Fluid (‘Iuara. oh’ czncis SCN group cars he deterrmnimme(I frousm lime above equation.4. i~)+ lJexP(—M i /I3)]/zc 9 (6. we ohluuumn. The dependeuncy of calculated boundaries on the C.48) cmmn be wrilteun in the simsnphe logarilismie fonss of Eq. Describe the C7+ fraction of the fluid in Example 6. Table A.=l4n+2 for nornmah umlkammc houun(laries. ummolectulmur weiglmt amid selected vmulume of ‘t. heconumes insignuificanl. t.uu’v End 239 Substituting the above distribution function in Eq. with M.(ô. ).ast u.(6. 14 ~\ M —t Ini expi I—Il— t~. normal hexane will be the component with the lowest rsnolecn.—c) 1 ~ j M —cj 0 t (6. Exannple 6.. 9 that of tine genrerahised SCN group has a molecular weiglnt of 539.mtjolt I 6.iiulccular weighi 422 St. their unnott’cutar weights sisould he used to identify the group houuumdmnries.’teri.38).17721 Sn) Note ttmmrt lIme normnnmuhised mole frmuctions.3 I) by rclumling M.9976 0. in Eq.9999 —t Eq.(6.50) which is similar to Eq. Aluhounglm the selection of ummolecnuhar weights of norumnal alkatnes as the boundaries agrees wiibm the convenijoimmul definnitious of SCN groups.577 18-0.40).3. For example. becomes. omuly when carbon nuumbcrs up to infinity are rnclumded. mis stuinwuu mum line following table for various cut-off carbon numnsuhers.55 I 8(m I — M. 1 logether.52) can be used to calculate am initial guess for B to solve Eq.3). ~‘ so lIne C. is insignificant. The value of f3 can be calculated from Eq. unmolc lrmuctuonn. fruictioun with SCM groups similar to those in the genermilised tumble. by the above approach.(6. are the upper and lower molecular weights of the comn’ipommcun)s presciml irs tine SCM group n. whmercuss ‘[‘Inis is dune tui preseunce of arousmatics and naphtlmeuses in the sanmple under consideration.. have been unnultiplied by Eq.2..238 15. 1 1 ‘Ilic SCM grouup nmolecuuhumr sveiglnl hounnsdmuries.4.9996 0. I~)— exp(—M. fraction.51) —~ (6.i (6.asmcarhonnum.

The results are as follows: .3293 0. with the molecular weight boundaries given in the above table.0164 0.(6. They applied the imsethod to 44 gas condetssate umnd oil smumnples. ‘p1.te fraction of C.5573 1)5162 0. i. [34].(6. as expressed by the integral in Eq..mus hccum adjnusucul no nuiakc the total mmmu. 530 531 ____~_9 _______________________________ 539 Selecting ‘r=90. The distribution functiomn.0331 C32 0. The parammmeters of y and ~1are optinmised by minimising the above stmumm.ttt)65 C43 0.48).0018 0.0049 C44 0. witlmin a toleramnee of ~ the upper boundary of the molecular weight is adjunsted..35).ue.lc equal to ‘1.ceriptionu of Flm..0325 C33 0.uI Cl 102 96 96 C8 113 107 1117 C9 128 120 121 ClO 141 134 134 CII 154 147 SCN Gromup Mole % SCM Group Mole % SCM (irmnip Mmutc % S(’N Grump Mole % C7 (‘8 (‘9 0.40).(6. ‘Fine use of SCM group data to tietermnnine the paraunreters of any continuous description is only reliable wincis the conceustratioms annul nunolcctnlar weigirt of sufficient number of SCN groups are known. instead of urssunmimsg yso I ausd using generanlised nmolectular weight datmu mis in time above cxanmmplc.(6.0043 C45f 0.(6.1 kg/kgmol kg/kgmnmol kgFkgumu. respectively.0191 C36 0.(6. C28 li. 372 3142 394 41)4 415 lii tircir proposed mnmetirocl a value f(nr y is initially mrssunred.3784 0.neteun.1)625 C27 (1. and values of t arsd ~ are calculated from Eqs.3.53) amid (6. l’lse urssummmption mmmd uudjustnsent of the upper msmolectnlusr weight boundaries are cointinued for otimer carhoum groups sequentially.tt135 (‘311 11.catuotn I 6.0101 0.4. and deternnmned time parameters of the gamma prohurhility distribution function for theism.0027 C40 C12 C13 CI4 CI5 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 C41 168 182 198 214 230 244 257 269 283 295 306 318 331 343 355 366 377 388 399 409 421) 432 442 450 460 470 479 161 175 19(1 147 161 175 191) 206 222 237 250 263 276 289 300 312 324 337 349 2)16 222 237 251 263 275 2’)t 300 \Viren sufficient inrfortmmuutioun our the distributions of SCN groups in C’y+ frmmclion and their moleculmu’ weight is avuuilahle. The sum square deviuttioums of curlctulmmtcd mmsolecunlunr weigints of the groups.49) Molecular Wg~lmt.0288 C34 0. so 426 437 446 455 465 474 426 437 445 zc M~/(t + )j~) 1 (6. ‘Fire arutimors conclrmded tlmumt ‘rand ycould he reasonably correlated by. in tIne original fluid. Tlren the upper boundary of the first group is assumed atsd its mass fraction is calcunlated by.4689 CI7 (‘18 C19 0. [341 proposed a procedure where the measured unass fraction of each SCM group is used to regress the three parameters of tIne gamma function while adjusting the molecurlar weight houundaries of SCM groups.240 6. Eq. umsing Eq.01)76 C42 0. In general time mnnelhod was found reliable when information on more than 15 groups were used in optimisation of tine parameters.1)116 (‘39 0.id F/eau’i’ Eiud ClO CII C12 CI) CI4 CI5 241 CI6 Table E6. Generalised SCN group molecular weight boundaries.~mm72l~1 3t2 324 337 34’) 3(n() (6. Winitson et al. Direct Application The continuous distribution fumrction cain be used in phase behaviour calculations similar to discrete comtmponents.1401 C25 C26 0.92%.0031 C29 0. F(M)= 0.(6. If the above calculated mass fraction does not matcln the experinmermtal valn. Whitsomm Ct al. tIme putrausneters of tire distribution function can be oplinnniscd by mnmmrtclming tIme unneastired group (latun. so I l0~ I — 11(1 + .2132 C24 0.42).0800 0.39) and (6.1784 0. respectively.2843 0..1073 0.00311 C37 11. After lime oplirnniscd values are determined the reliability of the model is checked by comsspariumg tire calculated mnoleculmur weigints and nnole fractions with the experimental data.0018 0.0614 C30 0. Ca. evaluated their proposed uuiethod using different numbers of SCM group data. from the measured vumlumes mnre Ilmeun evalrmamed. ~. up to the plus fraction.0016 0. I.54) 456 464 475 41)4 495 5i)2 490 499 507’ 484 494 503 C42 C43 C44 C45 517 526 535 544 512 521 512 521 where um and M are the umnole fraction and molecular weight of tlre selected group using 5 Eqs. Flmmuol (‘ha r.0013 0. the value of ~ is calculated fronn Eq. with the distribution function as.2436 C20 C21 C22 C23 0. the nn. SCN Upper Molecular SCN Group Molecular Generatised SCM Group Weight Boundary Weight.42) equal to 75.0244 C35 0. l)e.0034 1)0022 0.40).0104 ‘tIme untIe trmucuu.04427 exp(-M/75) The mole fractions of SCN groups can be determined from Eq.e. Table 6.0459 C31 00083 C41 0.53) witlm t related to y by tine above 360 371 3142 393 404 414 I leusce time unptinmnisalioim cams onmly he cousducted for y and eqrmat ion.n oI (‘.

Defining a mew variumble. to detennine the fugacity coefficients leads to complex integral equations which can ously he solved L f(X)exp(—X)dX (6. y and ~. tine suuunsc type of fuunction also describes tine oIlier equilibrated pisuise 1361. . in Eqs.(6. and the tisird is dime to uumleractmots hctwecmn lIme discrete aumd tIme continuous parts. Eq.(6. for lime Somnve-Redhiclm-Kwoumg EOS.! ( !. and the resulting derivatives fromrm Eq. I Jf(l)cXp(I) d(I) =~wkf(Ik ) (6.(4. F’(I) and Fv(1) are the distribution fummctions for the continmmomus fractions of feed.242 6.60) sinounid he unoted Ihat lime fuinctuoms provides lIme distrihumtioms of the constiluenls witlmin the contimmumotus pmirl. as follows. l’ire nnrethod approxumutles the vuiltue of integral numerically by ad(Iing the weighted values of a ftuusctioum usl mm tmunnher oi’ specified vuuhiues of the vumriahle.(6.4 I).uu.nu of Fluid I/eat’s’ E.(t) where ~(~) I ~--—. Similarly for the repulsive term.58) (6. are generally different. the nnetlmod of Guuussian quadrature has proved to be reliable and practical. It has been shmowmm tlnat whets a slistnihumtmon function.).55) t where root.4 I). hut otimer paraunieters. tmsnmsg time random mixing rsules of Eqs.4l). wilhm mmum additional equnaliors for tine countinu(nus fraction. ‘lIme unmaterual hunlumusce equumitions requn ired for plmase helium v our ca cmi lumlions. Anurongst the nummerical melimods applied sticcessfully 1361.63) and depends on the expressions for uuM) umund h(M). liquid mmmd vapour respectively. tIme sccomnd is that of the continuous fraction. are mulso expressed by contunuous functions of the variable I. J. the two parameters of a vain der Waahs type eqinunlmon of slate. willn mu total valuue of I. we get.(6.37) becomes. fV so I (6.30) (6.r. sumcls as Eq. b so ~x b~ + JF(I)b(l)dl 1 (6. which represent comprising coumnpounds. whrere he uses the molecular weight as tlne parameter representing compouunds. nt Fr(l) so nLFu(i)+ nVFV(I) (6.f(x)exp(—x)dx I (6.63) ~i (3.(6. wlrere FF(l).(6. called the quadrature points. k.60) to. Tire use of the distribution function. For mu mmtixttmrc (lescrihed by the semi—corstinuous rsnethnod.(3.(5.65) I I Ohvnously time functions ~(x) is duffcretnt to that inn Eq. utecd to he umnodilued also by incltuding tIme continumous description.td 243 replaces the concentration of individual discrete consponents.(6.73—74).62) wlniclm cats he shown as. 2~x a °5JF(I)(a(l))°~dI 1 3 where the first term accounts tIne atlrmsclionn hctwecmn time discrete couunpouuumds. to describe the eonlinuous fraction.(6. reduces tine instegrumls inn the expressions for a amid b.(a. such as the critical properties required in equations of state. XYICxP(_X)dX F(’y) so (6. Exuimples of such functions are those given by Cotterrnan [351.m 6. however.’ferisar:o. The equality of fugacity of eacir component in co-existimsg pinases mit equilibriuunn is expressed for the discrete and the continuous parts. imcnice.. 1 N ‘a. Applytusg tIne quadrature integration nmetlnod to Eq. I.3 I). are the same for the integrals as they all belong t(n the sammie class ((lauss-Laguerre) of functions. the umimulerial bumlance equations for time total unnixlunrc mind tIne (liscrete comsrponents remains the same as Eqs. or co-volume. the imrtegral in Eq.(6.56) X(M-t)/~ reduces Eq.64) r(y) Suhsluturtionm of lIne couumpositionsush (histrihution of Eq. are calculated as. SN on umunusuericutlly even for simple distrihutiots functions. for a mnxttnre described by lIme senmmi-coumtmnntnous umnetlmod.57) f”(l)= fn.59) a so ~~x x.61) The terms a(I) and b(t) are souse continuous functiours of I with values equal in pusratsmelcrs a and b. for compounds described by the comrtimrruouns description. 1—2).m.’rupti. lhnat is t in Eq.55—56). we obtain. For example. Sectlout 5. respectively. to tine fol1owin~ general form.. TIme pr’opertres of time components. lire roots utund werghts. N c” (M it “ tY exp[_-(M — t)I[IJ = fPE’(y) I (6. TIme range of cousnpounds described by mill three functions is the same.wk is tire wcnglst and f( t) is lIme vumlue of the function f(l) at the quadrature point. l)e. describes the continuous fraction of a pliunse.) I 5 +IJF(l)(a(l))°’ dl + Lu J (6. or Selccllmrg line gausrurma prohunhulmly functiomr. F/ui.63) for 5 F(I)dI .63).

stmch as those proposed by Twu in Section 6.2904) 0. the Watson characterisation factor is calculated first for the total continuous part.criptiouu ofFluid tjeau”.4). The same K~is then used for all the 7~ tu determssine timeir specific gravity. particularly as the molecular weight of the last pseudo component will become excessively high for which physical properties cannot be estimated reasonably. using tine measured values. representing the concentration of the last pseudo component.s.7. that is tire average nnolccular weiglnt wimicim is different for tine two equilibrated phases. Behrens and SandIer [321 were the first who suggested to use tine pseudo componemsts determined at the quadrature points of the feed distribution function in vapour-liquid equilibrium calculations. can be used to estinsate these properties. For mathematical sinnplicity.n. The above approach identifies each pseudo-component by its carbon number.7111 0. Time above treatnsent. M /S~1 5 5 (6. are bound to he different.1. with the molecular weights and mole fractions as given above. as required by Eq. K~=4. ~ Weight.. Figure 6. Furthermore. liquid. The use of pseudo components at correctly selected quadrature points is as effective as describing time fluid by twice as mauny pseudo components randomly [361. ~zk—l those developed by Alsmnned [191 using tine generalised SCN group data.5851) 0. however. y=I iii Eq.0389 9. the values of root and weight at each quadrature l’1oiust cats idemnlify a pseudo component.(6. Clearly. or a carbon group. I 6637Sn)~zkMk /(7. Wk Three Quadrature Poinis Root. vapour and liquid phases.3. (6. Higher numbers of the quadrature points hardly improve the results. The associated molecular weights of the pseudo components in each phase. however.66). w~ op~rat~mrePoints Root. They used two point quadrature integration procedure and deunmonstrated the capability of the proposed method.2943 0. so 6.69) Hence they solved tIne above eqtmation sinsuitaneously with Eq.. Root.~ 6. the value of ~3.74)) and proposed the following relation between the nroieculan’ weigint and specific gravity.67) (6. or molecular weight only.5556). should lead to the same values of a and h. the quadrature method.X Weight.2785 1.3574 4.3226 2. the C fraction. to estimate properties required in equations of state. They will become the same only whemn ~ is the same for all phases. Fluid Cbnara.Si78~-O 8457i (6.(6.71) The calculated specific gravity and tine nnolecularweight of each pseudo component are used in generahised property correlations. and use Eq.12 shows the distribution of SCM groups in time co-existing guns mind condensate phases of a North Sea reservoir fluid at II MPa below its dew point. or vapour. e.1r.6032 0.244 .(6. k. M )] 0 0 (6.68) and (6.66) where. A more specific approach for each fluid is to assume that the characterisation factor of all tine pseudo components are the same. tire roots and weights at the quadrature points are the same for all the phases.. pseudo comimpommeusts WImil sinus et mil. When the same type of function is used to describe tine feed.5366 0.4) and (6.2..n i-i 1 6. the distribution cams be assunssed to extend to infinity. 3 and 4 point integration. the selected pseudo components will be different. Approximate expressions relating critical properties to carbon number. i)e. 137 ohseu’ved thaI rusiung mu conrstaunt Wmnlsoim cimaraclerismnt iou lmnctor for mull lrsCti(Io componetsts leads to specific gravity values which do not correspond to the specific gravity of the mixture.2 in Appendix A. Any large molecular weight can be selected as the cut-off point of tIne distribution fumnctionm with little effect on the results.~Eund 245 = wkf(lk) = wkf(Xk) = Wk ~?— (6. C.4158 0. and introduced a different characterisation factor. respectively. tine selected values will he only at the qumrdnature points for time phase whose 1~ value has been used to calculate the group nnmolecular weights. such as . As ‘yr) represents the mean of the distribution function. They assumed a linear hogmnrithmic distribution fumnction.5579M° i. The calculunted mole frmucturns mire relative to tine continuous part and should be nornialised by multiplying tlncm witls ~l)~ Therefore. replacing the continuous part with a number of pseudo comsrponents equal to the number of quadrature points. is quite small.~•r.4) which relates the molecular weight to specific gravity.6I). as described further in Section 9. m~ single distribution function cannot reliably describe both phrases.g.’ierLcagio. with C as the last carbon number to describe a nunnber of oil mutmd gas condensate 50 samples. It is a valuable approach to reduce the number of components describing the fluid to speed up calculations. does not significamntly immspair the results in most cases.41).7458 6.8536 3. Eqs.3951 0(8305 Note that even with only four quadrature point integration the weight of the last point. The accuracy of calculations increases with increasing the number of quadrature points.(6. The roots and weights for 2. liquid and the feed. calculunted by.4142 0.1464 0. Table 6..0l08M~ un 4m C i 18241 (6. ~ In this approach.. Table A. 0.is generally differeint for the vapour.0104 .(6. N C = [o. Weight. with the molecular weight and nmole frauction given by Eqs. with tIne continuous function extending to infinity. tlmal of feed. P. Iiemncc depcmrthiumg on tIme distribution used. S so 0 1~zkMk]F[~i. as those by the continuous approach. Wk 0. Roots and weights for Two (‘r•~. are given in the following Table.68) That is.

12. NY (1975).74 0. 794. 1981). and the coimtrmbulion of the tasl pseimdo commspouncnui to it is qnuine summall.. ami(l I’iroozahuudi. Evuihuating the calculated values of specific gravity.02 7. The molecular weighi of pseudo-componeunts are cmuhculated frommn Eq.16 81. ElI. I 0. ()sjord. mind Kale.43) munsd.3951 0.40 164.5.8149 Rergnuiuums. N is determined by initially calculating the c so [o. 3. llerumaundcz..40 202. 01 The normalised uusohe fractions of the pseundo conmrponents calculated above should be nmiultiphieil by z.88 7. I lmummlaurd.8393 0. i-leriot-Wmntt Umniversity.7458 4 5366 9. F: “A New Method for Petroleum Fractions and Cnnde Oil Charactenismntion”. Al. MPhii Thesis.63 0.3574 0. Designation D2892-84”. S. A.0389 0.ceriplioru of F’ lmn.0392. 5: “Chuumrmnclcnisatiots of Norlh Sea Crude Oils and Petroleum Fractions”. 744-755 (1989).(6.94 430. Thesis.91145 0. = ~zkMk 5’ 5 ‘ k U. H. 1983).xausuple 6. A: “limermo(lynamics of Petroleum Mi xliii cx (‘onulaimi inig I Icmuvy II ymhmm ucam hssuis.0005 I 220.i 6. 8.7 I) provides the specific gravity of pseudo componenls as given in the above table. 403. J.P. The specific gravity of each component characterisation facior defined in Eq. IS).. Chronnatograpimy.S3~690 (1985). Edinnhtn’ghn.75 94.2 0 U ‘0 Me. (1987).J: “hntm’oc..huictioui to Ammumlylicuni (las Chnrotnatograplmy”. by 0. lIP. /Sc. b)escrihe the C7+ frmuction of tIne flmuid inn F’.3226 0. 163—170 Solutuo. we obtain.3.c. M(soX~x75+90 (1984). Varotsis.4 svithu 4 t~etndo connipuini&’umts (using I Inc quu adrat tire noel hod. Anmnual Book of ASTM Standards. 6. 3.i: As ysoh. 2 3 4 Total 1.. TIne critical 1 lununliertim’s of due identified ps<’unr mi comnmpommemsts cmnmm he cumhcmuimnted from Eq. 16637 x 0. 683-694 (Aug.22 0. 5. UK (1992). J.(6. to obtain lime mole fractions in the total mixture.X 149. II. 2. ~ Weight.25 78. Pedersen.0 8~1 we nhiain.81 5~zkM~SMSS 1(165)] =9.12. amid Castells. 8. mind ‘ruin.9981 0. 23.sow~from Eq. J.08 18.=0. AGA.(6. amid Fredeumsinnmnd.26 (I 7675 eM/S 89.96 t 6. 1649-55 (Nov.mlationns hny tuse of tIme Somuve—Redlichs—Kwouig Equumtioiu of SImile’’. 159-170 Figure 6. ASTM: “Distihluulion of Cnude Petroleum. 9. Katz. ‘I’hnomnimnscn.. Whitson Cli: “Chiaracterisimig Hydrocarbon Plus Fractions”.’ End 247 Suhslitmntiung the above value in Eq. Romsningseus. I.70). 6.Eng. I : Plmuise Fmmvelopc Cuulcn.61(32 M 114. ‘l’ek. F(y)sol from Eq.L. amid Osjord. JPT.(6. Miquel. a Method Combining Gas and Liquid (‘hiromatograpimy to (‘Immiraclerise Pelroleunms Liqui(hs . Reid.. Imnd.80826772 . Fluid (‘!mau’ncterj. N. Cimetn.’mtio.4 (10 5 10 IS S(’N (. t).. of Clmromatography. Dev.81 None utiat the cmulctmtated mohecuular weight of the mumixture is mnlmost equmut to thmmt of the unmeasured vahune. Rouninimrgsen.(6. Skjevrak. De. KS.d 11cm”. Pseudo-comp.3 6. N II’. which is the same as the mixture value. Emsg.. E: “Characterisations ofNorth Sea Petroleum Fractions: Hydrocarbon Group Types. Process Des. DL: “Retrograde Comndensation in Natural Gas Pipeliumes”.=(l. using I hueir mumolccunImur we ighit mmmd specific grmnvuty vmshues. [). SPE J.98 38. L: “Distrihution of Weight. SPE Res. zM”’~’0 S 36. 265-270 (1992). 4..6. P. P: “Microdistillation.246 0..614.66). mumnd Guieze. I Jnmiversit y of ‘I’rommdhseitnn (May... Density anel Molecular Weight ins Crtmde Oil Derived fronn Coniputerised Capillary GC Analysis”.: “Chimtracterismmhionr of Nortin Semi Reservoir Fluids”.F. MR. 1978). Energy and Fuels. J.45 with the results as given in the followiung table. I Room. High Res.~~ 20 25 REI”EREN(TES Perry. ksanuple 6.36 (1. 821-860 (1984). as..w=z t). 6. A: “Predictiung Phase Behaviour of Condensate/ Crude Oil Syslcmnis Using Methiunuse luntermsctioun Coefficiemits”. Dislribtutioms of SCN groups in equihihratesh gas and condetmsatc phrases of a Mortls Sea reservoir fluid. Deussity aurci Molecular Weight”.. z. Dekker (1981).2(1 iM 68. Monnogrmuphn Series.

San Francisco. Des.. 20.17 3. KS. Alrnmed... Ahmed.. Pet. 36. Calculation of Properties of Petroleum Products. 19. Glaysher. Whitson.248 6. 22. . 29. M. 21.. 26.L. Emmg. us ussass basis nneumsured by a FID detector. anmd Soreiele. 31. Ba.C: “Applied Hydrocarbon Ttmertsnodynaunics. 14.): “handbook of Malhematicutl Functions”. J. mind Datuhert. Cottcrmnman. 24. 37..R.75 0. amsd Robinson. ‘ 28. and Daubert. Kesler. AL. Cavett. Univ.37 0...B: “Calculating Viscosities of Reservoir Fluids fromn tiseir Conuposmitioums”. 434-443 (1985).K: “PVT Calculations on Petroleunn Reservoir Fluids tlsinsg Meastured mnmrd Eslinrsaled Compositional Data of the Plus Fraction”. Proc. Riazi. 32. Eng. 173-179 (1958).sa (1978). Pedersen. 7 and Mansoori. Gulf Publisining Compummmy. Katz. 22. Process Des. M. 18.. MS. Andersomm. mmmd Pu uuusmmitz. Characterising the Heptanes-Plus Fraction”. RH: “Physical Data for Distillation Calculations. Fluid Phase Equilibria. R. in mole has~smeasured by a TCD detector. (‘Inro. Fractions in Eqsialion of State Calculations”. (eds).I: “Improve Prediclions of Enllnumlpy of Fractions”.A.. J. and Daubert. 1-Jydro Proc. Res. and Meisingset. I I 6. 1986). 17(4). Lee. N.. SPE/DOE 14925.1. K. in “C . 1964). AC: “A Novel Sampling Method for Compositional Analysis of High Pressure Fluids”. 17. . R. 1976). R. JPl’. JPT.28 . 1171-76 (Oct. Ahrummmnowitz. IS. No. Characterisation”.. of Calif. 27. I & EC Proc.. P. G. T. Ilydro Proc. Twu. STP. RI. and Peng.mphy. ASTM. Conf. 12051214 (June. and Kesler. (‘hmuuo. (1992). 1983). F/ink! (lnaracier. 26. GA. ling. mnmmcl Slegtnn. J.bum 6. 443-448 (1978). T. ‘F.F. and Lee. J. 1985). 17-20(1984). Developmmrcnt umund Application of (‘ontimnuous Thermnmodynnamics”.A.. 153-158 (March.L: “Plrase Equilibrium for Systems Contaimring Vemy Many Components. MG: “Improve Vapour Pressure Prediction”. mind Story. Fluid Phmuse Equilibria. Sci. Cisemsr. 137-ISO (1984). 31. Yarborough.4. of 5th Symposium on 7 EOR. l.B. at Berkeley (1985).mces 249 13. and SandIer. Iimd. and Todd. and Harding. Ed: Chorn. gas and Ilttiid phases by gas cisroimnatograpimy. 1980). GI’A Research Report 28. Brmny. Whilson. PhD Dissertation. 1: “Hydrocarbon Phase Behaviour”. 11. Hydrocarbon Proc. L: “Application of a Generuilised Eqummtion of SImile to Peli’olcunr Reservoir Fluid”. L.H: “An Internally Consistent Correlation for Preelictimrg lime Ci’iticunl l’roperties and Molecular Weights of Petroleum and Coal Tar Liquids”. Ref. SPE 14266. M. Proc.. 115-116 (1980). 59(3). and liquid. 24.41 5. T. 577.17 2. 35 1-366 (1962). C. Proc. ‘lime commmpositionn of us live samniple Imas becur dctenssimred by flumslning time fluid mit line lmtbormttory conditions.cccc Couniponemml Guns Mote% ‘~‘‘~‘t~ 19 Liquid Weiglmt% 0. McTaggart. 16. J. are given in the following table. of 60th Ann.G.. Loimrenz. and van den Engel. 755-759 (1987). CII. B.E: “A Modmficd Somuve l:qtmmttuour of Simile’ I~nu’Phmmuse Equilibriuns Calculations I Hydrocarbon Systemsns”. Edmister. 259-278 (1990).5 EXERCISES 25. Ellilie. SI: “The Use of Sennicontinuous Description to Model tine C . W. Dcv.1(1 0. D. Robinson. 182. C.1. lloustotn (1989). (‘Incus. Riazi. 96. Advmmnces inn Clmemsnistry Series. Grahosku.. 1622 (1989).M: “Flasin Calculations for Continuous (Sr Senmicontintmous Mixtures Usimmg mtus Eqtuation of Slate”.Y: “Time Charmuclernsation of the lleptmmsnes amid Heavier Fractions for the GPA Peng-Robinson Programs”. 35.. ‘[‘tulsa (April. 16.0(1 (‘I (4 ‘I i’’5 6851 1401) (1(12 II 115 (114 tt 55 tI5l ~ t 68 2 81 I I’) 1.. I & EC Res. unnel Clark. 1: “Application of the Gamnma Distribution Model to Molecular Weigint ansti t3oihin~Point Data for Petroleunn Fractions”. 1378-1384. 23.ca. ~ 6. 33. Chemn. A. Consmrm. I: “C .. (Sept. Vapour-Liquid Equilibria”.R. American Chemical Soc. Curvers.G. Refere.G. ‘lIme commmposituon of gas.. High Resolution Clmronnatograpisy. Compressibility Factors and Equations of State”.E: “Simplify Property Predictions”.ulumlcd Distillation up to a Boiling Point of 750’C Using Temperature-Programmed Jnjectiots anmd High Temperature Fused Silica Wide-Bore Columns”. Dcv. 163167 (July. Behrens. mmmd mirnunlysing the collected. lnnd. 34. Characterisatiomn of Related 7 Equilibrium Fluids Using Gammsmnna Distribution”. 37. J.E: “Characterisation Parameters for Petroieumn Fractions”. 256-257 (1972). 35-56 (1989). D. 30. CII. (Eds. 12. ‘l’uI.84 III’) CS C6 C7 (‘8 1. Taylor & Francis. M. Part 4. Equations of State in Engineering. D: “An Overview of Phase Behaviour of Oil and Gas Productioms”. and Soreide. 57. New York.. Chorn.G: “Simulated Distillation of Petroleum Crude Oil by Guts Cinrommnuntogr. P: “Gums Chrommiatograpimic Metlmod for Sinmmn. of 27th API Meeting. T.F. Cmudy.C. T. A. 385-435 (1979). K. Dover Puhlieaiions Inc. L. A: “A Generalised Correlation for Characterising the Hydrocarbon liemuvy Fractions”. J. Proc. Calculate the mixture composition in mole basis. Anderson. 161-171 (1990). Danesh.F: “Correlation of Simntmhumted True Boiling Point Curves by Gas Liquid Chromatograpimy unrmd IS Plumte L)islillation l)mmta”. Cotiermmman. 81-94 (1975).

C4 (‘4 -(‘5 CS (6 ((.0069 MW S( N2 C02 (‘I (1(8)12 0. or evaluating the uneasmired values.00 0.877 (1.0226 C7 (‘8 0.48 3 3.04771.66 835.841 1) 847 0.01 749.05 0. Exefl’.1 321.96 764. 7 Describe tire C .0162 0.73 822.f fuaction of a gums condensate are 0.’acteri.00 0.7 151 t~idecaneun 5.ric factor).1)188 0.0230 0.9 164 Tridecanmes 5. Weight Ilepimuumes 2 I .63 4.5 Nonunuies 9.18)32 217.38 ClSi.46 Ct4 3. ‘lIne commiposil ionn of unn oil satrrple is mis follows 13 I ~immponctum mote Iraci n.64 832.c i-IItmianne 251 0.4 351.1)98 C2 I C22 (‘23 C24 (“25 0.ce.870 (1. respectively. Component MoIe% Densily. kg/mum’ MoI.0031) 0.0452 91.1 353 6. 6.0031 0. The mole fraction. fractious by a single.0111 0. fraction by two and mnlso fottr psetmdo connponents.8 332.4 10.5.794 0.293 C29 C30÷ 0.72 814.0146 0.0024 7.01 0. Flmmid Cho.875 ((.255 0.0 20(1(1 269. using the quadrature 7 time dew point and saturated density of time gas condensate at T=394 K using a nuretlmod.4709 1)0569 ()()439 (1. usirng lIne mnrcllmochs of Cmmvett (E.32 838.00 0.0294 393.0 204.67 785.866 and M=275 kg/kgumnol. The consposition of a gas condensate sample is as follows.0139 00103 (1(7122 0.7. is to relate the molecular weight and specific gravity by assumiming a cotmstant (UOP) characterisation factor.250 C9 CII) 6. Describe time C7~ I’rumctioum by a continuous function in terms of the molecular weiglst.0095 (1(1242 (‘2 (“3 i.20 Ct2 3.860 1)874 (1.5 206 Ftexadecaunes 3. description of the fluid is time saumme as lhmtt given ins Exercise 6.5 15 0.359 CII 4. Predict ptmase bclnaviommr umodel and describing the C .7 612. The concentration of C7+ fraction of a gas condeimsate is 4.0081) 0. Components Niurogen Carbon dioxide Meuhane Enhane Propane i.00 4.771 TIme C .2C).2. and Riazi-Dauhcrt (Lee-Kesler for lime micemitric fmuctor). volume and acentric factor for a pseudocomponent with Tb= I K.834 C16 Cl 7 Cl8 (19 C20 0.0039 0.7 31)1.4 192 Pentadecanses 3.0048 Mot% 0. and use it to estimnale time ninole fraction of SCN groups comprising time C7+fraction. (s. Compare the calculated results with those of C~reported in Tumble A.7 249 Nonadecanes 1.09 739.4.0203 0.5 220 Hepiadecanes 2.935 ..5 178 Tetr~iecanes 4.Pennanes n~ Pentane Ilesanes tlcpt7nncs+ 0.37 n-ttuuane 1.819 0. Extend the analysis to C30+ by SCN groups.59 1)52.57 Liquid Phase Molecular Weiglnt= 2(16 6.0 1(7311 1771) 190.0393 0.735 0.1 370.58 776.551 0.844 ((.6 138 tinmdecamses 6.784 1331) 48.4.1) 0.4 282. molecular weigirt amid speciFic grunvuly of C7.298 1. presstmre.00 0.mm (1.81)1 0.1 39 C26 C27 C28 (1. Calculate the critical 6 2 temperatrure.0176 0. S=0.0085 (1(1)197 11.72 79. Is this a reasonable asstmmption? 6.30 810.2 121 (I C9 CII) CII C 12 (‘13 C14 CIS 0.806 (1.5.9 105. two and four groups 7 (Measured values in Tumble 2.2.0 (1.dmister for lire acemnl.0053 0. Composition and properties of C7÷ fraction.895 (1.17 C13 4.u 6.0 235(1 248.1 121 Decauses 6.832 (1. One method of estimating properties of SCN groups.8 381.872 (1.cario.2 234 Demadecanes 2.886 0. 6.888 (1.8012.745 0.02 829. 62. 165 and 0.789 0.6 16 4.5 297.1 263 Elcosanes plus I 1..0323 0.6.6 0.0044 1)0(134 0.3.77 I mole % with tIre umnalysis as follows.71 796.0 89 Ocianes 15.

It can iunnprove tIre recovery tinrougim mnaitmtaining the reservoir pressure. the commtact between the phases results in mass transfer. the immiscible displaeemmment is practically 100% efficient. Compare the results (Measured value ~b= MPa). At the pore level.. and then applied to real reservoir fluids by presenting methods to àstimate miscibility conditions. 7 GAS INJECTION I Itnjecting gas iisto ~inoil reservoir to imncrease time oil recovery. pirase belsaviour concepts and nnodehlimmg methods previously described can be applied to investigate gas injection processes. The displaceunent of oil by gas becomes highly efficient when tire properties of the advancing gas and displaced oil become similar.252 6. as time lack of interface eliminates the I -c’ ~ retainment of the oil hr pores. however. fraction by the gamma probability function. Use the quadrature method to 7 .8. Hence. .ion 253 Describe the C . In this chapter. changes in properties of the two phases.ca. the two phases aclnieve complete immiscibility amid tire vapour-liquid interface vanishes.id C!naracierj. FIn. That is. and the experimental and theoretical metisods to evaluate and design miscible displacement. It is reasonable to assuumre (mull tine eqimilibriuns is reacired at the gas-liquid interface. two and four T=345. hence. As the injected gas is not initially at equilibrium with the reservoir oil. or vaporising time insternnediate and imeavy fractions of the oil. nmerit particular considerations. has long been applied. Predict the oil bubble point at represent the C 7 a phase behaviour model and describing C . fraction by two. by a single. displacing oil. and also four groups. using 23~7 groups. The concept of miscibility in gas injection. miscibility concepts are initially de~cribed for simple mixtures.

. they mmmc cmuhled firs. amid simmiihumrly of I and II. L 100% Ann imijeclions gas whiiclr is miol immiscible wills mun oil mit first couslact. Y. connecting line two plnases at cquilmhriummi is kmnowms as the lie line. I 100% 10% I) 711% i A’ Gas A 0 11100% 80 60 40 20 0 1. Y .3. or at very highs pressumrcs for lean systenms.1. CB. is the original gas L after it inas picked up some intenniediate and heavy fractions 1 from tIne oil phase. Figmnre 7.1.. 7. F. The process. miiixcd at any ratio. time immjeclioun gas. and the associated tie lines. Time line XY.Ie. moves forward and makes further contacts witls the 1 . simulating the injection gas-reservoir oil mixture. wlmen timey form a single phase at all proportiotrs. llemsce.1. l’wo fluids are considered to be miscible. First coustact miscibility. lIme chew poinrt curve. mmmd I. whereas tine right hand side. umlso kmmowmm mis tine plait point.1 by a ternary diagrammi. using a triatsgtular diagram. h: Internnedimrte. lIme overall mixture lies on the line connecting the two fluids.g. AIry nsmxlmnre..2. hiowcver~miniscible eilimer by enrichmmiemmt wills I to A” or by rumising lIme systenin pressure to shnrink time phmase envelope mis shown by the clashed phase etsvelopc.g. Note that the gas pirase. forns a single phase. I shows I Immmt lime hu usuu uc S ummmnlc of I. fornnms two equilibrated phases of hiqumid X mind gas ‘~‘l~ witln’anm overall nmixture F~. after contacting Oil A. kmsown mts tIne s’apori. Tire gas phase. It is evident tlmat any two fluids with thse operating line not crossing tIme two phase region within the phase ensvelope are miscible. lying on time phase boundary curve. I. Each corner of the triangular diagram represents a component as pure. X.254 7 Gas limjeetio. 100%. L mind ii forum a single phutse fluid whsems mixed only withninm a Iimssited ratio.e. I ignmne 7. e. Wimeus lire ins~eclmon guns ammd reservoir oil. may achieve miscibility during ummimlhiple couilmnets by gcltimmg etsriched tlmrough vaporising lIme intern’nediate fractions of oml. i. e. Miscihilin’ Coiucepec 255 two-phase regiouns. at constant pressure and temperature. Plnase envelopes. represemils smntsmraled liquids.scil. H: 1-leavy) at a constant temperature and pressure is shown in Figure 7. When two fkuicts of different compositions mire mmxcd.e.me. AC.s drive (VGD) is conceptually shown in Figure 7.1 MISCIBILITY CONCEPTS Miscibility concepts cats be expressed couivenmicumlly by exmtmmliliimmg I lie lilmuise lmclumivmour of mm ternary system. 100% 11 100 % Figure 7. wlmereums Gas A is mint. It cami hecomime. whilst all binary nnixtures are on the lines connecting the two corners. and its position can be determined by the lever rule. whiclm is called the dmhmmlnorm or operaliing !i. represetrts smslumrmnled gmnses. whcremms..m 7. time left hand side of the curve. The phase behaviour of a three component mixture (L: Light. and mu hiqumid plimise. mml equnmtubrmuunmm. Point D. i.1 resembles most of the practical cases. the bubble point curve..2 slnows (mat mm ins jection gas conrprised ommly of! is nniscihle when conlmmcted with Oil B. Ternary diagram presentation of fluid plmase equilibria at constant pressure and temperature. hut the diagramir shown in Figiure 7. The two pmnrts of tire curve converge mit mIsc crilical poimsl C. commiprised mit the light Ilimich onuly.silmg ga. The phase envelope is slnown by the curve ACB in Figure 7. and is quite adeqtmale for describing tIne miscibility commeepts. Any nnixturc outside the pinase envelope is mm siusgle phmuse umnder-saluruik’d flmnid. insude the two phase eumvelope formnis a vapour phase. or Irave a number of isolated Figtmre 7. Y . eo?mIa(’l nn. where increasing the pressure generally results in thm~ shnrinkage of the phrase envelope. Point M and its composition is delernmsinred by its posution relative to the corners. at diffcremmt pressures can be shown (mn time sanre diagram. A ternary system may form more than two phases. Any point witlsmn the diagratss represents a three component mixture. forumi single plnase mmmixburcs ~vlmen mmmixed mit ammy proportion. First conlmucl umuiscihility camm be achieved only for higisly rich gases.

condensing gas drive (COD). Tine process. as shown by the dotted boundary. It is evident that the nmiscibility he acisievecl when the oil composition and the phase envelope are at tire same side of tine critical poimit tangent line (critical lie line extension). lncnce. X . The injection gas displaces the criticud fluid. Then it miscibility displaces the original reservoir oil in a pislon-type manner. I. No phase boundary exists witlsin the transition zone.uu. Y . instca(l of raising the pressure tsr achmievc mmmiscihility. In tine condensing gas drive.. is described below.. It is quite evident. pure L.3. At thsis point it will be miscible with gas A. at tine ciurrent piessuure. Ga. Time origimnal oil coumnpssitiomm Inas urn effect on achieving tine ntniscihility slate in tIre condcnsiumg gums drive. X . This process goes on and the oil is enriched to the extent tlnat it finally 2 3 aquires the conmpositiomm of time critical oil at C. with tine liquid composition varying gradually to that of the original oil.. Conulcumsiusg gmms drive scimetnatic pimase dimmgramn at nnimmirnsum miscibility pressure. not forming first contact miscibility with an oil.ualiy in Figure 7. At MMI’. can be achnieved by raisimsg the pressure to shrink the phase envelope as shown by the dotted curve. as it is the only condition that equilibrated phases lose distinctions. A rich gas. that the compositional path must go through the critical point. 1. . Miscibiliis’ Commeepl. Schematic phase diagram of vaporising gas drive at minimum miscibility pressure. gas. and a continuous transition fromnm gas to oil can be achieved without any phase boundary. mIRm% H 100% Figure 7. The gas composition varies gradually from that of the injected gas till rcaciminng tire critical composition. I iOO% 00% H it)l)% Figure 7. Ilence. where the tangent line at the 3 critical point.3. i 00% GasA oil is the minimum required pressure to achieve miscibility. however. mIne injection gas mummy he enriched. which is the critical tie line with zero length.s 257 fresh oil and progressively becomes richer particularly in tine internnediates. as demonstrated in Figure 7. that is.. by raising the pressure sufficiently to shrink tine phase envelope. which is called the. tine uniscibility is achieved at the injection point. ‘rise gums pinase unroves forward and leaves the enricined oil X beisind to be 1 cotstumcted further witln tIme fresh gas A. however. with the limiting tie litre become the critical tie iimse.. winieR tIme critiemmh tie line extension goes through the injection gas composition is called the No phase boundary exists within the transition zone. The miscibility. mis tIme enriehmnent of the oil is limited to the composition of the tie line extenditsg tisrouglm lire injection guns composition (limiting lie line). the limiting tie line beconmes the critical lie hue as tIme gas phase enriches through multiple contacts with the original oil attaimuimsg the critical composition. 2 Y . as it is comslu’olled by tIre insjedtion gas cumrmposition. The ricim gas A forms two plnases. The vmiporising gas drive immiscibility iimr oil B cmnn he achieved. as the enrichment of the advancing gas is limited by the tie lime X’ Y’ thimrmiting tie line) 2 cammnot 2 which. in a piston type manner. however. is the minimum required pressure to achnieve miscibility (MMP). the nmiscibility is aclsieved at the fromnt of tine advuminciung gas. gcnes through the oil consposition. ‘lime inn jectioms Guns B.n Gas II miscibility pressure (MMP). tIne oil plsase etiricired in time intermediate through multiple contacts witim the injection gas uittmmins time criticuml eommmposition. however. The pressure at which the critical tie line extension goes through the conceplm. Tire emmruclminment level mnt mninimm’rutnm miscibility enrichment (MME). called the mini. The above injection gas. At MMP. does not acirieve mumltiple contmtct nmmiscihility with Oil B. resulting inn an oil even riclser in the imstenmmediates as shown by X . achieve multiple contact miscibility through condensing its intermediate fractions to the oil as shown . if extended. The gas ultimately becomes miscible with oil at C. as simowmn by Y .4. goes through Oil B.256 7. in equilibrium after contacting the 1 1 reservoir oil.4. wInds is lemitier ins tlmc intermediates tlman Gas A. can. The pressure mit which the criticuil tie lime extension goes through tire gas conmposition. In the vaporising gas drive. The gas composition appears to have no effect on achieving the miscibility state in the vaporising gas drive as it is fully controlled by the oil phase. and oil. does not form immiscibility.s Imujecthnu 7.

‘line mnnulhiplc contmndt unmiscihility inn nssumlticonssponenl systetmss is mncimieved in a dynamic process. As the oil is contacted witln additional rids gas. Note tinat the bubble point and the dew point curves initially converge. at MMP. Otherwise.nctniamc 20 I0 (71). conidutmomu wlucis’ mumuscihilily cumun just be unchieved. it vaporises less of these compounds whilst losing intermediates to the oil.6. hscnce mniscihilily.s l. it strips tine ineavier fractions. time nniscihilily conditions can be deternmined by phase behaviour considerations only. 1.-- 0 nnIc. umsing line lermnamy diagram. it can be affected by olhcr factors additional to the fluid phase beimaviour. the critical lie line. the nniscihulity us achsieved by line vapmansiung process.ng/vapori. Varimstioni of component grouups in comntacted oil at injection point wills tine ratio of injected guts volumme to contacted oil volcunne. Suds a possibility exists for mixtures with more than three components. Tine hmisic idea of multiple contact miscibility throingim minass exelsange between the phases. can be aclsieved ounly wlren the comrmposilmotnah pmuths goes through the critical state. Tine two limiting critical tie lines.. When the critical tie line coiimcides wills time linmiliung lie himme going lhroughm the originuml oil counposilion. The conceptual discussion on multiple contact miscible processes. At liighrer prcssuurcs. I lence. depends on tine local fluid mixture composition influenced . as determinred by mneasurimrg tine compositions of equilibrated phrases at the injection point and also at tIme gas front in a laboratory test. those with extensions goinrg timrough thre original oil and the injection gas. However. 11 S amrd C -C as the instermediate (I). Indeed lire prevailmng nnnechsanism for achieving miscibility in rich gas injection is often.c 259 at time tail. hut sonmewhiere within the transutmomn zone. is decreased. tine niniscmhnlmty will ohviosnsly he achievable. time unniscible cotrditmoun us icferrcd In time.6. When the critical tic line coineides witir tIne limnnihing tie line gommig lisrotigin 11mm’ injedhioms gmus composition. Tisis proces~. that is. the above memmtuoned case and not the condensing mechanism described for a ternary system. depend only on the original fluids.jecsio.si. mn descrihinig line hcliavimmr of real reservoir fluids in gas injection processes.‘. Figure 7. however. Mi. This oil eamnmsot becoumne miscible with the markedly due to vaporisation of the lighter frcshn injection gas. umund tine dimngramin shotmid mint he smscd genermully ins Ihse design of real processes. The phase envelope. Gas/ Vol. hence tine critical tie lime. if not always. tmence..cing gas drive. It is commnnon to group C . It is conceivable that at favourable conditions the combined vaporisationlcondensation process results in a state withiur tine tramnsition zone where the compositional path goes through the critical point.cunllesh lIne eommden. As tine critical compositiots. An exannination of the heavy end.g. however. e. the miscibility is aelnieved by the condcnsmmig process. it is possible tlmat neither of the limiting tie lines goes timrough tine critical point. mind mms’liucviuig nnmiss’iinility. hut miscibility still is achieved. and C mis the ineunvy (II) fraction. 0 2 4 5 5 10 Vol. Inn tIne following discunssiomn.o’ibmlmiy Concept. overall it tends to get enricimed in very incavy fractions and tirus becomes less similar to the unjection guns. tine miscibility is dclermuned only by the two limiting lie lines. C . demnonstrated by sisortening tie line lengtirs.u 7. and tire requirement of attaining the critiemsl corsipositiots. The reservoir oil in contact with tIre fresin gums iuiimialiy bccouines lighter. aumd then diverge. apparently lightening the oil in its path towards achieving tIme condensing miiiscibility.5. if the nimiscihihity is achieved by either vaporisimng or condensing gas drive mechanisms. winihst tine injections gas enriches the oil iun light internnncdimmte ramrgc. mnuiul N as Ihe 1 2 light (L). I-hence. and detailed by Stalkimp in 1987 50 --5 40 . (a. thuit is. In a real system. C02.5 shows the varialion of measured compomment groups in the oil phase at tire inn jedhion point for mu North Sea oil. This can be envisaged as a combination of the condensing process at the front. 2 2 6 7~ Pseudo-ternary diagrams imave been misrused. was reported by Zick El) in 1986. partucularly in estimating the ophinisuusr operating conditions such as MMP and MME. This will occur if the fluid attains a critical state not at the leading or the hailing edges. for a ternary system at a given set of temperature and pressure is uunique. . Oil Figure 7. shows llsmnt Ilmis fractiomn Iras increased 25 heavies.258 Miscibility in Real Reservoir Fluids 7. Tine injected rich gas sines not generally contain heavy fractiomrs whicis arc present in tIme oil.. The ternary plnase diagrammn of a multicomponent reservoir humid is ofteun expressed by representimsg the fluid with three pseudo components. and the vaporising process 0 Lighu Flea~y 30 ---. is not strictly valid for real reservoir fluids. 50 60 70 inj gas 20 80 90 L 50 40 30 20 10 Figure 7. As the forward moving gas becomes richer in heavy fractiorns. is shown in Figure 7. The coumnpositional paIls depends our other mechanisms such as multiphase fluid convection and dispersion inn porous unedia. but as it contacts more gas and loses only some of its lighter heavies. mmmc mill valid for real systems. Phrase dimmgrmtnn of a Nortim Sea oil and rids injection gas determined experimentally during comntact experimnnent. the cotucentralion 1)1 (. the existence of ml large miummrmher of comnnpomncmsls inn ml real reservoir hluid provides middimiomnmml possibilities for comnmpositionmmil vmurialimmns. The nruultiple conlact miscibility. acisieving miscibility. E21.

where the injection gas and time reservoir oil are equilibrated in a cell. Altsmost ammy shins tube. Displacement of oil by gas through a porous mediumsi. can be expressed by a series of pseudo-ternary diagrams. could then be studied in otlmer experiments of state used in modelling the process. a one dimensional nnodel reservoir. A schematic diagram of tine tube aurd tine auxiliary equipment to allow displacement tests. density and commlposilion of produced fluids are measured. or glass beads.9]. is mm nmnrrow tube packed witin smnnd. there arc two cross over tic lines connecting three pseudo-ternary diagrams in a five component systems. Considering the above. The number of the pseudo-ternary diagrams increases with the number of crmnponents. regardless of the design. and umsing compositional simulators. partieulummiy for ttmnimrg tine equumtion Slum tubes of differcmnt sizes mumnd orientatiomms have been used at various displacement conditioums. [6]. the estimation of miscibility conditions is not as straight forward. An ideal tube should provide a one dimensional dispersion free displuicemeirt of oil by gas. It has been demonstrated that dispersion. such as viscous fingering. the estimation of miscibility conditions based on the liunmiling tic lines is not generally adequate for real systems. As it is imnnpo. tmtilisimng mm analytical method to solve the governing phase and flow behaviour eqsmations with no dispersion. simulates time gas injection process more closely than other tests. are also conducted to determine tlne mixture pinumse behaviour.7. Static tests. one dimensional flow. Slim Tube Slim tube. E. Wisems tine two phases of vapour and liquid at equilibrium are present. using the injection gas tie line. Most tests have been designed to directly measure the minimum miscibility pressure or enrichment. The actumal displacement in a reservoir is influemrced by variouns nmechaunisrns. if Isot in all. Probably tIne simmmplcst test usinig a slim tube. Ihe oil tie line can be used to detennine the miscibility condition. witln the number of cross over tie lines equal to the number of consponents mmniumsms 1111cc. pressure controlled by a hack pressure regulator. the transfer from one tcrnmury diumgrummnm to time next must occur at a common tie line between tine two diagrams. strongly divert time flow and affect the recovery. and it is considered as the definitive test. Therefore. any of the cross over tie lines or tine limiting tie lines can become the critical tie line. Tire reports by Orr and co-workers 13-71. pressure and temperature. Whereas. it Pump may not represent the real process. called the cross over tie line. The aclsievemmnenl of miscibility is expected to accomimpany a gradual clsange of colour of (Ire flowing fluid fronts that of the oil to clear gas. extracted from the reservoir. (Sr injection gas enriclnuncurl levcls. Even if the key tie line cams be determined for a dispersion free. The pressure drop across the slim tube is generally small. tisey do provide accurate and well controlled data which are quite valuuihle. The oil is then displaced by injecting gas into the tube at a constant inlet. all immrportanmt to the success of a gas injection schenme. known as the slim tube. When tire process is known definitely to be vaporising. The authors demonstrate that tine displacememsh in a multicomponent system. it is logical to avoid them all in plnase behaviour tests.2.2 EXPERIMENTAL STUDIES Back Press.ssible to sinnulate all these inter-related tmrechanisnms in a slim tube. or evaluation and tuning of phase behaviour models for Figure 7. can be used In estimate the effect of pressure . It is nmrerely a well controlled experiment. gravity over ride ausd dispersion. is shown in Figure 7. or more often in a long and narrow sand pack. a proper investigation of the multiple contact mrmiscibihty should involve the simulation of fluid phase and flow behaviour as closely as possible to that in the reservoir. and/or the producing gas to oil ratio. The miscibility conditions are determined by conducting the displacement at various pressures. This can also be aided by visumul observatiomi of tIne how through a sight glass placed at the tube outlet. l’hese factors. Depending on the fluid composition. Schen’mmmtie diagramst of slim tube apparatus. The tube is initially saturated with the oil at reservoir temperature above the bubble poimst pressure. such as methane displacing an oil composed only of hydrocarbons. There are ample publications on mathematical simulation of multiple contact immiscibility as developed in a one dimensional flow.260 7. where the compositional path progressively moves from each diagram to the next. The miscibility is then achieved at that point.uperinuentol Studies 261 by flow factors.7. or more often outlet. the entire displacement process is considered to be at a single comnstant pressure. For example. for a four component system provide valuable insigint into tine rmrechanisnms of multiple contact miscibility. numerical simulation of the reservoir performance. is determination of time nsiscihihity comsditiotss. at different scales. with a length between 5 and 40 m. or even us a core. Regulator Guts Meter Gas injection experiments are conducted with several objectives. such as oil vaporisation by gas injection. viscous fingering and gravity segregation can impair the achievement of miscibility. Reservoir hetcrogeuseity. with valuable results for phase heimaviour studies imncludimrg miscibility evaluation. 7. Tine effect of tube geometry and flow paranneters on fluid recovery has been systensaticahly investigated [10]. The estimation of miscibility in rids guts drive. When the key tie line which controls the miscibility is one of time cross over tie lines. The shun tube effluent is flashed at the atmospheric conditions. tlrerefore. as suggested by Johns et ai. This is not to suggest timat such a displacement sinnulates tine process in a real reservoir. and monitoring line oil recovery. Gas !?ujec:ion 7. Although these tests do not closely simulate the dynamic reservoir conditions. causing two pimase flow in reservoirs in which they would be miscible otherwise [8. observing two phase flow is indicative of an immiscible displmnceuncnt. whilst the compositional path in a four component systemsm camn be depicted by two ternary diagrams. with a conmmon cross over tie line. Tests are also conducted to generate volumetric and compositional data for specific studies. The gas break through is detected by comitinuously monitoring the effluent gas composition. The displacement is conducted either in a core. and time rmnte of recovery. is expected to be unreliable in most cases.

TIme rumost acceptable definition is tire pressure. for justifying time assumption of onc-diunrensional flow iii lIne shiunm ttmhc. or gums cnmriclnmmncnt. Time recovery at that point is referred to as the ultimate recovery. a significant ainosunt of lIme liquid collected in time separator can be due to condensate drop-out frousm the produced gas. the mnazimum grain diameter of time pmickung material shrould he less tinmiti I/It) of the internal tube diameler [14).25 in. a 100% oil recovery is not generally expected. with the ultimate recovery determined at those conditions. particularly in efficient displacements. if ustluninable.dies 263 and gas enrichment on miscibility. tire snmaller time diaur’seter.171.15 Ml’a 28. lsas improved nrarkedhy at tine iniginer pressure. around 8000 vol/vol (40. depemids our tIne lube design and operating conditions. indicating an approach towards miscibility. that is. The S •S improvement in oil recovery. A gas injection rate with an advancensent velocity of ahotut 1. Tlme recovemy is expected to imrcrease by increasing the displacement pressure. where the complete liqmnmd recovery over I PV can be achieved. imence reduces the recovery gain when achieving miscibility. unless the condensate recovery in rich gas injection is included.) diameter tube is often used. Al high pressure conditions.10. as shown in Figure 7.c Iiujeeimoiu 7.5-2. such as 80% at the gas break through [15].3 tnmm (0. with gas injected from the top to promote gravity stable displacement. The length is to provide sufficient contact between the phases to achieve miscibility. The oil recovery. Its practice. of 100-200 nneshn size mire often used in packing the tube. A low gas injection rate can improve the contact between the phases in a short shiumn tube. using the volume ratio measured on the original oil. nniscihility is achieved almost at the tube entrance whets iso dispersion exists [4.’inue. Although at miscibility conditionns tIme displmiccunent is quite efficient. The low recovery at 24. Note thmnt thie recovery.25 MPa S 0 0 > 0 . Oil recovery by gums iunjedtion at two different pressures.15 MPa is indicmntive of aim immmniniscihle displacemnmerrt. As a long tube cannot be placed in a straiglnt line. Ga.13). is ofteni nmnonsitored to determine the miscibility conditions. Operating conditions. should be selected based on the tube design. Furthermore. Sand. Kmpe.2 pore volume (PV) gas. This cats reduce line accuracy in detenisining the miscibility conditions as measured by chammges in the oil recovery. 10000 S 0 0 • ‘F 0 •~O• •0•’O 0 0 The volume of produced stabilised oil in the separator ms generally converted to that at reservoir conditions.262 7. The oil recovery after break through drops sharply and can he quite small. The volume of recovered oil prior to the gas break through is almost equal to time injected gas volume. is nimore appropriate to determine miscibility condihioums tlmunnm seumrcimimng for a lmighn recovery. lnjecmed. 15 MPmm line gas breaks through at 38% pore volume (PV) gas injected. % Figure 7.111. At 24. however. whiclu Inigimlighnts cinmnnmges inn line oil recovery. A 6.9. 0 001) 0 0 20 40 60 Pore Vol. or 90%-95% ultimate recovery [16.2. 0 . particularly at imumsiscible commditions. I )J)~5flfl~ 0 reliable recovery data within a reasonable experimental tumne. provides a more definitive means for tine jlmdgemimenl (nf msmmscihrilily conimliliomns. lnave been suggested as the criteria for miscible displacement. with an ultitnate oil recovery of about 50% PV. the shorter the tube. particularly in rich gas injection. Recovered. It is generally slightly less than tire injected volume due to the shrinkage of the total gas-oil volume in contact. and is considered adequate. The displacement is often terminated after injecting 1. Figure 7. .1mSMu’~ E 0 0 > 0 50.000 SCF/STB). and the prevailing mechanistsi which results in miscibility.000-50.••• ~0 0 (ill ~ S 4(1 ‘I ‘S 0 2S2SMPa long as 36 meters have been recommended for displacement with nitrogens 112. Tine gas to oil ratio (CUR) increases sharply after the breakthrough. or enrichmntnemsh level. inn ltmhes of mml lemmsl 10 mrs ~. The volunsre fumctor for suds a liquid is different from that of the original oil. by increasing pressure or gas enrichnunsent. mnt tine bremnk over poiust of the uuhlinnate oil recovery as sinown in Figure 7. To usmimniunnise wail effects.scihle conditions. Thneorelicunhly. A slim tube may ounly deliver 80% oil n’ecovery unt msii. 20 0 0 5~ 0 U ‘3 long. it however. 0 • 0 24.8. ilence a long ttmhc. % 80 Figure 7. it is in be coiled preferably cyliundrical than flat. tubes as 80 000 0 0 0 0 0 0 0. The tube diameter should be selected small enotugh to suppress viscous fingerimig by traumsverse dispersion along the tube.9. or glass heads. Differeust recovery levels.25 MPa the gas break through occurs qumile late. the liquid recovery at suds conmditions is not totally by displaceunent. getserally shtoumld provide 50 iOO n50 Pore Vol. both the break through and the ultimate. Tire test nmay also be terminated at a pre-selected high producing gas to oil ratio. improves the recovery efficiency. At tire Inigher pressure of 28.5 muir. A tube length of 12 metres is adequate in most cases. Producing gas to oil ratio in gas displacement at two different pressures. hut the additional recovemy above MMI’ is gemmerally nsininmal. however.8 shows typical oil recovery plots at two pressuires. The evaluation of recovery changes with dnslmlmnceulmennt prcssunu’e. and allows miscibility mireasurement within a reasonable test period and fluid consumption.2.mtaI Stm.

Tire observation of a gas bubble hchavk~ur. that is. The relative location of tire banks are determined by the composition of the injected and reservoir fluid. A . should not. the change in liquid recovery ninuny not properly reflect the impact of the varied pressure or gas enrichment. including sight glass observation. TIne advmmntuuges of suds refinensenmls. The apparatus is simowmm in Figure 7. the bubble disperses very rapidly and disappears immto tine oil. At or slightly above MMP. Fnperinuenuta! Stnudues 265 0) 90 80 I) > 0 U C) C) ‘C •10 60 Wireur ussiscnhuhity is umchnueved by time vaporising gums dnive. Tine sums tube cmtul provide very useful pimase heinaviour infortnnation. al least theoretically.264 108 7. This S mnpplieatiomn will be described in Section 9. have also been suggested as measures of miscible displacement. The MMP detemuined by shun tube displacenrent does not necessarily correspond to the thermodynamic miscibility. to introduce miscible fluids into the core. 13. A series of tests are conducted am dilTerenmt pressures. the bubble develops wavy tail with tine gas-oil interface vanishing from the bottom of the bubble. The gas bubble coistimmuumlly comstacts tire oil tlsrougis its upward journey which results either in reaching equilihriummmm wills tine original oil. The compositional variation of produced gas in an inmmssiscible dispimtceumscmsl of an oil by nitrogen is shown in Figure 7. % Figrure 7. but the prevailing low interfuicial tension betweemr the two plnases still provides a lsighnly efficient displacement. is considered to include sonse of tinese factors. At pressures higher tinan MMP. line recovery of a rich bank may be delayed by enriclmimmg tine immjectiomn gas. flow factors.12. oo° 60 • 00 • 00 120 0 40 Pore Volunuic lunjecmcd.10. far below MMP. wInch can conveniently be detecled by fluctuating producing GOR. Determination of MMP by plotliimg ultimate recovery versus pressure. Conceustruntion of ummetimane ansd nitrogen in the produced gas. ‘I’lme use of reservoircores. as shown in Figure 7. 1. An absence of methane bank [19]. where tIme slim tube provides enough colmtuncting lenglin between tine pimases. Variations of producing gas to oil ratio with injected rich gas volunse. The banks rich in immterrnediate and heavy fractions contribute more to the oil recovery.% Figure 7. are open to questions. and a smooth profile of concentration of intermediates [hO].s mind di. A combination of the above criteria. the msmethamme comncentration exceeds that in the original oil. is often counsidered. often is used to identify miscibility conditions.splmncemmsent conditions. isemncc. svlncre mm smimahl gas bubble is introduced into time bottom of oil column throtugis a water pinumse. rising in a visual high pressure cell filled with the reservoir oil.12. or achieving nsiscihility depending on the lest pressure. An arramngemenl comnsposed of mm slim tube ahead of a core. it mmnay be mistaken as a reduction in oil recovery [181. create concentration. Rising Bubble Apparatus 0 Cl • 1000 ‘S • • S S S • 0 0 •• • 100 0 20 40 60 80 Pore Vol. the critical stale is expected to depend on flow and dispersioun factors. The dispersion and compositional vamimttiomns. Whems msmiscihihity is achieved within lIre transition zone.11. At the gas break througis. 10000 N•trogt’n 0 S S 20 0 09 0 5 S ~7 25 ). lnmns heeum suggested 1211 as a quick mimethod of measuring MMP. the achievemeunt of the critical state.11. Adverse effects such. particularly un micin gums iumjectiomm. for evaluating pinumse belsaviour models when applied in gas injection processes. affect tmniscihihity conditions as explained in Section 7. 20].m 7. This is due to the high volatility of methane which results in its vaporisation into the advancing nitrogen. as dispersion can prevent or delay thermodynamic msniscibilmty [9. MPmu Os • 0 40 • S S S • • 0 0 Figure 7. Injecled. where tuning of equations of state will be addressed. At pressures.3. Gas Injeciio. additional to MMP or MME. but its size is reduced as the gas is partially dissolved in the oil.2. acting as a buffer between gas and oil containers. however. and saturation banks along the tube. If Ihe displacememst us tentnimnunled before major liquid producing banks appear. too 1 40 45 50 0 0 50 0 40 20 25 30 35 5 MMP 00 0 1)isplaccnuncnn Pressure. the bubble retains its almost spherical shape. unnd tine bubble simape is nnotnitomed mis it rises up.

Dew Point A — Oil cj EJ C) (~~ 20% ~ 0 If) ‘C 40% Liquid volummnie Fraction 80% 60% 50% Needle Figure 7. density and commnpositioms of tIne equtilibrated plnases are measured in each conlact. or attains equm i I ihriummn witim it (Ii mnitiusg tie Imuse).26 MPa.s 267 gas htmhhle not achieving nmiscibility.2. I shnows lIne constpositiomm of equilibrated guns mmmd oil in a forward mumltiple contact test of mu volatile oil unnd umnetisumnuc tnt 373 K and 35. as occurs in gas-oil displacement. tire equilibrated plrumses below tine saturation pressure provide information on fluids with various degrees of proximity to time critical point. A knnown aunrount of oil is loaded into atm equnilibriuns cell and the injection gas is progressively added to the oil stepwise. it provides valuable durta for tuning of EOS. Liujecti~nu ( . simuiates conditiouns tnt time its jection frommt. slmowmng humid pirumses at start of experiment [211.15). Tire dew poimmt initially increases.15. time mnixture saturation pressure mmmd volume are measured. . witim little experimmmetstal effort. The volume. Gas InjeCtion 7. Therefore. witim increasing metlnane. finite volumes of reservoir oil and injection gas are repeatedly contacted. A constant composition expansion test can then be conducted on lIne mmsixtuire. particularly for calibration (tuning) of equation of stale models used in sitnulalion. The above procedrmre is conliuttued until Ilne injections guns citimer beconres immiscible with the original oil. and tine density and composition of equilibrated oil and gas are measured. point C. ‘Ilme static cquililrrituumr tests which closely sinruulate contimmuous contact of injection gas and reservoir oil are nnnuuhtiplc commtuncl expcrinmncnts. albeit at different pressures. ‘Fumble 7. the variation of mixture saturation pressure with added methane for a light oil.. inn wlmicim oil and gas are contacted at the reservoir pressure and temmnpermuture. wisere time nnixtume heisaves gas like with furtimer injection of methane. Figure 7. indicating an approach to the limiting tie line with no nmsiscihility adlmicvedl. Variations of nmixture saturation pressure with added methane to a light oil. html will uiot disperse. Allhoingh the single contact experiment. The incremental increase of methatie content of tire fluid results in a critical state. The measured MMP by the above mnnetbmod has been shown to agree reasonably willn tlmat by displacement using a slimin tumhe 1211. and lInen decreases.ts y 4’ Reservoir Oil 4’ Figuire 7. will also disappear into ami unmdcrsunturated oil. where time enricimumnent of advancing gas creates tine miscible fluid. Time equmilibrated gums in each contact is used in the next contact with the original reservoir oil. Batch-type gas injection experiments are designed to generate phase heinaviour data. prior to the next gas addition. Experi~neiutal Studie. known as multiple contact experiunents in PVT cells. The method is suitable only for the vaporising gas drive process. does not simulate lire commtinuous contuict between the phases. Schematic diagraums of rising buhbl~apparatus. In this method. Tine lures showing constumnt liquid volumumie frmsctiouns witlsinm tire two phase envelope converge at time critical poinsl. simulating gas advancement in reservoir (Figure 7. or single contact gas injection. The forward multiple contact lest. Contact Experiments Slim tube tests do not generate all the volumetric and compositional data required for evaluation and calibration of phase behaviour models. Flow diagramms mm usnunltiple forward contact experinment. 0 Metlmane Added to Oil > Figure 7. where the gas has become progressively richer by contunctimig oil. Time counsposition of equilibrated oil in the last contact is unimnuosl lime sumumie as thrat of tine originimul oil.14. It covers a wide range of fluid composition. to generate additional infornmation. The most common experiment is the swellioug test.13.266 7. Although the composition of the mixture does not follow the compositional path in a gas injection process. After each addition of the gas. gas immjeetion processes are often simulated in batch type tests. The bubble point pressure increases with addition of gas. and shrinkage or swelling of the oil.14 shows.

87 0.10 1. provides valuable infomsalion on the vaporisation effect of tIme iusjcctioms guns. however.81) 5.31 0.10 0.26 4.74 1.8 shows the variation of equilibrium ratio for the same sysleun as shown in Figure 7.000 .79 1.8. with rich gases the multiple backward countact test canisol generally provide miscible fluids in real cases as discussed in Section 7.8! 11.41 0. timat is.95 1.83 0 a C ..76 1. II 1.16 C3 5.05 (1.03 1.65 2.16 shows the variation of equilibrium ratios of the mixture counpomments due to compositional changes in different contacts.0 0 0~ ujO .ntacn Stage em 02 03 .66 0.36 I .47 0.24 munjccniot (.0o~.19 0.52 1.08 0.32 2.82 (1.85 0.66 1.17 0.01 10.78 0.65 t).13 010 1.92 1.15 0.01 1.63 0.07 0.55 2.13 0 0 Figure 3.55 2.69 5.85 0.24 57.47 1.69 1.69 5.16 2.27 (1.20 0.55 1.72 1.99 0.23 0.01 1.36 ~Oas~ ~j ~Gas 1.16 is also a revealing example of lime effect of fluid composition on the equilibrium ratios. 0000 -0_0 . Variation of equihihriuimn ratios of fluid conmponents in multiple backward contact test.26 2.59 0.21 0.60 0.04 5.15 0.51 0.11 0.06 1.1. C.33 2. Flow diutgram in mnnultiple backward comnlact experinreni.00 1.99 121 1.41 2.71 9.0! 00 U. 18 0.15 (1.76 2.86 0.08 I . F.75 0.72 10.49 2. Gas lnjectiouu 7.3 I 2.5! 0. A straight line can be drmmwmn through the equilibrium ratios in eachcontact.18 1.32 r I Reservoir (SI Oil Oil th1 0. 16 0. It is similar to forward contact test.82 0. Figure 3.30 1. 0 Component Orig.40 4..71) 1.23 1.C5 nC5 C6 C~ 4 1.17).40 2.70 .22 t).19 1.22 of equilibrated oil and gas in a four stage forward nmumltiple contact test.67 0.1)3 74.25 56.27 0.00 1.23 1. what lunkes place at the injection point.76 (1.14 0.268 7.53 1 C2 10.91 9. Each component has been identified by a plsysical property group as described in Section 3. test. 2 3 4 Oil (las Oil Gas Out ~ Oil (. Composition (mole%) Contact No.87 7.u 10 269 Figure 7.17.41 2.05 0.56 4. indicating that tire properties of time Iwo pirases diverge progressively.92 (1.29 0.69 0.57 9. Oil C 57.06 0.as ‘j’ 1. Time slope of tire line increases with each contact.4 i-C nC4 i.91) 1.65 3.12 0.36 0.38 0. 4 -2 1 0 1 I I ou)( I — ITt) Figure 7.. . II 1.98 0.46 57 II) 72.39 0.89 4.92 1. but the equilibrated oii un each contact is used in the next contact with the fresh injection gas (Figure 7. the line should isave become horizontal with K-values equal to I for all the components.09 I .41 0.85 1.41 (1.33 0.16. 19 0.39 0.36 1.00 8. Variuutions of eqnnilihriuunm rumtio of fluid counponenls in mntmlliple forward contact ~l 2.75 1.22 1.23 0.99 1.2.69 1.57 4.1)5 0.41) (1.12 0.41 2.uperiennetntal Sluu!ie.49 1.us 57.1)1) 4. Even.96 1.64 1)55 (1.62 1.06 5.36 2. simulates the injection zone tmiil.1)3 0.98 0.16 0..74 0.42 I .73 71.41 7.54 (1.92 1.27 0.97 Figure 7. Note that the slope of tine line decreases progressively with each contact.42 2.1.74 (1.65 0.24 0. 1)1)! -2 -l 0 (I +om)( I— tf’F~) .72 0.33 1.19 0.87 78.04 1.28 0.2. The experimlmemmt.77 0.81 4.16.06 1.97 1. In 0.58 2. Tine test is particularly valuable to simulate gas recycling of putm’tially depleted guts commdensamc or volmmtile oil I ••“~‘~ .76 0.15 0. as the temperature and pressure are constunnl.54 0. For achieving miscibility.26 0.) Contacu Snage St 02 03 reservoirs.54 t).0 0’ 1)2 __.16 1. Figure 7.1)2 1.25 (116 0.95 1.18 0. Table 7.02 .61 0.28 0.58 0. The backward multiple contact test.61) Cg C9 C’ Cj 0 C12 C 4 1 Cl6 Cu Cl 8 Ci9 C20+ 1.13 (1. but in backward contact test at the same temperature and pressuure.68 01 4 .

It is also often beneficial to deplete a Imigir pressure under saturated oil reservoir. At such conditions.270 7. Figure D.SPF.. Connceptuuml phase belsaviour diagranr of first contact minimum miscibility pressure for gas-solvent-oil systeusm. Note tlsat all the curves for different gases coumverge at time solvent critical poitnt.19. the associated critical pressure is MMP for the selected gas-solvent. First Contact Miscibility nitrogen has been studied by several investigators (13. when time reservoir temperature. As time solvents are expensive. or butane.18 may also be used to estimate the minimum pressure required to achieve first contact nmiscihility between propane. Vaporising Gas Drive Methane (lean gas). mmd displmmce oil miscibily by vaporising gas drive at lower pressures thaum by first co.mtact miscible displacemenmt at high pressures. mostly developed uusimrg simm lube displacement data. Hence. html sinotild not he relied upon. Figure 7. after being tuned to relevant experinnental dumla (Section 9. which provide informalion on tlrertnrodynaunic nsiiscibility. Intermediate hydrocarbons. At tenipcrulllmres above its critical point. the solveunt can never fortn two pisases wlren ussixed witis the gas regardless of the pressmre.3). or nitrogen can displace oil very efficiently by developing a miscible bank through vaporising the oil intermediates. because high pressure gas injection is also usually a very expensive operation. fornnm Iwo plmases with tIne reservour oil.ceibility Co’udiz joins 271 The values of MMP or MME may be estimated using empirical correlations. driven by un lean gas such as methane or nitrogen. 18. Gas t. can be used with confidence.19. which can be estinmated fronm Figure 7. or us compositional phase behaviour model. or UI very Inigh pressures. Tire single contact (swelling) test provides time first contact MMF’ data: it us time umnuixiummunun pressure on the phase envelope boundary as shown Figure 7. M~MP can be estimated by simulating the single contact test between oil and solvent using a pisase behaviour model.). are usually first-contact miscible witlm oil at typIcal reservoir eondilions. provide rouglm estimates of the nsinimum uniscuhihity pu’essumre or enriclnnsent. It unlay. they are generally injected as a slug.3 PREDICTION OF MISCIBILITY CONDITIONS 7.ujectuon 7. This can happen eitimer wills very rich injections guIses.— — ~ Locus ofCrimicat Poinls Ri 0~ ~ Ti ~ Td Tensperature Fugture 7. T . and several other injection gases 122j. The gas and the solveust msre simosvn by tiseir vapour pressure curves. The injection of suds a highly rich gas to displutce oil is not mnornmnuully ccononnnical. Hence. K 400 450 Fmgure 7. Phase behaviour models. 23-26]. Empirical correlations. 1 the gas-solvent behaviour controls MMP. the achievement of miscible displacement is controlled hy the solvent-oil belmaviour. it can he cslimsnatcd by simulating the above test using a phase behaviour model. such as propane. 1 in Appendix D shows the locus of critical points of various binumry mixtures. .Copyrigtnt. The minimum miscibility pressure for methane or Is I)) 0 3(11) 350 Teunmperatmurc. 10 predict the miscibility conditions. At any temperature. whereas the reservoir oil is identified by its critical point. a single component solvent and oil system. Reproduced lromn First contact nmmmnintntjm immiscibility pressure for gas-solvent . Any point above the curves is considered to he a single phase fluid. and proposed a correlation to estimate MMP for VGD processes. butane and luquefied pelroleuunn gases (LPG). Even when the miscibility conditiotms for a specific fluid system are experimentally known. The lean gas and the solvent slug should also be miscible for an efficient displacement. Firoozabadi and Aziz [23J used experimental shun tube data. 1221 wiltm rcrniniscioui Pt 0 0) — --. however. Td. They may be used for preliminary screening or feasihilnty sludies. I’redjction of Mi. At a temperatuire below the critical temperature of solvent. Figuire 7. ‘lire loci of the critical points of mixtures formed by mixing gas and solvent or solvent and oil at various ratios are shown by the dotted curves. known as solvents.---. 19 slsows counceptunally lIne mmmiscilmility heimunviomnr of mu simnglc counmlxnuscuil immjectiomm guns. tuned phase behaviour models are often required for compositional reservoir simulation of gas injection processes. 30 25 20 The injection gas and the reservoir oil should fou’tts a single pluase flunid whets mmnixe(l mit tiny ratio in this process. is above the critical point of tIre solvent.14. though it was considered more reliable for methane than nitrogen injection.

Time calculated vumpour fraction is monitored.5) MMP for nitrogen. Most methods that advocate using a phase behaviour nnodel to predict the miscibility pressure. Tine results were presented by a set of curves correlating MMP with the concentration and molecular weight of the inntertmnediumte fractions of tine injection gas. hence. As poimnted out in Sectiomr 7.saumne br Oil Ii. though generated on a four component mixture.(l. MMP is affected by time gas composition. I.udjtiopus 273 65. Prediction of Miscibility Co.1). yet quite rigorotus. Tlmey concluded that the oil tie line becomes tine critical tie line for low nitrogen to ur’uethane ratio. and also helpful to select realistic methods of estimating MMP. will produce equilibrated plnases with counipositions as tirose al the two ends of time tie lime.06x~.8T—460Y”~) 1~ 2.~ 460)0 25) (7. )( For M~ 2~6 =34 (7.5% mind 25. is also strengthened by the fact. the critical tie line exteinsion goes through the oil composition. = 792..10 5 e 2 (7.(5. such as displacing a hydrocarbon mixture willn metimamne or pure nitrogen. 5 anrd tire temrsperature. MPa XC2CS = = = mole fraction of intermediates in oil. Gas Injec(iouu 7. umnelhod is linunt of Jemmsenn umnd Miclrelsen (281. Koch and Hutchinson [24] showed.o4— I. As the tie line lengtls decreases and nhiscibility is approached.nk et al. 7. (l. hence. In tlsis process. that MMP declined wlsen a lean gas was added to nitrogen.3. Benlmummin et . For pure nitrogen injection. a cross over tie line becomes critical. x~and yj mIre llme mmiole fractions of conmponent i. = Wlmen immiscibility is achnieved by tIre vaporising process only. the limiting tie line length decreases approaching zero tnt the critical point. however. ‘Fine mixture 2 X unt tine hobble point condilion.74 —11. equilibrated (nil and equilibrated gas respectively. MMP can he calculated quite simply by a phase behaviour model. Pm = 38. Eqs. the value of n” decreumses approaclning nnninus infinity. The view that MMP for nitrogen and mnnetlnaise is tine same.. 2 MMP. are quite informative in explaining the apparent diverse views expressed by various investigators. /(M~.(7.s that amsy nmixture on the tie line extension. that injected nitrogen vaporises tine Imigimly voluitile metinane to such an extent that the advancing gas front is very nnuch dominated by msretlsane inslead of nitrogen. which is the same as the operating line.777xtO’ M ‘‘ c 181— 46(1) (7. The above correlation wlmich provides the same vunltue of MMP. ‘Fhme umulhors studied the problem by analytically solving the governing equations for displacing a four component mixture with nitrogen-methane in a dispersion free one dimensional porous medium. as follows: 53 4 S 258 1198(1 M’’t t \ 1 = 43. Condensing-Vaporisimig Gas Drive l’Inc coundennsimng_vmm~sorisiungmntuscibmlmly is mmclmieveml geunerumily at lower pressures llmann Ilnose of time vaporising guts drive. hut with a negative vapour volume. The above conclusions. 2 and Y’ respectively.2) where. A simisple. relies on the vaporising gas derive comncepl. As sirown conceptually for a Ilirec colulpoumemnt nmmixltuuc inn Figtnnc 7. [7] reviewed the literature on miscible displacement with unitrogen.ml. TIme muccuruney of tine uthove corrcluulmomn ins predictiirg MMP for nitrogems was founmd (271 to he comsnparuible to Ilmuui of 12(137.3.3% respectively.1) where.1 27M )y + ~t).8T .3) = 6 52 wlmere z~.8T_46O)~25)] 4~ (7..8T_460)023)+ l430x l0~[x(. searching for a large negative number. winemm line gas Y’ is incrementally added to time undersattnrated Oil B. hence. time achievement of immiscibility by condensing gas drive alone is not generally expected for real reservoir fluids. nun tire tie lime.(l. mum a commnpumnmilivc sttm(ly oi MMI’ correlations [27]. 1-2) we get. for exumnnmple. Furtlmer a(lditi(rn of the gas will lake uultaiiss the composition 2 tIme mixture into the two-pima. the nnixlure composition enriches in the2light fraction by moving towards time connrposilion X’ . with a standard devimmtion of 11. which is independemnl of the injection gas composition. ethane to pentane incluusmve molecular weight of heptane plus Temperature.1 752M —(32 23—11. lime liumuiliung lie liunc anmil lime fiinunl opcrmttiutg line are line .=x(I_nV)+y. mn’s’ is the vaporised fraction of the feed (original oil) wisicin will be negumtive in this case. The MMP for nitrogen is generally higher than timal for nsnethane. As time pressure increases and tine trmiscihihity is approached.1. Hudgins et al. the oil tie line controls the miscibility.6) . simnmlar to low nitrogen gases. I) was found as tIme most reliable MMP correluutioum for lcuunn guns ulnnd nnmlnmngcmm iunjcciiots. (29( missurned tlnumt tine 3 critical tie line is parumlhel to the L-Il uuxis in time pseudo-ternary diagu’arn In develop MM! correlatiomns for rich gums immjection. wlnen flashed at time prevailing pressure amnd temnipcrature. I(M<. (I .272 1mm 7. MMP can be determined by flashing time oil at the reservoir tenmperalure and successively increasing the pressure above the bubble poimst.. Iluids witlm a high methane content. Glaso 1251 fitted curves to the results of Benlnam et7ai. linumt us.se region. winich is based on the ideun of mmcgmnlive liunsln cumlctulullioun described in Section 5. Dindorm. As a pruuctical rule values less than -It) immdicate proxumity to MMP[281.I58x l0 x~ /(M~. and suggested some explanations on the apparently conflicting views presented by various investigators on the effect of injection gas and oil compositions onr MMP. wimere time equilibrated gas and oil are sisown by X’ .296x lO5Xe c I(Me. where mmsiscibility is coinlrolied by tine original oil composition only. MMP is independent of gas composition.mmS~ i=I.(7. hut the difference decreases for oil samples with high bubble point pressures. I lemncc.. propose conducting the forward mnultiple contact test. lnvokiimg tire eotmsponncrrt nnmateriuml bumlance in flash calculations. the mmmolecular weiglrt of tIme reservoir oil C +. . K Mc + 7 T Eq.4) The symbols are as defined in Eq.. The test is to be simulated by successively raisimmg tine pressure and monitoring the approach to tIme critical state. in the initial oil.2 N (7. I). For gases with a hugh concentration of nitrogen. rcguurdlcss of tine imnjcction gas composition.39 e~X + 25. [13] concluded that the oil methane content is an imnportumnmt pusraumneter f~r achieving miscibility in nitrogen injection and proposed the following correluntmoms to estimate The above analysis imndieate.

3. i.00 17204 D-l 0695591 F=-0. 1 Contammminalion of CO witin gases of Irigher volatility. calculated by the 2 weight averumge mixiung nule. 275 = 3804—0 58 l326M —(55. with a standard deviation of 13.00l0102 whmeuc xi.10) where y~is the mole fraction of methane. (7. (“ulaso inehinded lime effect of oil type on MMPby calculating time nrolecunlumr weigint of time stock taunk oil C +. is generuilly quite low. using tine molar average mixing rule for calculating the pseudo-critical tenrsperature Inave also been proposed [34].e. ramsgimmg generally fromnm 10 overpredicted to 40 MPa..7/(S~.482X10 0 0. tun low temnmperunlure reservoirs. which are based on the criterion of cntical inlection gas tie line. increases MMP..7 138599 E= -0. Tiserefore. N and C . Tine umtntirors sruggestecl to use a value of 325 K for the critical leusspcrumtuures oil 1 S mmmd elinamse. instead of their actm.05x hO 6(1 . I x~) 0)16 6 8 (7. 7 M=572. . represent propertues of tine injected follows. usmng the Peng-Rohmumson EOS. inn gas mixtrure.7yM~° )(I. tine C02-oul mnixture may form tlnree phases of vunpour.8 hmi41~l. 100 (Yc~ +O.wr 460)J 2~5 5 15 where y is the mole fraclion.8~ I’c _460) where ~ in K.=6. Pedrood [31] simulated the displacement of oil by ricim gases using a one duussensional compositional model. Alston et a!.12) 18. M.274 7 Gas l.7807248 C= 1.14) The above correlation was demonstrated to be superior to those of Benham et al.~ 5 2 02 ) and .. aund Glaso in a comparative study [27]. 2 ( 87. and Tc is time critical 1 1 meunnpcrunlunrc of coninpomicunt i. The predicted values. Ennick et al. y~ ME~FrMcO~ = (7.730el356.9) (7. and Mc5+ is the molecular of C5+ in tine oil. Predictio. and various correlations to estitnmalc MMP imavc been proposed. 2 Otlner correlations. 6 ~=(l y~. and Mc2.9909715 B=-0. The validity ofthe above methods. nespectively. mis.79—0.muml values to inmnprove the results. . dip. C .3%. = I wlserc w is tine weiglnl frunclious of conmspomuent. 0t36 respectively. The estimated addition of less voluntile C lowers 2 3 MMP for CO can be corrected for time effect of 2 impurities by empirical correlations. T( ~wi(. tO predict the miscibility conditions for a number of oil and ruch gas systems.x. 2 P.us . For oils witis point pressures less tlsan 0.935j— IInn~ I (7. even at moderate pressures. (7. m is in MPa.8y~. N ). An extensive sensitivity analysms of the parameters affectmng the miscibility resulted in tire following correlation: I’~49. for real reservoir fluids is in doubt. [33J proposed the followiung correction factor. 2 2 higimer pressures are requmired at higher tennlperalmures. (l. 7 7 Kuo [301 simulated the backward multiple experiment. Hence. ll S)1 its line (nil. l’he values of the constants in tIre above equation are: A= 0. 1321 reviewed 17 correlations proposed by different inmvestigumtors. or miscthmlity. y~ .4 is the mnoleculunr weight of C to (‘4 frunclion us 2 the injected 1m gas.20 t 2 54 W 2 gas 5 = (7. and ‘F is inn K.+0. Alston et 2 uul.13) I~ —460) 1\ I . as where 0 and s~. and P~ and ‘J~ tire in MPa and K. ultm(i x mIme lIne untole fmunctioun of volatile (C .8 ~ 87.r_4~ 44 16 5 t~ M 520e21706YmM” ){l 8’~ —460 (7. is tIme pseudo-critical temperature of the impure CO gas. MMP for 31 C0 . and 2 1 MMP.i.68630+2.of5%.C0 . to he multiplied to the estimated MMP of pure CO .46——-—— ~ (I 8T_46O)TIM~. [33] developed a correlation based on a large number of MMP data for pure CO .11) umuid reservoir onl. CO is often a super-critical compound and behaves as a strong 2 solvcnml extruncting connsponenls as Ineumvy uss C . Tine minimmnultr miscibility pressure.35 2 value 2 of (x~/x ) MPa.l72xl0~ lM3..8) 2~6 where ~m is MMP in MPa. Miscibility by cumrhon dioxide iuujectionr has been studied extensively. slnowed an average deviation Time Benham correlation the results with an absolute average absolute deviation of 37% [311.~570) where S~ i ÷ s the specific gravily of C + fraction.7) I For M~ ~ 2 = )/IM . whilst 2 connponents such as H S. 51 18—0 1772M —(5069—0 t47M)y +(3 392xIO 1 Time predicted MMP by the utbove correlation was compared with slim tube data on II oil reservoirs.u of Misc jbj!jty Conditip. T is the temperature in K. MC2. and iumternnediate connupommenls (C 1 bubble 2 2 C~. TIne solvency of CO iuncreases with its density.C6 is the molecular weight of the C to C fraction in lIre mnjectiOmm 2 6 gas. Al reservoir conditions.8’F~—4fi0)’° M~ (x.I88M)y +(t.iectiopu 7. y is the mole fraction of methane imr the insjection gums. The results were correlated as. i. to increase lIne CO density for achieving 2 two liquid phases. the is taken as unity. =54 For M~ As it is known that non-paraffin oils achieve miscibility at lower presstmres.l50. respectively. (‘(‘~2rids liquid ummnd imydrocarhon rich liquid.

Sl’E 22637.M. and Mcm.. of 62nd Ann.. (Oct. Proc. . Estimate MMP of the following reservoir oil and the injected rich gas at 367 K.T: “Nitrogen Miscible Displacement of Light Crude Oil. Johns. Hagoort. 1990). and Ch~mng. JCPT.J. SPE 16715.T. s~i”~522I5 MMP=35.09 5. SI’E 15493.50 8. Jolmns. of 70th Ann. and Orr Jr.7). The selected mathematical parameters to solve the governing equations. and Nouar. The predicted valume assuming miscibility by vaporising gums drive is expected to be higher than those by the condensing process. D. 2. atmd Diimdoruk. B. of 61st Ann.. Diumdonnk. Component Cl C2 C3 iC4 Oil. Eq. is. Eq. L. (Sept.. and Orr Jr. Orr Jr. (Oct. mole% 84. Stalkimp. such as the backward multiple contact test.(7..M: “Effect of Gas Enrichment and Dispersion on Nearly Miscible Displacements in Condensing Vaponising Drives”.81 4. SPE Advanced Technology Series.3..32 MPa 0 4 04 36 84 Interpolating between the above values for Mcm. 4.M.05 7 calculated as 205. Flock. 7. 44 and 54 at 367 K. Fl: “l)isplacemrmenl Behaviotnr of the Condensing/Vaporising Gas Drive Process”.. Llave. J. 985-998 (Oct. cannot generally produce the miscible bank.. Proc. predicts MMP=36. Conf. Eng. SPE 30771.276 7. Conf. the proper simulation of the compositional path is essential. 16 MPa Kuo Method: The calculated MMP by the Kuo correlation. 1(2). Lutrse.S: “An AnaIyti~~’ Model for One-Dimeumsional. and On Jr. J. with M~. F. The simulation of simple batch type experiments. Proc.. 80-88 (Sept.T.51 MPa. 3.K. 1987).M. Proc.n 7. A: “Parametric Analysis of the Determination of tine Minimum Miscibility Pressure in Slim lube Displecements”.c = 4 37.Eng. Example 7.. 7.65 C6 C7+ 2. Pande. also affect the results by introducing numerical dispersion [14]. Conf. 26-34 (1993). and Orr Jr.=56. mole % 54. RI: “Theory of Multicomponent Miscible Displacement with Nitrogen”. F... Dindoruk. 1984).84 The calculated MMP for ~ of 34. W.l).Eng. ConI.K. 100-106. F.(7. time Firoozahundi-Aziz correlation.99 MPa.11 1. fraciion by Eq. Jolmns. 7-16(1993). MMP=40. and much lower than the answers by Glaso and Kumo metlmods. SPE 19668.. 725-738. such as the number of cells describing the tube and the time step.33.78 Gas.9.. (Oct. Glaso. we obtain.39 23. Reservoir Hetrogencity and Cross Flow in CO Floods”. 2(2). 13. 24. respectively. Silva.= .4 REFERENCES I.. F.M. 1991) 5. usimsg its specific gravity. B.. 0: “Miscible Displacement.40 C7+ Properties: M=209 S=O.82 0. F..87 MPa The umneasured vunltue usinmg shuns tube data is 39. 1995).. and Risseeuw. A.(7. 1984). B: “Developnnenl of Miscibility in Four-Commnpotsemmt Gas E)rivcs”. A Laboratory Study”.~ =56. The most common method is the use of one-dimensional flow coummpositional rnnodels sinrulaliung displacement in a slim tube.-Oct.I I) are calculated as. Johns. Eq. 12. is Glaso (Benham et al.(7.(7. 1989).. of66th Ann. Recovery Tests with Nitrogen”. 10.63 8. Orr Jr. II.. 169-179 (April.c.8). MMP=54. Further details on using a one-dinmnensional compositional simulator are given in Section 9.’E’. A. SPE Advanced Technology Series. .6). (Feb. 6. Res. SPE 2 Res. R. FM: “An Analytical Theory of Combined Condensing/Vaporising Gas Drives”.!. Gas lnjectio. (Oct. F. As the miscibility is determined by a cross over tie line.= 186.94 nC5 1.17 iC5 0..I0). FM: “Comnposition Palms in Four-Component Systems. 0=1124 resulting in. F. or plotting the predicted liquid recovery similar to using slim tube experinsental data. Monmroe. Effect of Disolved Methane on 10 CO Flood Performance”.8323 Solution: The adjusted molecular weight of the C . Three Component Condensing and Vaporizing Gas Drives”.(7. R. Conf. 8. using Eq. R. of 64th Ann. SPE 30798..9). SPE Res. Proc.. 423-432 (Aug.T. R. SPE J. 1995).. Payers.. and Eq.. Dunnore. The model also requires correlations for calculating the relative pensieability. MMP can he found by monitoring the commnpositiommal vunriations along the tube. Prediction of Miscibility C~onditio. SPE Res Eng. F.27MPa P .A: “A Conishinsed CondensingIVaporisimmg Mechanismmn in the Displmmcemenl of Oil by EirricIned Gases”.M. 7. (990). 6168 (Feb..66 C02 1. =53. K. 2 6 M~ _~=[~XCMC]/~XC 2 6 =36.L. 1990). M.us 277 Phase behaviour models can be used to estimate miscibility conditions in rich gas and CO 2 injection. However.19.W..L.iek. and Orr Jr. 1986).54 MPa Pedrood Method: The two parameters representing gas and oil in Eq. F.M: “Interaction of Phase Behaviour. are as follows: P .3. Proc. The molecular weight of the C -C is determined as.M: “Miscible Gas Displacement of Multicomponent Oils”. and Johns. viscosity and interfacial tension.. of 70th Ann. Hudgins.(7.62 MPa P. Comnf. Any reliable EOS may be used to predict the phase behaviour of injection gas and reservoir oil. which is only slightly higher tlnann the answer by Pedrood method.) Method: nC4 2. 2 9.

Eng. 373-378 (Aug.41 0. No. 19-47 (1990). SPE Res. and Azuz. SPE Res. 1991). Boersma. 523-527 (Nov. 1985).c~_~C~. J: “Displacement Characteristics of Nitrogems Flooding vs. 3 I. Wlmuut is I Inc mmmlmitutuimnum reqtnmed cotrceunlrmntnon of propane1 in 1 a guns11~ consposed of (‘‘ -(‘i Inn mmiisci hI ~ (1151)1 ace mini oil cotumposed ol (‘~(60 umsol%) ullm(l nC ~ (40 moi%) at time above courditiours. SPE Res. D.L.A: “Miscible Disphacenments of Reservoir Oil Using Flue Gas”. and 1-lagoort. 1972).E. A. 1985). 2 1312-1318 (July.27 N2 C02 0. and the injected rich gas described mr time followiumg table.ue.57 ç4 ~ç~5~C~ç6+ 1. P: “Prediction of Minimum Miscibility Pressure ims Rich Gas Injections”. HoIm. described its Exercise 7. 2 7.37 23.2..c 279 14. 1982).. 575-582 (Nov. Thesis. 1985). 1-17 (l99t)). 2076-2082 (Nov.. Eng. What is your recomusrended pressure for gas injection.51 35. Firoozabadu.. Correlation for lnrpure CO Streanmis annd Live Oil Syslenns” 2 34.J~_Jc~4. Tehran University.30 8.3. estinsmatc the minimum miscibility pressuire at 360 K. Nornnnal huntunnic IS 10 be nmscd mis tlte solvent slug in a tnnellmane gas injection process. 26.33 S=0.6. CouiuponenuCl . Eng.W._cL. Methane Floodirsg in Volatile Oil Reservoirs”.2. G. SPE 3. 87-98 (Feir. 57-59 (AprilMay.. Dowden. Alstonm.. 0: “Generahised Minimum Miscibility Pressure Correlation”.N. (‘uulcumluule MMI’ inn lime above exercise. R. Proc._C6÷ 4175 7. Winat is MM!’ uml 410 K? 7. London (1979). V. H. 35-41(1994). Wenger. The reservoir pressure amsd teminperunlure are equnal to 82. of 2nd Internationuul (‘onfcrence otm Clscmntistry un Inndunstry. 8 1-92 (Feb. 14(1).S: “Preduction of Miscibility for Enriched Gas Drive Processes”.5. N2 1.A: “Correlation of Mininnum Miscibility Pressure for Impure CO Streaunms”.12 0. 18.75 MPa).3. A(’S. SPE Res. Trans. 7. 927-934 (Dec.surennent of Minimmmumsn Miscibility Pressure with the Rising-Bubble Appratus”. and Renner. Pedrood. I-IA: “Acid Gases and Their Contribution to Miscibility”. F.L: “Porous Medna.5 EXERCISES 7.75 MPa and 387 K. D. Commnpare various correlations (measured value=32. Enik.P. Eng. 27. R.M. and Coslunims. F.A. 7-10 (1958).R. amid Kuniznnnan. 1981). AL...J. 22. 24. SPE 14152. RB. 15. A..9(1 C3 3.. 16. Tajdar. JCPF. is to he mniscibly displumccd by a gas commnposed of 90 nmnol’X (‘02 annd tO numol% N2.S. umsumig lIne nmegative fluislm nnethod. ML: “Calculatuoun of First mind Mtmiliple (‘ountuict Minimnsum Miscibility Pressures”. F. Ituilsrmiini (Oct. 2!.ç’~ 9.9! jç4 0. W.05 1. Z. I .17 0. Coin~nentCI Oil. Novosad. iloldcr. 33. T. LW. Benham. R. In Situ. ElK: “Rapid Mea. 2 1988). 17. G. 33. 229-37 (1960). B. and Elutcinson Jr. R. 8. Telrran (1995).6 K mmmd 28 M l’ui. Kokolis. K: “Aunalysis mmmd Correlaliomr of Nilrogenn amid Leanr-Gas Miscibility Pressure”.T: “Study of a Possible CO Flood in Ranmgcly Field”.. Use mu plmmmsc bclnmmviour nnno(ldl to develop a tcrnnuury diagrann for C —C —rmC at 377. AIME. 32.F: “CO Minimum Miscibility Pressure. 213. M. Walsh.. Dulhien. B: “A Thernmsodynamic Correlation for time Minimum Miscibility Pressure in CO Flooding of Petroleum Reservoirs”. mdc % (‘6+ Properties: 7. 261-265 (Nov. 1986). 7. Koch Jr. JPT. Ref.4. F. of 60tln SPE Ann.M: “Prediction of Miscible Flood Performstammce. Acadcuumie Press... Yurkiw.6! Out.77 M=l7i 0. JPT. S. mmmd Morsi. L. Estitmsmmte tine mimsinsnum miscibility pressure.8527 C02 4. Jacobson.M. Christiansen. 14(1). (Sept. Conf.. The oil is to he displaced by unmclisuune. and Gozalpour.60 . Sebastian. The comlmposiliomn of a reservoir oil us given ins the following table. mmuotc % 74. The m’escrvoir oil. A 2 SPE J. 1994).G: “Metlmodology for tIne Slrceificumlion of Solvent Blends for Miscible Enriched-Gas Drives”. Glaso. 19.. described its Exercise 7.Sc.99 2. 0. F: “An Investiguntion of Oil l)ispiulcemsmcnmt by Enriched Gases Usnng a Compositmonush Model arid Its Applicmitionn to Kuirunnj Reservoir”.A: “Effect of Oil Comrmpositions (1mm Miscible-Type Displacement by Carbon Dioxide”.~ Injection 7.90 7. Assunmsinsg lIre reservoir oil behaves as normal decane. JCPT. Stalkup. 268-274 (April. atnd Flock. Kuo. T.. E. Graue. 28. C...M. .61 4. and Zana...’re. SPE Mousograpir Vol. Wi: “Miscible Fltuid Displacement. and Mnchelsenm.. AIME. Jensen.. 219..26 0. Eurg. SPE Res. respectively. and On Jr. 29. Proc. and I-lames. FL: “Miscible Displacemetst”.278 7 (. 1987). 20. C.L: “A Consparative tnvestigumtion of Miuninsmummsm Miscibility Pressure Correlationms for Enhanced Oil Recovery”. 8 (1983). Trans.2. 30.. 1994)..4. Prediction of Miscibility”. 1985). Estinnmunte MMP of the reservoir oul. HA. 25. and Jamrres. Sibbald. Danesh. tue Effect of Dispersion on Composition Paths in Ternary Systems”. In Situ. Fluid Transport unud Pouc Structimre”. and Josendal.

is a drive nseclnannisnn whicls is well recogunised inn the oil recovery. defined as the force exerted at the interface per unit length (mN/nm dyne/cm). A quantitative index of the molecular tension at the interface is tIre interfacial tension (1FF). A tension always exists at the interface of fluid phun. ninny strongly depend on tine interfacial tension [2]. The interfacial tension is very small for near critical mixtures and approaches zero as the critical point is approached. the vmnpour pressure over mn nneniscus inn a pore whiclr is conmcave toward the vapour plnase is snmmallcr than tisat over a flat surface and decreases as the radius of curvature decreases. hnowever.281 8 INTERFACIAL TENSION Stnrface forces affect fluid phase equilibria. It is generally neglected in reservoir engineering studies. Hence the effect of temperature on 1FF depends on the relative position to tlse critical point. where an unsaturated vapour forms condensate in tight pores is a manifestation of tIme above effect. It has been established also timat tIme relative penneahility. wisere the interfacial tension increases with decreasing pressure [22]. The application of (FT depemident relative penunneability un time dynnamimic evaluation of pinase behaviour models will he described in Section 9. Tine evaluation of gas-liquid interfacial tension is of a nnajor interest in gas injection processes where the relative magnitudes of surface.1. winch describes tine mnultiphase flow behaviour its the reservoir rock. becomes only significant in very tight spaces. For a pure compound. Tine variation of guts-oil interfacial tensiomn witis pressure for a nunsber of reservoir fluids is shown in Figure 8. hence. It is a common assumption that the liquid drop out by retrograde condensation in reservoir pores is imnirohile.scs. due to unhuuiumnccd nnnolcculumr attractive and repulsive forces. lmowever. affect the onset of formnration of new plnases and also play a major role ins multiphase flow ins hydrocarbon reservoirs annd in pipelines. An equation describing the reported data is also shown. Surface forces. lmence. Capillary condensation. For a gas . TIme capillary pressure is the concept wlnicln is often used in reservoir studies to consider the effect of surface forces on the fluid distribution within a reservoir. gravitational and viscous forces affect the recovery. Recent studies [3J have imndicated tirat tire condensate recovery by gravity drainage can also be quite significant when the gas-condensate interfacial teunsion is small. It. The gravity drainutge. commtroiled by tIme balance of gravity and surface forces. notm-recoverable unless re-vaporised. tIne tiglmt corners are filled with water and not open to the hydrocarbon. because the rock in majority of gas condensate reservoirs is water wet. The capillary pressure is related to the interfacial tension aurd tlse pore characteristics [II.3. ~.

38488 .39528 .47272 .45134 .40001 .66805 2 .46116 .69450 .63852 .44178 .39178 .40361 .78886 .79 0.88430 .50656 .42344 .46834 Time gas-liquid interfmncial tension at high pressures is conrmnmomnly nmreasured by mm peurdanrt-clrop apparatus.51470 .74 0.84431 .48316 .38946 .39062 .73 0.1 MEASUREMENT METHODS .53322 .30586 .77434 .34195 . The most widely used and reliable methods are described imn tins chsuiplcr.70196 .6 K anmd 23.67990 . Tine pcmrdamnt drop nnetlmod can also be mmpphicd to mrieasunre the interfacial tension of hydrocarbonwater systetns.76864 .2.54193 .42089 .33(86 .31594 . 1.81)375 .41091 .mple 8.33789 .49234 .37256 .34913 .346(11 .40602 .37699 .68230 .2.82859 .42729 . lET measurement by pendant drop issetinod.86719 83471 .3461)4 .84 .37810 . I.35120 .70448 .49860 8.43118 .50818 .59248 .30688 L.3532% .4908(1 .45974 .30483 . as slnown schiennuaticmilly in Figure 8.31394 .481)15 .36280 .696911 0.74639 .42858 . is a function of9~ = d~ ide. arc mulso availmmhle.6775 I .56551 .37367 . deternsinred by relating tine pressure difference across tine interface to tIme insterface curvature.35473 . 20 where.36067 .3439% 33386 .48165 .31086 .37147 .88087 1 9 .9! 0.c 283 condensate.80677 .47420 .74367 .59 MI’a are eqmnaI to 143. Menus renuen! Metlmod.58265 . respectively.87746 .32930 .53494 . .75187 .77148 .56738 .82525 .30891 . is deternmined and related to tIne gas-liqunid innterfmncial tensious 141 by.32588 .40724 .41586 .43249 .387(6 . 5 .38035 .57494 ._pV) (8. IFT is expected to decrease by decreasing temperature.69946 .58852 .33286 .34706 . 1’.67(140 .90 0.7 .35960 .82 0.77722 .53150 .81594 . controlled by the halmmrmcc of gravity and stmrface forces.41214 .57304 .30790 .53668 .472 nmm.7(465 .61701 .98 0.81903 .60051 .85 0.41462 .78301 . where tine opposite is expected for an oil sample.48620 .40481 .36928 .51800 . MPa 0.32849 .55446 .37922 .600 and d =O. or the maximum horizontal diameter of tine drop and d~ is the diameter of tIme drop measured at tine imeighnt d~above the bottom of the drop.282 8.73028 ..75 0. lnierfacial Tension 8.44044 0.43910 .41963 .72 t).74912 .860(. The vapour-hiqunid inmterfacial tension of a methane-normal decane mixture is measured by nIne pendausl drop method.53842 .87407 .62764 .66107 . ~=~~(pi.54017 .42472 .92 0.45551 . Prediction metlmods.48926 .32887 .72241 .41338 .31793 .6921(4 .687 IS .6(1458 .65192 .47568 .55084 .62123 .72764 .31 94 .49390 .65419 .37477 .48468 . 9~.52133 .uau. .8 I Time interfacial tensions between fluid phases at reservoir and surfuuce comrditmonns mire nmneasunred by various tcchmmiquues.61912 .44449 . vs.39764 .35749 .37037 .72502 .46980 .39882 .44585 .47865 .32092 .97 0. Tuihunlated vaimnes of (‘. The gas and liquid densities at the test conditions of 377.33890 .93 0. reported by several investigators [4.35641 .63414 .94 .76 Rcpruxliuccd .75463 .36387 .67276 .675 13 .5].40846 .38374 .099* in Values of time dmot slnmll)c functor I’ [5~.95 0.32191 .59849 .5230(1 .44313 .54725 .38147 .45691 . respectively. a liquid droplet is allowed 10 hang frommi the lip of a cumpillaty tube in a Inugh pressure visual cell filled with its eqtmilihraled vapour.64295 .66338 4 .80981 .46690 .40241 .34296 .58656 Copyrighi 0.70700 0 .89122 .77 .45832 .80074 .56179 .63632 .80 ((.41837 .58460 .7918(1 .31294 .55811 .55994 .52638 .47716 .50950 .34809 . Calculate the interfacial tensions when the liqunid droplet dimensions are deO.51966 .76299 .33487 .86 0.79477 .!.38831 .57114 .51306 .3t694 .88 0.2.87 .36711 .srF from 1221 wiih permission.83790 .43644 . g is the acceleration due to gravity and pL and pV are the liquid and vapour phase (mass) densities. as shown inn Figure 8.50176 .44858 . rube 0. witln mm acceptable engiunecriumg mmcctmrmmcy.31494 .52213 .58071 .99 1.70 0 0 10 20 30 40 50 Pressure. In this technique. Variations of interfacnal tension of gas-oil witim pressure .45272 .31093.43380 .49546 .71208 .70379 lip 0.73828 . (lie drop shape factor.68959 .61282 .1) Figuure 8.62551) .35016 .90(74 .36173 .55628 .85407 .5281(8 .73560 .46401 .61491 . are given in Table 8.31992 30992 .7i1 .39411 .76019 .76581 .46258 . I is C tO (-0 03417Rt’) IFT= 9.435 12 .88775 .57686 .00 .85716 . I t) . 59447 .65876 .4t512t .59648.87069 . .69 0.36819 .35224 .47126 .51)018 .37588 . The shumpe of liquid droplet at static comnditiotss.78011 .70954 .75740 .60662 .59050 .83 ((.64741 0. !muisle 8.61075 .44996 .36603 .39294 .42600 .54547 .34093 .44721 .61)868 .55264 .66571 .32986 .89822 8(.50336 .56926 .36495 .54904 .63196 .51634 .83154 .52469 .74097 .33688 .54371) .78 0.39646 .57878 .1.5 .56364 .33991 .71981 .64073 .49702 .7! 0.6(1254 .46545 .62980 .68472 .32290 .38260 .51142 .41711 .5297% .42216 .32787 .5 and 544.35854 .62336 .79774 .65647 .645)8 .31893 . where d~ i~ time equatorial diamnmcler.71722 .7 kg/mu.73293 .32688 .81287 .48772 .35338 .96 0.4(1968 .42988 .38602 .64966 Figure 8.84110 .84755 .89 0.45411 .8947t .85080 .50496 0.78593 .43777 .33587 .

The interface between the phases is curved due to surface forces. h F2y(1_smno)12 L (8.(8.3. Gas-liquid interface curvature near the wall of a flat window. At static conditions. inowever. 2 c~9.4) known ins time Macleod-Sugden equation.284 Solution: 8 !uuIu’tfucn~nlTe. Hence. by vmnrious .l) results in.2) (pL~pV)gj . Tine relatiomr between lET and. as depicted in Figure 8. respectively. Tire thicknness of time hand increases with 1FF as the curvature becomes more pronounced at lower pressures. requires experimentally detennined paranmeters for all the conmponents and their bimmaries. followed by the scaling law relying on the corresponding states principle. usiung Eq. Laser light scattering techniques have been used 16.002399 N/m a=2.5)/0. um. down to values of the order of l0~mN/rn. as.3) The measurement of liquid rise on the equulibriutn call window provides accurate interfacial tension data with almost no extra effort during conventional PVT tests. Because of its elaboration and lack of immmproved resunlts relative to other mnethiods. due to light scattering. This approach.1. density has been extended to nmnulticonnpomnemnt systems successfully. is a more practical arrangement. as a tlnird pInase with properties varying between those al the hulk of tine two pinases. 1.787. Hence Eq.001 mN/rn).4 mN/rn At very low IFT values. it has not received nnuch attention in the industry.3. determining very low interfmmcial tension values (0. ~y=(pi. Although the methods rely on some timeoretical foundations.7.4) Figure 8. known as the panwIuor. is the contact angle. Time use of a thin wire. where the interfacial tension is close to zero. wirere 0. for tire drop to hmnog from its tip. Figure 8. The vapour-liquid interfacial tension of pure compounds has been related to various fluid properties. a shape factor of ~=0. It can be applied successfully to measure low IFI’. tIre pendant drop msrcthmod mummy not he applicable. 8.0006) x(544. and nray be assumed zero at low interfacial tension as the liquid completely wets the window (9]._pV)ghl/2 (8. The msietlnod has hecmr successfully applied to binary systenrs [13].~uid Film Parachor Method Lmqu Meniscus It was first reported by Macleod [9].5905=0. resulting in a number of practical and widely used metimod. Low interfacial tension values have been detertmiincd successfully by nneasurinrg the gas-liquid interface curvature in an equilibriunn cell (8(. mmppears as a hand with a finite thickness between the phases. It is considered to have a unique value for each consrpotmnd immdepcndent of pressure and temperature.uuuennen: Alei/uods 285 For a calculated value of ~R=0. Mea. in 1 gmnol/cmn and ~ is in mN/m. Tine parachor values of various pure connpounmds lsave been determined from measured innterfacial tension data. The interface curvature in a visual.u.o.I 43. under the ttube. has been extensively addressed by 0 Stmgdcn( 14]. compressibility [Ill and latent heat of vaporisation [I 2J. P . the interface curvature can be related to the surface and gravity forces. instead of the tube. This behaviour is indeed omse of time sources of error in determining phase volumes in equilibrium cells by measuring iluid interfaces and assuming them flat. is given by: wimere p~ and p~ are the molar density of the liquid and vapour phase. It.600=0. where the interface between the vapour and liquid loses its definition. The two mnsost widely used nmsetlmods of predictinmg the interfacial tension in time petroleum industry are the paracinor metlmod. equilibrium cell.ses equihibriunmi timermodynatsnic concepts by employing an equation of sonIc to cmdctmlmute tire required properties from volunmictric datum. the hanging liquid drop becomes very snmsall. or windowed. (8. requiriumg a very nnarrow tube to remain stable. lime proportionmuulily coumstmmnt. At conditiomms close to linc critical point.s ins the oil mnnd gas industry.3.472/0. such as tine density (10].8 I x(0.n 8.2 PREDICTION OF INTERFACIAL TENSION The interfacial tension between reservoir fluids can be predicted by several methods. Window Gas id Phase — Band L~~L. resulting in differential equations which can be readily evaluated with the hotmndmury conditions depending on the geometry of the equilibrium cell [81. as mm pmmrmmnmmeter representing the molecular volummne of a connnpound under connditions where tIne effect of temumperature is neutrahised. they require experimentally determined paratneters. reported by several investigators amsd reviewed l)y Ali 1151. Ans interesting approach is to counsider the interface.71 to Ineasture tire propagations of tlscrmmmunlly excited capillary waves at the vapour-liquid interface.investigators. The rise of liquid on a limit window.m.5905 is read from Table 8.(8. tlmat the vapour-liquid interfacial tension of a pure connmpoumnd is related to the density difference between time phases. h. known as the gradient timeory of inimonsrogemmeous fluid.

2.9 225.=0.9 3.91125xl6.(m) (P 01 4’ ~ (8.414 3. (22] detem’unmined parmucinors for crunde oil frmnctions of various molecular weights annd proposed the following equnationn.u Parachor values of homologous lsydrocarhons slsow an alnnost limmear relmmtiomsslnip willn tIne molecular weight [16-17]. Tine paraclsor value of a componsent in a mixture is the sausne as that wlsen puure.(8.822 “The given value is for ninrogen in hydrocarbon misiurcs.7 3. Parachor and ~ values of pure conmnpoummds.8) = ~~z~z~P . . sucin as the denrsity. Lnaiuuple 8.3 3.fneia! le.ireuf~meiolieuu.6 K is 23.5 3. v~ 0 3 where the critical temperature T~ is in K and the critical volumme v~ is in cmTn /gunsol.2. has been extended to mlmixtures by incorporating various mixing rules.5447 methane unmole fraction 0.99+2.4).4x 142.641 nCt2 514.0 433.681 ‘lIne rclmntiouu hetweenr tIne pmnrunchor mmmd line mnnolecuiar weigtmt of imydrocarbon groups.M.687 3. (8.324T.0 3. 5 Table 8. Eq.used ins petroleutsu indiustu’y.748* 3. P~jjis the average 1 pusrachor of commnponmeumt i aund j.726 It 312. 01 where z is the insole fuactiomn of connnponment i in tine hiqunid or vapour phase. Weinaug and Katz 119] proposed simple tnrolar uuvermuging for lime parachor. The exceptiomn is tlsmit ut nutrogen in reservoir fluids. Ilugill and van Welsenes 1201 proposed a quadratic nssixing rule for estimationi of tIme pimase parachor.0 150.59 MPa. A reservoir oil tsmns beeun umnodelled by a mnnixtuure of Cl and nC~~ (60-40 nnole%). to he used in Fq.(8.i. I? 4 P =0.0 3. 1 respectively. aronsratics and cyclic compotunnds in various SCN grotups are not tine suutnme. Firoozahadi et al.(8.695 3.3.5 351.0 3.286 8 1. ‘rIse ratio of paraffins.5).7) The insterfacial tenrsion describes lIne nature of nnolecular forces at the interface.815 nCt3 555.uion 287 (8.505 3.(8.25 . Preducu:oiu of Inlr.795 nCl6 676.043-t-0 Oh 75xI42.6x16 043 u-0.1435 0. is conssiden’cd to deviate signilncanlly from linearity 121.5) 8. = iC4 nC4 (‘5 181. A relation for the parachor of pure norunsmsl paraffiuns is ums follows.2 3.6000 0.23M - 0.8 3. P =21.0022M 2 (8. as given in Table 8. nC8 nC9 nuCtO 393. (.9825 Esniunianc tIme gas-oil uuutcrfmucitut lcussnomn at mIsc above conditions. This trennd simouuld Ire expected mis tine pmnraclsor-nsmolccular weiglst relation varies for various hydrocarbon houmnologuues.221.865 3.4 mssN/m.892M 0 Parachor correlations in terms of critical properties Irave also heeur pumblisired 1181. ‘lIne unsiutar dennsuty of tsunt Is plumuse.409 The sinimple nmsolar unvermiging as proposed by Weinatug and Katz. are as follows: t’luasc Oil Gas density.872 nCl4 595.m 01 wIrere x and y~are time insole fractions of counnpommeusl i ins the hiqunid amid v:ulsouir pinmuse.4 3.1 3.8).cjo. Paracisors of a number of pure compounds. whereas the density or tIne mnolecumlar weighmt are hulk properties.682* -11.18).9) where C~is a temnlperunturc dcpcnndent interaction paraurseter.5 271.0 4t.=0. Tine unicasuured valunc is 2. It is advisable to determine it experimentally. ~ ~ =~P (x p~—yp~) 1 (11.0.285=l 8. Eq. determined experimentally using lET dmuta our binary nrixtuures. is time nsmethod widely u.10) nCS nC6 nC7 231.(8.820 nCtS 636. The values for compounds heavier than nC have been estimnated frousm Eq.630 3.c mire calculated as M’ =~xM. P~is the paracinor of counponent i.285=66.5 3. In general all prediction methods which relmntc lET to sommne huulk properties. The properties of the oil phase at the mubove coimdilionns and its equilibrated gas. The Macleod-Sugden equation.5 189. mire given ins Fable 8. 5/cuss’ 0.2 1191. The nunixture bubble poinst pressure mit 377.0’ 77.54 g/gmoh g/gnsmoh 0 M =Zy. * Calculated values from Eq.4 -i. using tIne parachor nsicthod.4). = ~- (8.597* 3. are not reliable for nnixtumres with component distribution at tIme interface different than tisat of the hulk.852 simounkl be noted tlsmml genserahised correlations are nsot expected to provide a reliable parachor vmmlue for time oil imeavy eurd. winicls geuserally contaimss a highs concentration of asphaltic and surfmmce active mrmaterials.‘ouuuponenl Paraclnor t value (‘02 N2 78. Cl C2 (‘3 108. The value for pure nitrogen is 60.Soluuimo.2.2. resulting in a nonm-hinear relation. such as siunglc cmmrhxnnn ntununbcn’ grnntnps.855 nCtl 474.

~=0.008I86 gmol/cm m ~=0.007862 gmol/cun’

8. Iuurerfaeial Tu’rn.cjoui

8.2. Predicsio,n ofhuferfneial Ten.ciouu


where ~ and~ mire tIne nnohardemnsities of the liquid and vapour phases, respectively, and the exponent (dO) is equal to (45/I76)=(l/3.9l11). The coefficient P~ is equivalent to the parachor in Eq.(8.4) and is given by. P =A~ 0 45~76 v~/ ~ (8.17)

The parachor values are read from Table 8.2 and used in Eq.(8.7) to calculmute lET.


0081 86-0.9825x0.007862)+ 433.5(0.4x0.008 186-0.01 75x0.007862)

a=I.708 mN/m Corresponding States Correlation (Scaling Law) According to the corresponding states principle, Sections 1.2, fluids lrelnmuvc siummilmtrly wiucnm scaled properly relative to their critical points. For a pure fluid, time vapotur-hiqunid imslerfacial tension decreases with increasing temperature and heconmmes zero at tine critical point. hence tine following scaling can be considered, IT (I

wlnere v, is the minurlmur critical voluunsse and time value of ~ is estiminated from IF!’ data ots piure comrnpounnmds, as givens mum l’mihle 8.2. It Inns been rclmnted also to the critical conmsprcssihihity functor, mis 1251.

1.854426 ,~-it.524lt2




almInougln tine correlmstiuun does mmml midcqtuumtely nnuitcis lIme reported valn.nes. For nsni5turcs, unnolar avermugi ung us used to calculate vmu lues I~ c I’c’ ‘I’ c’ v C amnd ~, for cutch phmnse to deternnni ne its pmnraclmor froism Eq.(8. 17). The immterfacial tension is Linen calculaled from Eq.(8. 16).

where T, is the reduced temperature and the exponent 0 may he estimmnated experinsnenntally or theoretically.
213 3 Brock and Bird [231 incorporated the dimensionless interfmscial tensions grornp of c~I(P~ Tc” ) in the above scaling, adopted theempirical exponent value of 0=11/9 reported by (Iuggenheinn [241 and proposed,

Comparison of Predictive Methods An examinatiour of time above two methods revemmis timmst they are basically the sanme. Both unse experinsnenrtmnlhy deterumnined paraclmor coefficients, directly in the former and indirectly related to tine criticuil property by ~, in tine latter. Usinng a function relmiting the parunchor to critical properties. suds mis Fq.(8.6), ins line first method, will make the two even more sinnilar. The first nmnetlnocl, however, applies nmmixing rules directly to calculate the mixture parachor, wimereas tine pseudo mixture properties are initially calculated in the scaling law to determine the mixtunre parachor. The main difference is the value of exponent inn tine 1FF-density difference relation. This, Inowever, does not himil any of lire two methods to specific exponent values. Hough and Stegenneier [27] proposed an eqn.uation similar to Eq.(8.4), but with an exponent of 1/3.67, deteumnineil using lET dumlum of propmune and butane in tine critical region. It has been shown [6) tisat tire ilough-Stegeummeicrequmulion is nmore accurate at low interfacial tension conditions ( < 0.05 usrN/nn). ‘[he IF!’ density difference relmitiour can be generahised as,
vv (T/m = (P,~’p~I~ ~1 where i~ inas beens uussunmsmed to he constunmst in time above methods.


Ac (1 - Tr)’ 1/9

(8. 12)


where, (0.1 32f~~ - 0.279) (P c 2/3 Tc t/3~ I (8.13)

I~c is the slope of the reduced vapour pressure curve, plotted vs. tIme reduced tenmmperature, at tine critical point and can be estimated from, ~

(1— T~ /T~)



where Tb is the boiling point of the substance at lime atinmosphmeric pressure P. . 1 Eq.(8.I2), developed for pure fluids, cannot be used for inmixtures as time conmmhx)sition of vapour and liquid changes with pressure and temperature. Lee and Chien [251 replaced the temperature scale with the liquid-vapour density difference,, as it also vanishes at the critical point, (pL pV) (T~ ~T)E (8.15)


Figmnme 8.4 shows IFI’ of a Nou’tim Sea gas. condcnrsate measured during several tests, including tine coumstmtunt connposition expansion, constammt volunne depletion and methane cycling at 383 K. All the unmeasured points follow time same trend when plotted against the liquid-gas density difference. The relation is linear on the logarithmic plot, but the slope clearly changes around IFT= I mN/rn. Tine change of slope for other systems has been reported also by other investigators 128]. Tine deviation of predicted lET by the Weinaug and Katz correlation from experimental data on seven hydrocarbon binary systems, including 213 data points, is shown in Figure 8.5 [29]. Note that the nmetimod generally uumder predicts at low lET conditions, whilst it over predicts at

They assumed e=~/I6as theoretically determined by Fisher [26] and proposed,


~vv ~ PM)


higln lET conditions, tine unost accurate results around IFT=I mN/m. A sinmilar trend was also observed for the with Lee-Chico method [29).

z 290
8 I,iii’ii~ic,alI(~i.(lOII 8.2. I’redieuio,u of hue ufaeia! Tepi.uio,i


!‘inc above muno(Iilications reduced tIme average absolute deviation from 23% to 14%, wlnen tested against 65 data points on tnulticonumponent model fluids. A similar improvement was also observed for real reservoir fluids iumcluding gas condensate and oil samples [30]. Schechler and Guo conducted us comprehensive survey [16] of reported 1FF and density data and clearly demonstrated tlnat time optinnunss value of E, particularly for hydrocarbon systems at low lET conditions, is less tinaum 4. Based on experimental data and molecular models, the authors concluded that a sinsgle conmstant value of E=3.88 in Eq.(8.19) should suffice to predict IF!’ witluinm ml range wimere tIne critical point scahinng is applicable, that is less than I mN/m.



~P ,(xp~, 0 1

y p~) 1


As clummnsginmg tIme vmultnc of exlmonsennt rcsunlts mr clnminnge of lIme parachors, lhney calculated approprimnle parunclnors for a large mnununhcr of punre connpomnnds, using experimcnntal lET data. I’lmeir cuilcuuluiied vmulumes mire giveun ins the plnysicunl properly table, ‘l’ahhc A. I, in Appendix A. ihe it lain s unhso k’vekm x’uI I inncmnr com reluntionss betweu’ur tine parmmchor and nsnolectnhnr weight for 1 vminious inydrocunrhonr isonnsologumu’s. lime correlation for alkanes is as follows,
I)cnsniy l)illcrcnce, g/cuuu3

l’~=l l.73+2.9871M


Figure 8.4. Measured gas-condensate 1Ff of a North Sea reservoir fluid mit 383 K.

A linear rclmstiomr between puiracimor vunlues and nnolecular weigirt was also suggested for all types of hydrocarbons, witim a deviation of 22%. as follows: P =3.72+2.95l9M 5 ‘lIme above correlatiour ntay he mused to estimate parunchor values for SCN groups. (8.23)

S V S. V 0. C 0

!~~oniph’ 8.3.

Predict tine gas-liquid IF!’ of tlse ntmixture described inn Example 8.2. using the Lee—Chienm n,nd Sclsumclsicr—Gnno mmci Imods.


Suuhuuine,,u: L.ee-Chien Method

TIne counmponent criticuil properties are read fronn Tumble A.l in Appendix A. The values of ft for each coussponennt is calcumlated using Eq.(8.I4),

01 .1 iO 01)

ft ,-I330947

3 ,ç~


tvr, nuN~m
Fugunre 8.5. Deviations of preducted IFT by the Weinaug-Katz mumetlmod for binary nmnixtuu’es. Botls correlmntions cmuo he imsmproved by nmmiking tine IF!’ expomsenit, l/E, a functions of mIne liquid— vapomur deursiny difference 129]. The optiurrised value for tIme Weinsaung-Katz cuimrelation was determined by regressung E to ummiuninmuise the devimstions of tine predicted hinsmmny results mis, E=3.583 + 0.I6(~-p~) (8.20)

Vunlues of ~ for nnuethmmne and nsornnsal decane are read from Table 8.2, equal to 3.409 and 3.855, respectively. TIme values of v,. T,, P,, ft anscl

of each phase are calculated by molar averaging and siubstitunted in Eq.(8. I .1) muusd Emq.(S. 17) to determine A, and P,, , respectively.
l5uaw v, cuuu’/guuuot


‘I. K

I’,, Mt’s





3.6034 4.5554



A,, mN/rn 28.2673


195.970 64.104


3 wisere p us mn gmol/cmn . The contribution of time second terism imr the above correlation is 51 in most cases, resulting in a constant exponent in practice. negligible

Suihstuniting tIne mnlmovc values of t’~ aund nmnol mur dcnmsities, calculated in Example 8.2, in Eq.(8.l6). we obtunin,


8. Inierfacia! Tension

8.3. Water.flvdrocarbon iumteufacia! Tension


l95.970x0.008l86-64.IO4x0.OO7862~l.10024 Connprehensive data omr multiconnponent hydrocarbons-water, particularly real reservoir fluids are scarce. For reservoir gases, time trend is very nsuch similar to that of methane, Figure 8.6. witim tine presence of heavier connpounds in the gas reducing 1FF. The effect of pressure on oilwmuter IF!’ is mininnmul above tine oil htnbhle point. The reduction of pressure below the oil bubble point generally reduces tIme oil-water lET due to release of gas out of the liquid nmixture. The oil-water interfacial tension is expected to decrease with increasing tenmnperature, but resmnlts contrary to that at some conditions have alsobeen reported [35).

a=l.453 mN/rn

Schechter-Guo Method The parachor values for methane and normal decane are read from Table A.I, equnal to 74.05 and 440.69, respectively, and substituted in Eq.(8.7), but with the lET exponent of (1/3.88), ~‘>=74.05(0.6x0.008 I 86-0.9825x0.007862)÷ 440.69(0.4x0.008 186-0.01 75x0.007862) a=l .864 mN/rn

a z






The interfaciai tension of pure hydrocarbon-water has been measured over wide ranges of temperature and pressure by various investigators [31-36]. ihe reported data often show substantial discrepancies as reviewed by Firoozahadi and Ramey [37]. The variation of methane-water IFT with pressure and temperature is shown in Figunre 8.6. ‘fhe imsterfacial tension decreases with increasing pressure andlor temperature over the tested regiomn.








Pressure, MPa

Figmnmc 8.7. Water-tn-octane inmerfacial. Pcmroteurn
wimtu joeruuuissi In.

Suucicmy umi Cuiunatla

Copyrighu. Rcprixiunced



E z E

Altlnough paraciror values, about 52 [25, 38), have been reported for water, time use of vapomnrliquid correlations, Eqs.(8.7) and (8.16), to estimate lET of hydrocarbon-water is not recomnsmend. Timese correlations can pn’oduce higlnly erroneomns results, even for sinsrple binary systeunns [371.

Estiusmale the interfmmcial tension between tIme gas inn Exanmuphe 8.2 anmd water.

Connsidering that the gas is predominantly composed of methane, Figure 8.6 may be mused to estinnuate gmns-wmmter lET (~,=43mN/nnn







377.6 K and 23.59 MPa.

Pressure. MPa Figure 8.6. Methane-water interfacial tension. SPE Copyright. Reproduced from 1351
with permission.

Figure 8.7 shows the variation of n-octane-water lFl’, witlm pressure and tensnperature [36]. The interfacial tension decreases with increasing temmnperature. Ann iurcremise in pressure, however, increases lET, but the effect is small. Tirere are reports sinowing sliglnt redmuction of IF!’ by increasing pressure [33], contrary to that in Figure 8.7. Tine effect of pressure on lET of pure liquid hydrocarbon-water is generally small and can be neglected in most cases.

Firoozabadi and Ramey [371 denmonstraled that IF!’ between water and pure hydrocarbons. over a wide range of temperature-pressure, can be described by a single plot shown in Figure 8.8. Tire 1Ff frunctioms is as follows: II’ I I’u.uinctnonm


li2S t,~u,W“(p

. ‘.5 03125 P S )j( .1/It



(ml frrfacial


8.3 tVoiu’r-Flwlroearbo,n /,ute,J’acial Tensio,u


where, ahW is in mN/rn, pW ~ ph are the water and hydrocarbons phase deunsity its g/cnnn , respectively, mmd T h ns the hydrocarbon pinase critical temperature. 1 The reliability of correlation was demonstrated for various compoumnds ranmging fronn nnethanme to n-dodecane. The plot can be represented almost by the following eqmuatiois. (8.24) whicin is also shown in Figure 8.8.


Neglecting the solumbility of Imydrocuirbon in waler, tIme water density at 377.6 K and 23.59 MPa can he estimated from Eq.(2.88), as in Example 2.15. AV,,~.0.0057RI p~=l.040 g/cnn’ i\V~ =0.046034 0 t3,,=l.03999

Tmnkinng the uniolar averuige critical tenssperature of mime hydrocarbon vapour and Iuqnnnd pluunses as calcuulmstcd un Exausiphc 4.3, neglecting the solubility of water in hydrocarbon pliumses aund using I:q.(8.24), tIme interfacual tension us calculated.

. -. .--. =.., ... ... . .1 . -







‘F,. K


1FF, nuN/rn








198,04 361.42

1.9070 1.0448

44 51

. . . -. ‘ . - — ‘

TIne interfuicial teunsions hetweenm the hydrocarbons liquid phase and water is expected to be lower nlnan tlnat of tine Vuiponir plumuse, cuuuntrary to the above calcnulated values. Using the original plot mu Figure 8.8. unsiead of Eq.(8.24), results ins a calculated vapour-water imuterfacimil temssion of 49 nurN/m.

. -..;.

Equiauion 8.24
— .

. . .



-. .

. .

1 I




- J. . - .


I. Itmim’duumn, C. amid I .uunsgcmoun. I ).(: ‘‘Imnt’luuenncc (it Very I_ow Imnterfacnal Tenmsnon on Relatnvc l’ernunemubility”, SPEJ.. 391-401 (Oct., 1980). 2 D munesin A Kruuius D lhcnsderson G D ansd Peden J M Vnsuah Investugatton of Retrograde Pirenousmenron and Gmms Comndensate Flow in Porous Media”, 5th European
Synmsposiuusu on Improved Oil Recovery. Budapest (1988).


. -






- .-





‘1 Andreis J M 11 truser E A ‘md Tucker W B Boundary Tension by Pendant Drops I’rcsensled ‘ml time SOtIm (olloid Sympociuns Cannhrudge Massaclsmnsetts (June 1918)

~ 0.2
0.4 0.6 0.5


I .0

Densumy Dufference, g/cisr Eugmure 8.8. Generahmsed correlation for wunter-Imydrocarhon nnterfmucual lemsslon of Canada Copyrigini. Reproduced fruin 371 WIl ti peru ussioni

4. Niedcrlnmiuser, 1)0. mnnsd llmumtcll, FE: “A Conected Table for Calculatiour of Boundary Tennsions by Pendmrnst t)rop Metlmod”. Researcim onm Occurrence and Recovery of Petroleum, A ConnIrihuutionr frourn API Researcin Project 27, 114-146 (Mar., 1947).

5. lIaniff, M.S. uunsd Pearce, A.J: “Measuring Interfacial Tension in a Methane - Propane (imns-Corudensmsle Systeun tJsimng mi Lumser Light Scattering Technique”, SPE Res.Eng. 589-594 (~ , I 990) 6. l)orsinow RB: “TIne Siumunltmimseouns Measuretneunt of Interfuiciai Teursion and Oil Viscosity for Prumdhoe Bay Fluids by Surface Laser Light Scattering Spectroscopy” SPE 22633, Proc. of 66tln Ann. Conf. (Oct., 1991).
mit Resem-voir Comsdiliours

The mshove correlmituon was evalmnated for estimating the oil-wmnter IF!’. wisicis uusdicmnted ern’ors exceedumsg 30% (37]. The presence of surface active connpommnds iii oil nsay proisuhut tlse use of ammy generalised correlation wlnicim does nsot take smucts effects into mmccount. Wiseur tine 1Ff value at a siurgle point, often at the atmospheric conditiomss, is known, mm parallel crmrve to Ilsunt in Fmgumre 8.8 may be used to estinniate 1Ff at other pressure-teurspermltuure vmtlues 1371. The presence of salts in water may alter its unterfacnal tension with oil shugintly at typical reservoir conditions. TIne 1Ff may decrease [39), or incremsse (40) by uncreasing the salt concentration according to various reported data.
E.mauuuple 8.5.

7. Pauresls, A , Todd, A.C , Sonsnerville, J. and Dandekar, A: “Direct Measurement of Innterfmuciai Tension, Density, Voluunsne, and Consnpositions of Gas-Condensate System”, l’rans. tChensnE, 68, Pant A. 325-330 (July, 1990). 8. Cmnhn, 3 W “Cu’iticah Point Wettinrg”, The 3. Chem. Physics, 66, No. 8, 3667-3672, (April, 1977). 9. MacLeod, D.B: “0mm a Relation Between Smnrface Tension, Density”, Trans. Faraday

Estiunnate tine oil-water and gas-water interfacial teunsion for fluids described mu Exununuple 8.2, using the generalised hydrocarbon water correlatioun.

Soc., 19, 38-43 (1923).


8. Funfrufa’niF Te,n.ciinn

8 5. Erern’i,ses


hO. Mayer, SW: “A Molecular Paraisreter Rclaliomsslnip belweenr Surfmmcc ‘hemmsionm mmnd Liquid
Compressibility”, J. Phys. Chem., 67, 2160-2164 (1963). 11. Sivaraman, A., Ziga, J. and Kobayashi, R: “Correlations for Prediction of lnterfmmcial Tensions of Pure Alkane, Napthenic and Aromatic Compounds between their Freezing and Critical Points”, J. Fluid Phase Equilibria, 18, 225-235 (1984). 12. Carey. B.S., Scriven, L.E. and Davis, U.T: “Semiempirical Theory of Smurface Tensionm of Binary Systems”. AIChE, 26, No. 5, 705-711 (Sept., 1980). 13. Carey, B.S.. Scriven, L.E. and Davis, H.T: “Semiempirical Theory of Surface Tension of Binary Systems”, AIChE, 26, No. 5,705-711 (Sept., 1980). 14. Sugden, Sr “The Parachors and Valency (Romntledge, 1930); A List of Pmnrumchors”, Brit. Assoc. Report (1932).
15. Ali, 3K: “Predictions of Parachors and Petroleum Cuts anti Pseudocommmpomrents”, J. Fluid Phase Equilibria, 95. 383-398 (1994).


llunygens, R.J.M., Ronsdc, II. and ilagoort, J: “Interfacial Tension of Nitrogen and

Voluntile Oil Systems”, SPE 26643, Proc. of 68th Annr. Conf. (Oct., 1993). 29. Dmmnesh, A., Dmmnmdekar, A.. Todd, AC. and Sarkar, R: “A Modified Scaling Law and Paraclnor Method Approach for lnmmproved Prediction of Interfacial Tension of Gas-condensate Systems”, SPE 22710, Proc. of 66th Ann. Conf. (Oct., 1991). 30. Dandekar, A: “Interfacial Tension and Viscosity of Reservoir Fluids”, PhD Thesis, Heriot-Watt Unniversity, Ediumburgim, Scotlammd (1994). 3 I. Elomnglm, E.W., Rzursa, M.S. and Wood, B.B: “Interfacial Tennsion at Reservoir Pressures and Tennperatures, Apparatus and tine W~ter-MethaneSystem”, Trans. AIME, 192, 57-60 (1951). 32. Micinmmcles, A.S. mmnsd llmumuser. E.A: “lnmterfmmcial Tension at Elevated Pressinre and Ieuumpermmtmmm’es II”, J. I’hys. ( ‘hncnnm.,55, 408—421(1951). 33. Ilmrssans. ME., Nielsour, RE.. Callnomun, iC: “Effect of Pressure and l’ennperatmure on Oil-Wmmter hnmterfacimul Teumsiours for mu series of llydrocmmrhons”, Trans. AIME, 198, 299-306 (1953). 34. Jennings Jr., 1I.Y: “TIne Effect of Tenniperature mind Pressure on Interfacial l’ension of Benzene-Water and Nominal Decane-Water”, J. Colloid & Interface Sci., 24, 323-329 (1967). 35. Jennings. lI.Y. arid Newnnan, Gil: “The Effect of Temperature and Pressunre on tine Interfacial Tension of Wunter Aguuinnst Metlnaune-Normmral Decane Mixtures”, SPE J., 171-175 (Jmmnse, 1971). 36. McCmuffery, F.G: “Measmnrenmnent of Interfacial Teissions and Contact Angles at Iligln ‘l’eunnperature and Pressmure”, JCPT, 26-32 (July-Sept., 1972). at 37. Firoozahadi. A. anal Rannney Jr., H.J: “Surface Tension of Water-Hydrocarbon Systenos Reservoir Conditions”, JCPT, 27, 41-48 (May-June, 1988). 38. ilmnkinm, D.l., Steinberg. D. ammd Stiel, LI: “Geuserahised Relationship for time Surface ‘l’ennsion of Polar Fimnids”, lnd. Eng. Cheun. Fund., 10, 174-175 (1971). 39. Bmtrtell, F.E. mmmd Niederhmmmnser, DO: “Film-Fornning Constituents of Crude Petroleum Oils, Fmnndaunenlmul Researclr on Occmnrunnmce and Recovery of Petrolemntin. 1946-1947”, API. Marylmmnd (1949). 41). Aveymnrd, R. ammd I Imuydomm. D.A: “iimennsodynannic Properties of Alipinmmtnclnydrocmmrhonm— Wmuter lustcrfmnces”. ‘Frmmns. Farmudmmy Soc., (ml, 2255-2261 (1965). 8.5 EXERCISES

16. Schechter, D.S. and Guo, B: “Paracisors Based on Modern Plrysics mmmd Their ttses inn LET Prediction of Reservoir Fluids”, SPE 30785 Proc. of Ann. Commf., l)mtllmms, USA (Oct.. 1995). 17. Baker, 0. and Swerdloff, W: “Calculation of Surface Tensions. 3: Calculunlion of Surface Tension Parachor Values”, Oil and Gas Journal, 53,87(1955). 18. Fanchi, J.R: “Calculation of Parchors for Compositional Sinnulation, Aim Update”, SPE RES.ENG., 433-436 (Aug., 1990). 19. Weinaug. C.F. and Katz, D.L: “Surface Tension of Metirane EC, 239-246 (1943).

Propane Mixtures”, I &

20. Hugill, J.A. and Welsenes, Van, A.J: “Surface Tension: A Simple Correlationn for Natural Gas + Condensate Systems”, 3. Fluid Phase Equilibria, 29, 383-390(1986). 21. Ahmed, T: “Hydrocarbon Phase Behaviour”, Grulf Publishning Conimpany (1989).

22. Firoozabadi, A., Katz, DL., Soroosh, 11. and Sajjadian, VA: “Surface Tension of Reservoir Crude Oil/Gas Systems Recognising time Asphalt in the Heavy Fraction”, SPE Res. Eng., 265-272 (Feb., 1988). 23. Brock, J.R. and Bird, RB: “Surface Tension ansd the Principle of (‘orrespoirding States”, AIChE, 1, 174-177 (1955). 24. Guggenheim, E.A: “Thermodynamics”, 3rd Ed., North-Holland Pub. Co., Anuisterdam (1957). 25. Lee, S.T. and Clnien, M.C.l-l: “A New Multiconsnponent Surfmuce Tensionn Correlation Based on Scaling Theory”, SPE/DOE 12643, EOR Synmmposiummr. Tmmlsmn (1984). 26. Fisher, M.E. and Scesney, P.E: “Visibility of Critical Exponeunt Remrornnalization”, Physics Review A, 2, 825-835 (1970). 27. 1-lough, E.W. and Stegemeier, G.L: “Correlation of Surface and Interfacial Tension of Light Hydrocarbons in the Critical Region”, SPE 3., 259-263 (Dec., 1961).

8.1 . The gas-liquid inrterfmucimuh temnsion of nmsetlnane-non’unmal hmmtane nmnxture at 311 K and I 2.07 MPmm is mmicasured by tine peurdant drop usnethod. Calculate the interfacial tennsion wlmen the droplet dimnenmsions mire d~=0.228 and d =0.325 mnn. 5 8.2. Tire vapomnr-Iiqumid equilibriumnn dunta of a five-component gas condensate usmnxtmnre at 353.1 K ins a constammt conmnpositiour expamnsion test are given in the following tables. Conmrpare tine ummeumsmnred IF1’ values with those predicted by the original Weinmaug-Kali. nnetimod annd its modifications Eq.(8.21) by Scheclnter-Guo and Eq.(8.20), and the Lee-Chien mnetinod.

298 Gas condensate composition. Component Methane Propane Mole Fraction 0.8205 0.0895

8. !uulerfncial Tension

8 5. Erercises


n-Pentanne 0.0500

0.0199 0.0201

Liquid_phase_properties_and_gas~1iguid_interfacial_t~nsion. Presuure Methane ~j nPentane_~caim~ MPa Mole Fracmiour 30.43 0.68130 0.1073 0.0772 0.050) 29.06 0.6640 0.1115 00827 0.0564 27.68 0.6414 0.1133 00886 t).0634 26.30 0.6187 0.1186 0.0940 0.0689 24.92 0.6003 0.1208 0.1001 0.0743
Vapour phase properties. Pressure Methane

Connpare the measured 1FF vunhues witlm tlrose predicted by the Weinsaug-Katz nnetlmod as modified by Scheclmter-Guo, and tine Lee-Chien method. It has been suggested to improve the prediction by adjusting the parachor value of time plus fraction to unatch the experimental data. Find the optirnised parachor valune of the plus fraction.
Densiny 1FF


0 480

(it 18 0.229 ((.39)) i).536 (1.738

8.4. Estimate the interfacial tension helween tine gas in Exercise 8.2 and water, at the gas isydrocarhon dew poinl of 31.98 MPa and 353. I K. using the generalised water-hydrocarbon correlation. Connpare lhe results with the value obtained by assuming the gas as pure methane.

0.0854 00933


(1497 (1.513 (1.524 (~535

Pruu’uani~ .._n~’~nuan

inc 0.0167 1)0145 1)0127 0.01(18 0.0095

un-t-tcxmudccauic 0.1)137 0.0(199 0.1(1)73 00054 0.004)


MPa 3042 29.04

Mole Fraction 0.8362 0.8448

0.0869 0.0863
0.0857 0.0844 0.0841



0.0465 0.0445 0(143) 0.0414 0.0398


1)298 0.278 026) 1)246 li.23 I

8.3. The interfacial tension, consnpositionm and dennsity of gas miund condenismile plnutscs were measured during a constant volunse depletions tests. ‘fine results at two pu’essuircs are mis follows: Pressure, MPa C02
Cl C2

34.47 2.42
78.06 6.71 Liquid 0.4) 1.72 49.82 612

V~~q9~_ 0.65 1)26 2.59 1.39 78.88 35.36 6,90 5.43

Conm~p~nent,Mole%V~ppur N2 0.65

C3 iC4 nC4

2.99 0.60
I .25 0.48 0.59 1)73 1.10 1.01 0.68 0.47 0.33 0.25

3.30 0.74 I .68

(1.59 I .25 0.48 058 (1.84 .02 0,95 0.65 0.35 0.32 1)22


I .94
0.95 1.23 21)9 3.38 4.03 3.29 2,68 2.26 2.19 2.09 2,27

C6 Cl C8 (‘9 ClO CII C12

I 48 2.25 2,53 1,96 1.51 1.22 1,17

Ct3 C14 Cl5 Ct6

0.22 0.26 0.19
0.12 0,11 0.10



1.01 0.77 0.87

0.06 0.04 0.03

2.11 1.63
1.51 1,47

Ct8 Cl9 C20+ Molecular Weight
densiny,g/crn’ Measured IF)’, mN/rn




16,91 120.62

28.05 97.44 0242 0.593 0.372

25.32 0.143 1.389




Phase beinaviour nmsodels are used extenisively in pctroleunsn insdustry. A nmiodel can be used to evaluate tIne consistency of memssured PVT data, or to gennerate such data as input in black oil reservoir simulation. The nrodels are also used in pipeline and weilbore multi-phase flow cmmlcmmlmntions. Ins tIme design and operation of surface facilities, phase behaviour nnodels are ennsployed to determine the properties and the amount of equilibrated gas and oil. The main application of phase behaviour models, based on determining the fugacity of components in both plnases by EOS, is however in conmmpositional reservoir simulation. in a simmrulator, the reservoir is couumuusonly divided into a number of grid-blocks, or cells. The fluids witlsin eacln cell mire considered to he in equilibriuns at the cell pressure ansd temperature. Time clnmunmge of reservoir conditions with time is investigated by determining average values in each cell during successive susnall tinme steps. The equilibrium condition over a time step is determined by flaslm calculations in eacls grid block. As reservoir calculations are generally itcrmmtive. nsnore than one equilibriums flash calculation per each grid-block at any time step is reqmnired. For a large reservoir, tire total number of equilibrium flashes may exceed many milliouss, consunning a large comnputumtional time and making the simulation very expensive. As the number of equations in conventional flash calculation increases with the number of components, see Section 5.1, tIne nmnmber of components characterising the fluid is conmimonly redmnced by grouping to reduce line computational time. Ann innnpou’tminnt conmsideruution ins applying a l)lmase behaviour model to reservoir studies, is wide ranges of composition and pressure wimich are to be modelled by EOS. In tlre integrated nrodellinsg approach, where the phase behaviour model is to cover reservoir, wellbore, pipeline, scpmmrators, etc.. in rune sinrnuluutinn, time task becomes even more stringent and tIne model often i’mmi Is Inn provide smil isfuiclony results. ~IIme connnmmunnm mmppromncin is t(n calibrate, or tmnunc line nsmodel. agaiunst experinnental data. lime selection of required data and parameters of EOS for adjustment

in tIne tuning process and the use of

relevant methods constitute a major task for reservoir


9. App/ieariouu inn Receunoir Siuuuuilatiouu

9. 1. Grouping




Exanup!e 9.!. Describe the C7~fraction of tine oil in Exannple 6.3, identified to C , by a number of 45 pseudo-components (using tine Whitson nmethod. S(,!ustzo,n: ‘The last carbon nunnssher describing the C , is 45. Hence the number of pseudo7 connponcnmts for lime C , frmmction is calculated from Eq.(9. I), as 7 45 N~=Integer 11+3.3 log( -7)]=6 The componenls connprising each psemido-component are identified by calculating the molecular weight boundaries of each pseudo-conmponent. Using Eq.(9.2), with the generahised msnohecmular weigint of single carbon number groups, we obtain the upper molecular weight of first pseudo-comsnponent, M~=96 {exp[( l/6)ln(539/96)J
J = 128

The concept of grouping has long been eunployed in fimukl description, html this is done nrostly due to limitations in the compositional analysis. Time nrost convenmlionial nnsetinmnd is to describe the hydrocarbon mixtmnre with discrete componeurts to nornral penltmnne and imexminses emich as a single carbon group and lump all the heavy fractions as the heplanes plmus (C ,). Tins is not an 7 efficient method of describing a reservoir fluid, particularly in conmnpositionnal siumiulation studies, where it is desirable to minimise the number of consmponents winile still retainming tIne reliability of predicted vaimmes by phase behaviotnr models. It is expected that the fluid description requirennrent varies witim tire complexity of tine process which is to be modelled. The phase beisaviour of a reservoir fimmid unnder pressmnre depletion may only be modelled by two components [II, whereas more than len eonmmponents nnay be required for miscibility studies. The key points in component grouping are: 1. The number of groups required and the distribution of components witInin emscln group. 2. The estimation of group properties required in pimmuse hehmmviou.nr nniodclhunig. 3. The retrieval of fluid description in terms of the original componeurts when needed.

I iemncc, C , C mmmd (‘~. wills time last Immiving a usnolecumlar weigist of 121, are assigned to 7 5 tine first psctndo-connmponmenl (gromnp). Similarly, for otiner groups we obtain, (;runut) No. k
~(pperM honinduury, M~ 28

Comptunenis in Group
(‘~ (

Group Selection Many investigators 11-13] have given recomnrendmmtions on selecting tIne nuimmmsbcr of pseudo components (groups). In general, 4-JO pseudo-conmponenrls are considered adequate for simulation purposes. A simple approach is to add nitrogen and carbon dioxide, at low concentrations, to nnethane and ethane, respectively, amnd to combine iC with nC and iC with nC . The C frumction is also 4 4 5 5 7~ characterised by a numunher of pseudo-conrponensts mmnmd iuscludcd. Whitson [51 proposed representing the C , fraction of a mixture by N~psetndo-connponents 7 calculated as follows, N~ = lnteger[I + 3.3 log(N —7)] where N is the last carbon gromnp number. The boundary betweenm the consecutive groumps are based our tire molecular weights Mk, given m M {exP[+]lts(?J]} k = I, 2 N~ (9.2) 7 (9.1)


227 303 404 539

C cCus C1 -C~ 17 2 C çC,u C 2 .C s 71 4

The mipplicunlions tnf coustinstnomns descriptions to select 3—5 psetmdo—conmponents (nnntnlti carbon groups), unt (luadrmulnurc poimuls, discunssed in Sectionm 6.3, is time reconnnnnended method of dcscrnl)insg the incavy ensd. ‘line selected pscmndo-comnuponenls will be as effective as choosing twice as unany, selected randomly or at equal intervals I l4J. Selectmng 4 psemndo-connponents by (lie quadrature method to describe the Ci+ fraction and following line siunnple uupproacim of addinsg isonners to normal hydrocarbons, described above, wnll redmuce lime tolmil nsmnnmnher of coumnponennts describing a fluid to around ten. l’he number of grounps, however, cmnnm further be reuluced particularly by grouping the iiglmt fractions. Lm cI mnl. Ill J proposed to group compousents on the basis of their volatility, using equilibrium runtuos obtainned by flmusIminng line fluid at reservoir tennperature and the average operating pressure. Tlmcy prcseuuted dnffercnut conTcimoiomns for groupinng ol highl and heavy components. Pedcrsen et at. 1151 suuggesleul tim grouup tine cousupouncunts hunsed ms nnass, llrat is, each group containing muppu’oxnnnmmmleiy tIne saumnc umumuss fumiclion. A ntnnsnher of fluids were described by 41), 20, It). 6 mmmd 3 psemmdsm—connnponnents mmmd their smnttmratiu)n points were predicted usinug EOS. They consclmmded tlnat a 6-connsponsetnt rcpucscnntation was .cuflncient for an accmmrate prediction of the smmtunruutiomm point. Cotternnsan and l’raumsnitz 114) used the criterion of equal mole fraction to select groups. A representative fluid descriptions is expected when tire groups are formed by due consideration to the volatility and the concentruntion of comimponents in time nnixture. Newley and Merrill [12], suggested a method of grouping based on minimising the difference, L~,between the apparent

The components of the original fluid with molecular weigints falling witimin Mk1 to Mk are included in group k. MN is the molecumlar weight of last carbon group.

some component properties. 30 —.304 9.2 Np (9.’e. critical temperature. the mixture saturation pressure and the connpositions of equilibrated phases at the saturation point are calculated by the phase behaviour model. 25 C 0 . molecular weight.(9. Methane.0 ~z~tnM i(k) 1 —(k/Np)~z1tnMj 0 i N k= I.2. V > 4: Number of Groups Figmnre 9.nu!alio.n’oir Si. ore + I.. or their combinations can be used to describe the relative volatility of components in mu mixture. is the apparent K-vaiue of the pseudo-component k. 2 K~=!~ __ ~xi i)k) the employed EOS and grouping nrethod [13]. Table 9. An example ofsuch a trend was shown in Figure 3. The last component in the group k.1. A grouping method based on the concentration and the molecular weight. 2 Np (9. I and 9. Effect of the number of groups describing fluid on predicted results by tire PengRobinson EOS. Effect of tIne nsunnsbcr of groups describing fluid on predicted results by tine Valderrama modification of Patel-Teja EOS. The volatility of fluid components at high pressure conditionns. is smaller. defined as. of components has been proposed [13).4) a 5 C C y and x are the mole fractions of component i in the vapour and liqunid plmmnscs mmt line salmuration 1 1 respectively. should not be grouped with others except nitrogen at low concentrations.6). It can be expressed mathematically as. Several EOS were used to simulate the test results. dcpenrds run line nmmixtnurc composition at a given temperature and pressmure. the order of relative volatility of components rcnnainms (lie saumme. A number of 25-component oil mixtures. The average absolute deviations of predicted l’esuits by different methods are shown in Figures 9.5) or (9. Note that the reduction of the number of groups down to an optimum value did not impair the predicted results. the molar concentration and the molecular weight of 1 component i in the mixture. Altimougls time cquilihriunmn rmmtio varies witis the composition. pressure. The original components are arranged by the order of their normal boiling pointtemperatures and grouped togctlser in an mnsccnding order to form N~ groups so that the values of ~ z~ lnM~ for all the groups bcconsnc nearly equal.1. The components are then ordered mmccording to their K-values and grouped initially by the equal mole criterion. were subjected to single and multiple contact tests. and i(k) denotes the components assigned to the pseudo-eomponment k. The above conclusions were independent of where K~. . using grouping method of Eq. A(KIKk) In tin) K (93) 1 using different grouping schemes.u 9. fully described by N components.‘~ ttl. depending on which inequality.6) where z and M~ are. Minor improvements by grouping observed at sonne conditions are due o the cancellation of errors. It appears that describing the oil by 4-6 groups is sufficient to model gas addition processes.8. such as the boiling point. respectively.2. Note tisat lowering the number of groups below the optimum value results in a drastic innpairment of the results. Grouping 305 equilibrium ratio (K-value) of the pseudo-component and those of the original components comprising it. The fluids were described by various numbers of pseudo-components ranging from 2 to 25 groups 4: Number of Groups Figure 9.uck Oil)B) & Memtsane ‘~‘-‘—O’—— ‘‘•‘-- Black 011(13) & Carbon Duoxjde Black ()it)A) & Rich Gas ~z InM~—(k/Np)~e InMj 1 i(k) 1 0 k=l. ilence. musing the full compositional description of the fluid. due to its high volatility in comparison witin other hydrocarbons. would be either. In the above proposed method. representing the volatility. N 0 C 4: Si. Application in Re. musing eqmual unole fraction grouping.5-6). (9. respectively. simulating gas injection processes experimentally using different gases[ 13]. The grouping is then adjusted by moving components within the adjacent groups to minimise the objective fmnnsction A. I. (9.5) 2)) 0 V C C .

00000 0.97 4. Table 9.802%.90131 5.2t9 0.t44 t.025 0.4% 0. SCI9 nC2O Toial A ((.= 4692.72 I .19254 5.2 Describe the oil reported jim Table 9.72016 0.67 0.082 0.77 C2 (3 36.33 5.27994 0.4 is used instead.2 kg..61043 .59566 1. nuseltuod: ‘lIne vuitune for cacti c’onsmpuunncuut us d’mnlcimlancd.—nC.51658 8.564 0.03220 0.. G-ltl. Pres.68 0.715 (1.593 0.3).05942 0.32 1.199 0. Adding components 0 unsu (‘7 downnwards.34 1.43 32.47649 0.5-6) to that by equmal mole frmrclionm.15 099 0.69 0.79 0.~I 81 ..05546 0.03 0.lncne nC 8 o’Xytcne Sat.32 0.4) mnusd (9. Addinug coruspounents from C downwards. I.271 n .613 0.390 0.08350 nCI4 SCIS nC 16 nCl7 nCtg nC g 1 nC2O nC24 1. Group-I will consisn of C.mt .24556 5.10420 0.833 0 045 0. 1 C 2 (3 nC 11. nC.luene 0.29 1. A.39 034 0.80937 7.03351 32.68242 0. winlu mu value iui 111.73610 1.75 (1.48893 1. respectively.00742 0.19S93 0.5 m 907 2.00008 0.36 2. ~ x.53/2=111.!.101)76 1.79 4 (. with the total weight of C -nC.83 0. Gronmp-l will 7 with 29.68 31 .03979 0.0331 94.75 t).99 3.17 5.)2_8.glcm’ 0.542 0.1 unmnd misc rest. 1~qunmilweight (mnrass) umnethod: TIne wemglnt of cads comnponneunt is calcnlaned as x. as suiggesled by the mmulhors.57626 3.06303 1.89 0.03223 0.42 0.85 0. A.82 I 5. wills 23.0’) nC4 7.70778 0.60 052 11. -usC with a weight of2473.22 ((. (3-lit. Appli’caiiauu mu Re.09762 0.73) 0.-nnC.21718 3.25 2. = I I I . G-lt.81 1. tmunlil tIne lowest value of A is unClnieVe(I.01946 0.44 4.66912 1.14 12 17 74.79 24.4 I 0. the measured comnnposilionm of the vapour. 5 ~ K.87721 I .47 0.03090 2.66 uunsd the rest.14637 1.32258 0 28913 (1 279(12 (1.091 nsnole% and lime rest.217 0. with an objective value for eacim =52.20 8.56 0.08645 0.70233 6. Compositions and properties of model fluids mit 373 K.1364 21.00 11.04 1.41211 1)04412 0.192 0.56 .02927 0.19686 0.41096 0..02 1.66 1.74 1.43 .94 0.302711 (1..17352 0.26852 022212 0.. wutln tIne total valume for C. anud Newley-Merrill.119 (1. Tine first coursponent of Gronnp—llt is injection study am 373 K.g/cnnm” PreSsU!~MPa — 20.46 2.034 0.07065 0.22184 0.17 .261 1.01 nC~ nC6 McI Cyct Pent Cyct Hex 2.77 0... t0683 0.399 nCt3 nC 14 nC 1~ n(’tó nC ~ nC1g 1 1..70 1. A.30 - II.58 n(’9 unClO nCl u ~~‘t2 0.uui~II unnud line corresponding valnne of A is re-calculated for the new grouping.88 0. h~ituumuI xlnnM. G-III.M..93394 32.wntln ~ x . in conmsist of C.25335 0.98 0.78 nakens innno (Jm.956 006t 0.13896 0.28 0.601 (1.22194 32.I wull conmsn Si of (‘ nC.89574 0..40257 2.91 1.711 unrole%. A. ~ 307 A comparative study [13) of various grouping methods.70 0LQ~_~.059 4 34! 4 1) 61496 (1.38868 2.05402 (1.647t6 1..12357 0.71 0. indicated a preference for the metlmod described by Eqs.62 1.11 0.79316 4.82908 0.1.St997 .-C.49976 Mel (‘yci mmcx i’.545 0 192 .1296II 0.27036 (1.28 15.295 (1. 19 nC7 Mci Cyct Hex ‘J’. Meu CycI Peal CycI tIes iC7 (.36 0.57 1)48 5. Coun u.255 0. mum Griumup—Ill. for 100 kguunotes of oil ~ s.7 2.73 0.o’rcoir Siuuuulalion 9.18357 1.03457 0.36 0.31)1 0.M. . The ohit’cljvc v..991% 31. with a weiglnl of 2219.401 .6S - 1..49 0. ‘l’hc objective weiglnt of each 2group is =4692 2/2=2346.23910 1.lusM. A. Densuiy.96 0.569 0.567 0019 0.—us(’.00183 0. G. as reported in Table 9.634 11 48’)S13 0.279 m 463 0. A.67476 ((.27 - 0.07038 0.30 0 42 nCg oXylene nC 9 nC~ nC 1 nC 12 nCI3 1.77883 0.(9. 12547 3.65741 0.382 0.16 2.87.1)1 5. particularly as tine grouping is for a nselhmunle iunjcction snudy and the rest is grouped into Iwo pseundo-componensts.35 69.87 0. eqnu..45 0.00436 0. In this example.nlune of cacti gruumup =223.75992 It 473 9 1)41 (1 713802 1.03240 0..012132 0. Aildimsg counmponeunms frousi C”. .220180.23198 0.0 1332 . C -nC. in 7 75 Grouup-Itt.0? ‘5.03874 0.982 (1.648 0 422 0 090 1)423 1) 125 0 174 0247 1) 32437 0. ( ronnp.00540 0.27992 1.448 0.45 0.10728 0.26767 3.95 0.04446 2.22300 2. using the methods of equal nsass. 7~ ui(’.0139 0.58 0.(9.744140.72 0.112 1.802/2=26.05 5.550 0.78 32. 4 0 Grouup-llt.2154 0.461 I) 35544 1.89 0. G-tt. mM.389 039613 .64246 2.237 0. equnmnh numole.tm. A.91 ((.15626 0. I 8 ((.21343 0.1 1514 0.1c9 011(A) 011(13) 011(A) 011(0) ~t mus 4680 8. Newley-Merrill nmielhod: Tine consposition of vapouir mit tIne bubble point umrunst be calculated using a tuned phase behaviour model..71 2. TIne conmnponenmts of C.00615 9. [Ii) as the least reliable metimods. = 223..13 t 4.-mnC.53 1.22241 2. Example 9.73 237 2.0751)1 Solution: m4.1)3870 0.63 0.5 1408 Methane is selected as Group-I.0.53..32 73.4 by three pseudo-compoineunts for a numeilmanne guns Equunl mole mmnetlsuxl: The total mole% of (‘irouup-lh anid (6roump-tll is equmal to 52.46080 20.16927 0.95706 0.77.923 0 353 0.86 0. 1 3 34.646 0.557 0.05297 nC~ uuCt.08 3. with lirose of equal mass fraction and Li et al.. are initially grouped inn two by equnal mole and K’ and A are cmulculumted unsiung t:qs.767 1.04626 1. llse calculation results for tIme first and lIne Imusn few iteralionss unre slmowns in tIne following Tumble.22018 0.97594 7.1)2 0.297 (1. using 4 or 6 groups.00003 0. A G-ttt. Denns. downwards.306 9..00310 0. I .73600 0. InM.66 2.77 2. G-It. ‘nuuruponenn Black Black Votauile Vutauulc kuclu ( uuu.151(61 0 12427 0.05687 2.01103 0.76 I .197280 77178 (1 t 4480 1.23 27.06581 0..07471 0.1036 1. MPa Sat..

particularly for gas condensate fluids factor. Applncatioin jim Reservoir Sinuuilation 9. are tine predicted ussole fractions of connponent i.085 winere tIme weiglnting fmictor.a1)2 /x~ (9.17) ilk) (k) = 0. Several methods have hen proposed to calculate the properties of pseudo-compomments required in EOS[4.7) where xk is the mole fraction of group k in the mixture.(9.11) (9. eqxnal mmmuuss fractious and tinmmt of Winitsons.Z. P~.2905 — 0. The authors also suggested using the above weiglnting fmnctor.. instead of time mole fraction. = (9. Grouping 309 The lowest value ofA is achieved when components C.~(K)~ (9. Imowevcr. Tinis can cause problems. = ~ ilkl ~x x (c. are determined from.~~xmxj(vJ + 8 i(k))(k) (9. = where the retrograde condensate phase is over predicted.. dcteriorales inn flasin calculations wisere tine disti’ii. x~.(9.14) en. or the molecular weight.~). The study for a lean gas condensate denmmonstraled time stuperiority of their method. Time binary interaction parameters between the pseudo-components of k and q. xii ilk) kq (9.8) 9 represents the component property.(9. respectively.s between the psemndo-components.is defined as. factor are calculated by molar averaging in the above The calculated properties of pseudo-components arc not directly incorporated in immost EOS. 5 ZCk = j ~ cii ilk) . probably due to the cancellation of errors.1. l’hey applied Eq. in time liquid and vapour at the saturation point.15) The most common method is molar averaging.!. Ncwley mmmd Merrill 1121 conn’npmmred Ilmeir proposed grouping metinod with equal urnole fraction.5. Group Properties b~ ihkl ilk I (9.l5]. q~. 17 ) to tlneir own nuetisod and time itnolar averaging to otlners to estiunnate the properties of groups.18) = Z~RT~ / van. Grouping is commonly conducted according to the concentration of componemmts in the feed.16) to calculate the binary immtermuct ion punrumnnnelcr. 2 p =(x~y~)’’= 7.~ 1 1 + c )‘ / x~ 1~ (9. The results depended on the selected EOS and the number’ of pseudo-components used to describe the fluid. as inrprovements relative to those predicted using tIne full composition wer~also observed at some conditions. hk and ck. y. acentric The molecular weight and the method. applyiumg mixing rules directly to tine parameters of original components to calculate the parameters of pseudo-counpouments seems a where. [15] suggested using the mass frmmction iimsteumd of tIne tmmolc frunctionn inn Eq.ution of components in each pseudo-consponent will be different in the two plnases.hk) + (9. Newley annd Merrill [12] suggested to calculate the critical properties and the acentric factor of pseud~-connnponentsusing a weiginting factor. It.13) . This approach is jmnstilned in predicting the single phase volumnnclric bclnavhntnr mnnd to sonnme extent the saturatioun pressure.9) T. reasonable approach [13].l2. in Eq. hence. are the paratn’ieters of EOS for the pseudo-cotrmponent k. as the properties of the heavy pseudo comsnponents are those of tine original gas and not the fornimed liquid. such as the critical properties (Ta. oflen tine original reservoir flmuid.16) (nh (9. based on splitting of the original fluid at its saturation point. with Xylene-nC~ in Group-Ill. whereas Wu and Batycky [10] proposed to calculate group properties by a connhinnation of mass and mole concentrations.-nC~ are included in Group-Il. with the equilibrium ratio of K and zj is the mole fractioun of component i in the feed. but are used to calculate the parameters of EOS.308 9. Pedersen et al.lO. = ~.~x. = ~ (9.acentric A comparison of time above methods did not indicate a clear preference for any of them (13].12) 0. using the full description of the fluid.7).x (i 1 ilk) jIkI — k1)(a.10) (9. The Lee-Kesler averaging method for critical properties [16. °k ~ (in) where a~.17] has also been used in the industry.v~. .

equilihriumn rmmlios of time groups.36 1.31 142.07 42. aind c are constants.66).25 0. Ins (isis procedure. the use of group properties generated frons the original commsposilmon umsay be iuma(Ieqlnmnle for mm unccurunle prediction of the phase behaviour.(9.qruilihriunmm ratio. Table 9.7 shows the equilibrium ratios measured in a multiple test where Black Oil (B).096 (1. C. I. K 105.15 s (1. 18). Time conspuitationuml (CPu) timnne for simulating tIme above process can be reduced by 75% due to groupiumg mns shown ins Figure 9.3.73 18. I. are used to detenisiimre the conslannts of the above equation by tIme least square imsetlnod. Otlrerwise tine rclnicvmsl umund re—grusupinng caur k’(uule excessnvely Iinnse consunisiung.(9.01282 (178802 (K)”s.lpp!i.608 41.38053 0. For example. Tine equnalion is tiseum eunployed to calculate the equilibrium ratios of tlsc original consnponsents and retrievimng tine full description of both phases by material balance calculations.61% 11473 7. Solution: The comnponent properties are read from Table A. The properties of the group using tIme original compositions will be equally weiglmted for the properties of C and C .(3. 0..059 30. where the concentration of C in (he group is reduced to 42% of C . Eq. up.s.4-5).(9. insstead of nnole frunctions. Mt’a 117. The variation of equilibrium ratio for each component mmnixture composition.iu I.26894 1.’.ij.(5. when contacted with ten volumes of an injection gas in a backward multiple comitact test. Componenl (2 (3 nC4 1mm K =co+c (l+wi)(l_1J 1 1 (9.‘.. I imm Appendix A and umiolmur averaged. Note thmml tine conmposition retrieval improves the results even for systems described by mm large number of groups at the higiner pressure where phase compositions changes markedly. backward contact gas injection by tsmethane at 34. The above problem can be alleviated by retrieviung time fluid description ims lerms of line original components at some stages of cell to cell calculations in reservoir sinmulation and forming new groups aecordingly. MPa 6.7). K t’~. Clearly tine above melirod would be practical only for rapid groimpiung umnetlnods. wlsere tIne relative cotncenntratiomm of fluid components within each gromnp varies significmsnmtly.‘oi..85 0.. If fn. was vaporised repeatedly 373 K.471) . after 7 9 contacting the gas. 0.‘. to retrieve the fluid description using Eq. .re sisownm ims Figure 9.277 ((.3 9.11(8 11)05 (1(1181 (1(158(1 99. obtumined by flash calculuutions.1164 (1.5j. time imnixture detailed compositional description can be mused lo fornnn unew gnotnps. w~.276 000 Composition Retrieval In some processes. ...58 16.0588 11. ‘p ((.1(469 ((.01 II -l 0 (I+m~~)(I—h/Tr) Figure 3. and c. 1.i. Eqs. consider a group formed by the three eoussecutive single carbon nunnbers of 7.19 Z~.42 1.2 comprised of C. hint wilts tIne weighliiug factors calculated from Eq. and nC.11012 0. as shown in the following table. and 373K. Figure 3.38615 T~. acentric factor and the reduced temperature respectively.18)000 Mx. Molerauio C /C ClO/CI2 C /C 7 9 1~ 15 I . using Eq.77 43./.2 shows tire variation of concentration ratio of some couiiponcnts of mu North Sea oil.’.81 P~. Equihibriuimn rmntios ins un test simulmntinng oil vaporisation by mettmane at 34.61496 0.1432 0 ---a em 3: Tise method of Newly-Merrill is the samnne as line above.4. It 587 16 780 13.5-6).7. . Cousmponenst K.i.1 0 .42867 up.5 11.23413 1. The above function..I9) has been developed 1131.(9. Group-Il nsolc% 11.34491 0.58 MPa and is only due to clmatnges in the can be expressed by a linear . 7 9 .01 ua On o0 i~’ Contact Stage 02 03 C2 C3 0.up. such as lisose descrnhed by Fq.eanuple 9. Time effect of compositional retrieval at the lower pressure becomes only significant when less thanr six groups are used to describe the fluid. 8 and 9.2) and Eqs.urtiser flmnsim cmmlcmnlmmliomss are required. uns follows. 9.0538 (1. (rounping 311 Calculate the critical properties and acentric factor of Group-Il in Exausnplc 9. Table 9. Time sinsulaled results of hydrocunrhon recovery by gas cycling at two different pressures a.38534 ((.310 E.51 ISIS 7.38289 0.1(74 (1.29856 1.2. Note that the log of equilibrium ratio function as.1.001(00 114.49 Original oil 1(10 After conuact 0.975 Tx. beating the purpose of the exercise. It also exhibits tlmat tine full composition retrieval and regrouping do not siguiificumnhy increase tIne compulational time.19) where K.(9..ilii.0343 (1. Clearly such properties will not be representative of Ilnat group.. suds as gas-oil displacement and gas cycliung.65 14(1. is a modified form of the 1 Wilson equation 18]. up.45 1(1.76 I .33 362.53 357 92 8. Molar concentration ratios of oil components befpre unn(I umfter cormtmicting gums.58 MPa Table 9. (n) and Tr mire tine e..06 An inverse groupinsg ussetlsod.11)7 nC4 Group-lI 0.

00029 -l. 0 C 0 a.02035 0. the commmposition of equilibrated phases are cumlculated as shown in the following table.04264 0.00911 0. 20.47198 Oil Comp.09273 0.) Ink — 0.16771 -(1.30150 llt(nC -nC2O) 0. 0.00314 0.00375 0.072 12 0. The oil reported in Example 9.00006 0.09435 -0. 2.8049 0.01310 0.920282 0. are given in the following table.2181145 -1.4.46807 0.894982 * “~‘ ~—‘ Winln Retr. Effect of composition retrieval on predicted recovery of C .1)1937 0.1160492 -11.32964 0.19) are determined.-nC2O) T.01542 0.2t)449 -1.01)979 -(1.01505 0.28657 0.32445 K.49474 (1.00079 0.31463 0.49474 0.02592 0.00004 .81626 -1.1432 0.8 MPa Is Number au Groups 20 25 Connponent.00043 0.00718 0.00062 0. The predicted results by a phase behaviour model.508 19 1. 34.4861 (l+w)(l-IIF.92 626. as given in Example 9. 7. 14 nC~ nC 5 nC16 17 cC 18 nCi nmC 9 -l. . 20. 0. Ix.85759 -((. The oil was described by methane and two component groups. using the equal zlnM isnethod and molar averaged properties.334l6+2.71332 0.00144 Figure 9.0207 I 0.8 MPa lnK~=_0.01153 20 -2. U U I-.00329 .02698 0./X~ =0. 0 U U — ‘l’he critical teussperature and acenntric fmsctor of the three groups are calculated by molar averaging and Ihe coefficients of Eq.02027 0.5100 0. K 19(1.00563 0.02151 0.0.73393 x.18696 0.01874 0.91)576 -(1.1. E 0 ••~~••~~• wimh Reir. mole ‘5 C C1 2 C 1 nC 4 nC nC5 6 Met Cyct Pent Cyct flex nuC 7 Cyct lies Met ‘riuluene nCg o-Xyteume nC 9 (t+w)(l-tIJ’.4.00133 nC nC10 11 0.2 was flashed mmm the reservoir temperature of 373.8 Mt’a *--.01206 0. 0 21) 25 Figure 9. Group I (nuicilnamue) Il (C. =0.00194 0.65952 -(1.04214 0. Grouping 313 Solution: 80 60 (a a.21781 0.3.28419 Gas Comnmp.511654 0. using the above fluid description.58 Ml’s without Reur.-~-e 0 5 IS Numnunher of Grinups 10 wIth Reir.00009 0.00429 0.u inn Rem n’rnoir Si.(.22652 5 Liquid mole fracnion=0.03383 0.72225 -1..74148 -1)73432 -0.0 K.30953 -1.-. Applucatio.15457 0.534l(I+Wi)(l_~~~_) Smnhstimniing tIne muccintric factor and redunced tcrnnpcruntmurc of e~ncin conuponent in line above equnalion resu Ins inn mime cqniilibriuinn man ios of tine original coumnponemmts.58 MPa 40 20 g + en I-) ~—~a— Wiuhoui ReIr. 20.03001 0. mole fraction 0.00150 0.02135 0.0553 nC nC12 nC11 .10936 0.00090 0.26533 0.56 357.312 9.1)9131 0.00322 0.0814% 0.40954 -1.10824 (1.00576 0. 34.04506 Group l(methamme) II (C -nC ) 2 4 Feed Comp.91179 0.46958 -0.5952 I acentric facior 0.00740 0.43761K.01066 -2.(9.8 MPa 5 10 wiihouni Reir.38616 Equilibrium Ratio 2.02428 0.56239 0. fronms Volatile Oil A by 31 methane cycling at 373 K.56239 in the above.70604 0.00117 0.03293 0.3.00021) 0.01069 0. 20.01697 0.18831 0.01013 0.12620 0.00013 0.) 0.01929 0.11136 0.. = nL +(t— nL)K 1 Substituting nu. Calculate the composition of equilibrated phases in terms of the original components. 0.97900 -1.05991) 0.00068 0.56239+0.51451 N 0.-nC ) 4 III (nC.02373 0.115o -1.0115 0.01864 0.unulat join 9.52701 . Computational time of simulating nmiethane cycling.67 Tr 1. Example 9..00446 0.02012 0.13460 0.19950 (1. 0.13087 y 1 0.16 194 0. 0. lIme conmnpiscncnmt huiluuumce fur emuch connnponent results inn.01482 0.04623 -0. 7.95739 1.

are considered adequmite. namely the Zumdkevitcin-Joffc umsodiincmition of Redlich-Kwong equation (ZJRK) [23]. rcspccuive)y. the evakiation should cover wide ranges of composition and temperature.04 77.mupari. proper considermmtioun of all pertinemst factors when evaluating EOS is essential. 5 (2) Ph and Vh are ulse nsisuure bubble point pressure and v. .cunui Pe.oij. Cousmparisomr of errors in predicting saturation pressure at 373 K by various EOS.:. such as replacing eaelm single carbon group with its ptnre cqunivmmlent its tIne nun(sdcl fluid. 31].:: ~ A A :: en At A A A * 0 vp’r ZJRK PT • • It) 0 I • 2 3 Mole Injected Rich Gas/Black Oil A Figure 9.MPa 11)9. Table 9. fluid clnaracterisation.34 24. The experinnental datum arc given in Table 9. the Sclsnnnielt-Wcnzel equation (SW) [28] .79 and 31.3. the Soave-Redlich-Kwong equmation (SRK).464 0. respectively.1%) 61. .72 14.MPa Oil Gas 1(11. 22.~.34 21..58 24.61 2463 — 134. by unslung dala 11mm umnodcl fluids.314 9. Tinese nriximsg mimics hmmuve bceun used in almost all the comparative studies of EOS. instead of real reservoir fluids.81 11.73 34.1. have been evaluated by several investigators.73 9.. Tinese eqinations were described in Sedlion 4.cm’ V 5 P~. where nnany fmunndrcds of dmntui poinls on various nrsodel and real reservoir fluids. Connmpumrisomn of errors in predicting saturation volume at 373 K by various EOS.36 25. than sclectinmg a particular equation. I’S. botim described in Table 9. in a general cotsipmmrative study.2 9. IS £ A SRI< l’R 1: ° :“. however.64 24.69 -s (I 2 Mole Inujected Rich Gas/Mole Black Oil A 3 Vc. Any phase behaviour model is hotnnd to carry errors intro(htnced by inmmnccumn’mmIc imnptnl (Immlun.5. tine Patel-Teja equation (PT) [291 annd its nnodilmcation by Vmsldcrranra (VP’F) [30]. shown Ihat certain equations exinihit a higiner overall muccunracy. (‘o. 22].4pp/ucoli.93 28. were measured xi 20. For hydrocarbon fluids. described in Section 4. Hence.s. g/cuss’ 24.264 (I) Added oil and gas volumes.MPa 1 . A number of conmpmnrativc sltmdies 19-221 Imunve. ‘l’lie evaluations of capumbilities of van der Waals type EOS for reservoir studies is of a more inlerest in tlnis sectiomn.7’) 97. in comparative studies of FOS.u 9. but also on the mixing rules applied to its parameters.96 36. etc.29 Figunre 9. line rmnmmdonnn usuixing mimIcs. are compared in this section.8l 48. The capabilities of tine equations presented in Section 4. ium a swelling experinment wlnere Rich Gas was progressively added to Black Oil (A). The accuracy of predicted results by any EOS depends not only oun lIne n’climmhihity of thmml equation. in addition to conventional PVT tests..40 163. I.. The performance of a number of leading EOS. generated at simulated V~’cisu’ Eq.nu in Ri’.6.61 (~7.Sipnu. inmto tine predicted rcsunims. dunn produce reliable data witin conclusions applicable to remnl fluids. The use of many componenrts with remnlistic c(utsceuntrumlionms.2 and many other van der Waals type equations.tumc.3.’. lIne problem can be alleviated.smi of I’A)S 315 COMPARISON OF EOS (3) An sonne snages nhc pressure was lowered below nhe bubble poiunt and Ihe properties of nbc equilntmraled phases (e) were nicasured.hutj.3..73 (14.13 Ml’s.36 83.85 2)5% II)) .61 85.MPa1 V~. The studues have resulted unainly in a general conclusion that none of them can be singled out as the nmnost stuperior equmation to best predict all properties at all conditions.Cin’ 5 4 t .58 24.. 5) E > em C ho o • a t’R3 PT O SW • SRK3 O • C A A 0 VPT ZJRK cc.5 and 9.16 .2. Time experiummermlmml data sisouuhd be obtained preferably in tests simsrulating various pertinent reservoir process.57 Oil Gas Oil u. Tine above equations have been selected either because tlmey are widely rused in time indiustry. the Penmg-Rohinsous eqdnation (PR) (26] and its three-parameler form with the volumnme shift (PR3) 1271.6 compare deviations of predicted saturation pressure and smmturumtiomn volunne from experimental data. such as nmuubtiple contacts and gas cycling for gas injection studies.2. or they have been shown to be reliable in reported conimparative studies [19. ~ Phase State V d .80 24.c[ns P~. . C 0 S U 0 0~ a a 0~9 em 5) 1) 0 5 Oil Gas Oil Gas a 101.52 57 14 0.9)) 1(11. The presented data are given as typicmml exumummples on the perfornsnmmmrce of Ihese equalions as reported in [19. TIre results indicate thaI each EOS could be nnore successful dependiumg on tIne compositional range.124J mmumd its three-parameter form with the volume shift (SRK3) 1251. estimated critical properties of the fluid components. particularly the properties of single and multiple carbon groups. V dd. respectively. Figures 9.9(1 23. 5) 07 47 58 51(17 62.43 20. Experimsncntal data on umddition of Rich Gas to Black Oil (A) at 373 K.Dcns. Therefore.

247 0.089 0. The comparison of average percentage deviation of predicted equihihriummnn ratios can be misleading.8 1. positive or negative depending on EOS.733 1.295 0.174 0.4. Neverilneless.198 11. Fum’timernnore. nC 9 nC~ nCmu nCi 2 0 nCun nCm 4 nC~ nCi 6 nCii nCug 1. TIne equilibrium ratios mnt lime muhove conndilionms predicted by various EOS are compared witin time expcrinncnrlai clmilmi inn Figure i)]. Vol.301 0. interfacial tension and the density. TIme average absolunte deviation of predicted equilibrium ratio by EOS.05 -1 (I +w)( I lrrr) 0 n - Figure 9.112 1. Component.059 Gas nC 1. ad 5) 0.261 0.833 0.2.545 1. mole % Cm C 2 C 5 cC 4 nC 5 6 Cyct Pent Met Cyct Hex nC 7 Cyct Flex Met Toluene nCg o-Xyteune Oil 47. For example. where each connmponemmt inmus lmecmm idetmlilied by its reduced temperature. as also shown in Table 9. The concentration of ineavy consnponenmls in tine vapour pimmuse is relatively low resulting in a high relative error band experinnentmmlly.~-0 0 t) q ti~. Figure 9. A.4.045 0. g/cm 0.6 2.3.264 0 40 0.0 Redmnced Tenmperature Figure 9. This cans produce mm large deviation between the measured and calculated values.034 0. 0 ‘1 1’ E ‘as .448 0. for heavier compounds.618 11.199 70. gemmerally predict the composition satisfactorily.79 MPa and 373 K. U en SW 7.646 0. — C ZJRI( w 0’ .019 110. on which EOS models are based.5. are given in Table 9.353 0. but also in predictimmg otlner properties such as the viscosity.5.7.Dens. cm tm E~ui.389 0. increases systennatically. The heavier a compound is. Application ui Re.316 9. as tlmey are strongly influenced by the lmsrge values of lneumvy counmponents with tow equmiiihriummn ratios.SRK PR ———. particularly the attractive term. Consparison of predicted equilibriunm ratios by various EOS witim experinmnenlal 60 —a PT • SRK O PR O S data.956 0.8 imiglnligints line reluntive errors of predicted equilibrium ratios in the same test.473 7.735 0. the parameters of EOS.061 0. 9. Phase Composition The predicted composition of equilibrated phases is not only important in deternnmining the phase behaviour in subsequent flash calculations. All the above leading EOS. where 120 cm of Rich Gas wums added to 60 cmn of Black Oil (A) mtt 20.423 0. the composition of equilibrated plnmuses in tIme first 3 3 contact of a test. have been correlated using vapour pressure data biased towards the light components as described in Section 4.192 0.219 1.461 0.634 0.287 11.. Composition of eguilibrated phases at 20.041 4.4 0. were used in the comparative studies.082 0.4939 0.79 MPa and 373 K.090 0.2 1. for a large number of commnpositional data 122] ame slnown in Table 9.341 0.2238 .119 0. This trend slnould be expected for a number of reasons.767 9.aersoir Sipnudaiion reservoir conditions.422 0.all the equations. The deviuntiouns of predidled compositions are quite acceptable and ins most cases comparable with error bands of experinniental data. 0.382 1.. A nmore unseftul commmparison is thmmt of the average error in predicted composition.923 1. the furtimer its behaviour deviates from tlmat of a compound with simple spherical molecules.025 flCn 9 nC 20 3 Equt.297 1. tine percemmtage deviations of the predicted equilibrium ratio by.8.60 0.982 1.648 1. Comparison of LOS 317 10’ • Exp..125 0. SW —p’~ — VI’S’ —— ‘-.567 63. Comsnpmmrison of em-ron’s in predicting equilibritum ratios by various EQS. Otimer examples can be found in the literature [19-20].279 1.06 0.2.463 0.144 0.JRK £ a vi’i~ 2t) 0. Table 9. Note Ilnat all the equations predict the equilibrium ratios similarly.

TIne deviation of predicted values by VII’ for CO ricin syslenns 2 us relatuvely high . ratio Equation % OnI mokfracuon Gas SRK SRK3 PR PR 3 SW 16. All EQS generally requmre bunary unteraction paransselers for hydrocmmrhorm-C0 . A sinnihmtr uncctnraey is expected for gas condensate systcmsms. It is not summustimml to himid tlmree-paratmrctcr EQS predicting the liquid density more rehiumbly (humus tismit of its cquilihrmited gas.9’) 3. were nmoticcd using SRK. Average mmbsolute d evialion s of predicted saturation pressures. (‘onupari.72 14. Smulnirmnui(.57 362 1. TIse deviumlionns of predicted dew point pressure frommm experimenmtal data.35 18. wlscre tIme timird parusnsmelcr is included for improving density data.04 2. Saturation Pressure Table 9. with a deviation of about 2%. particularly for gas condensate systems 1261.91) 11.n Average Absoluue Devnalion % SRK ‘t’hse gums deunsity is gcmncrally predicted nmnore reliably tlman that of the liquid by two-parameter SRK3 PR I’R3 SW 4. As tIne tlnird pmsranmnelcr imums been generally correlated using saturated liquid volumnies.0021 0(1018 0(8)17 (1. Avermige msbsoltule devimutiouns of predicted liquid smmturation volunme.0011 0.38 2. tIme sumccess of these equmunlions in predicling tIme bubble point is expected. EQS slmould predict hotim lIne phumse cousspositiomm mnnnd time nmnuslmmr volunnme of a fltmid with known cotmrposition reliably.0014 0. imscluding Ilnose with non-lnydrocarboun gases added to tlmenus in swclliusg tests 1221.0011 0.33 7JRK 2.19 5. differential liberatnon and gas cycling.6 lists the average deviation of predmclecl bubble point pressure for mm vmiricty of oil satnmples. All tIne 3-parmnmsneter equimumions.34 16(i) 4. 1’Iuc errors assocumsted wulin n’r’ueasum-ed conspositional datum of equilibrumled phases uising poor Practices wend described inn Clnmupter 2.80 2. can exceed 20% [31]. ‘line exception is 1. SRK3.0019 0. mis discussed inn Sectioms 4.56 17.05 2. The equations are generuslly capable of predictung tisc bubble poimml pressure willninu 5% devimitioum for hydrocarbon systems over the whole range of phase envelope itncluding nemur critical condmtions.22 3)3 1205 12.6. emsltmmmnccd its cmnpmmbility to one of tine leading equations [22].71 2.1 R K.35 4.318 9.0014 0.. . described in Section 2. eveur for well defined synthetic model fluids.57 3. emits he used to estimssale tIme incrcunse in liquid density by pressure. by time leading EOS.3’) 2.80 2.0020 0.29 12 29 9.un ‘8’ 6.78 2. Devimmtiotss.61 2. the predicted phuuse compositions by EQS for properly characterised fluids could he as reliable as line cxpcrimsscnnlal dmita. A ltinommgiu it is mu I am u Pammmnmndter equmit ion.77 6. IligIn deviations in rcdiclcd cquiliimriuunum mat iuss oh lscmmvy conunponneusls should. Alternatively. sup to 25%.94 685 3. ‘Ilnis is unuoslly dume tin time use of smihuraled liquid detssity data in correlating time third parameter in Ilucsc EQS.77 477 4. hut tiscir idcntiimcuntiotn anmci characterismution are also quite demaunding. Conrsidering Ihe reliability of EOS for prediction of equilibrium ratios of light consponents.31 3. Table 9. Average absolute deviations of predicted equilibrium ratio and composition from experimnmental. 2 Table 9. hut tIme inclusion of the voluune trmnmrslmitiotm.44 3. i’lne behaviour of Ilsese compoumnnds are not ommly difficult to mnmodel by E()S.87 8.16 6.son of ADS 319 Ahmed [19] compared the performance of eight EOS for predicting lIne pinmmse belniviotur of ten real gas condensate systems after matclming the dew point of cuiclr fluid by adjuslinmg tine interaction parameter between methane and lIme plums fractioun. TIne deviation can be nsuch lniglmcr for real fluids due to tIne presence of very large nsolecules.27 16.22 4.45 18.i 9. empirical PT VPT ZJRK 6.3. Ahmed [19) evumlunaled line relimuhility of lemiding EQS 10 predict the dew point of a nunniber of gas conilensunle mixtures in swelling tests.uu Voluuuuuu’ I .16 4. TIme perfornnnmsmmce is eqtmaily well for both phases witlm thnee-paramelcr equations. lead In tnnreliahle 1 estimmnmulmon oh the dew point.36 10.0012 0.70 21. Equit.52 . Density ‘l’ablc 9.‘oir Sunuualao. as the bubble point jsrcssnnre is nununiunly counlnulled by lise lrehimuviounr (mf light colsnpounermts.. It is advisable to calculate tIne smitsnrmmted liquid demnsity by EQS amsd then adjust it for conrmpression due to the excess pressure mmhove tine bubble poinrh.83 4. EOS may predlucl erronneotns deunsity for highly tinder-saturated liquids.80 4.45 8.05 equnmnliouns. Note tlsmul ins (sr(lcr to produce rehimmhle denusity of equilibrated phases. which strongly affect the dew poinsl..7 slsows the mivermuge devuustioni of predidled saturation volume and liquid and gas dc’mtsilics in vmmrionns gums injeclions teds )22). The deviuntuons are generally iniglmer for flunids witlu isigim concentrumliorns of non-imydrocarbon gases.91 1 39 23.1)02(1 0. All line mubove lcmmdimsg EQS predicted the concentration of major componmenls of tise vapour pisase un counstannl voltunune depletion tests within a deviation of 2%.i in Rise. tIme devimitionm of predicted values after adding gas exceeded 30%.61 0.7.. and (men muse mi tuned phase behaviour unodel to prcdmct the produced fluid composition.18 tnj Gas Flyb’ocmnrbon N2 C02 Overall E~iaii.i Iu~u~ I )eunsily ( mis l)encity I ‘Suiat ion Average At usotulc I )cviaui. ‘Fable 9.0012 Considering typical errors no measurung compositions in tests suclm as colmstmnmrt volunsme depletion.5.44 2.20 2. munich gmms mmnnd liqtuid densities mit equulibruuum’n.55 10)16 SRK SRK3 PR I’R 3 SW t”t’ VP’F 6.02 4. evens at low concen(ratiours.35 3.81 2. It should be noled tlsat no binary inleraction pmlrmsusselcr was used in VP’F.73 4.0014 0. it uses (Ienmsity datum to delenninne EQS parmnnnidters. imowever.2.17 0(1021 0.2. Although tIne dew points of original fluids were initially nsnatclnccl by tuniung EA)S. App(ueotio. In suds cases nt ms probmmbly nnorc bcunelicimnl to chii’cct lIme ellorl towmsrds characterising lhe origunal fluid aund genermnting reliable PV1’ dmmta. mire moore uchimible tluusum tIne 2-paranmueter equations.63 2.53 6. ‘I’hc isotinermal compressibility coefficient.0019 0.02 11.2. The VET and ZJRK appear to be overall tniore accurmmlc than (lOners.0011 PT VPT 7JRK 22.52 1.

96 5.cuns Eq.24 25.402 (1.nrc rcdticmioun below tine bubble point can vaporise almost lmatf the liquid volume.213 1)181 nC’2u) (1.2.02 11..iqmuid GaalLiquuid 32. The volumetric behaviour of a gas condensate. Table 9. Single Coniact Gas Liquid GaslLiquid Gas Met (‘ycl tIcs ‘l’uuluicuue 1.51 4.53 19..4327 0. Hence. is generally inferior to that of gas-oil systems. (las Conimponent.204 11. Appheaiioun in Re.876 (1.11 32.70 14.650 (1.94 32. where tine systenn behaves oil-like.9. as predictect by several EQS is shown in Iigtnre 9.479 4.71 17.8 demonstrates the average absolute devimmtion of predicted gas anmd liquid volumes for a large number of data generated in various simulated gas injection processes [22].320 9. This generally results in compounding errors.soun of LOS 321 methods of estimating oil density. Va~~. an over estimation of one phase is generally acconnpanmied by under estimation of the other.515 ((. Time error in predicting time retrograde liquid volume below time dew point can be redumccd uinarkedly by tuning EQS to tsmatch the dew poitst.n 9. First contact data of tmmettmane-Voiatile Oil (A) at 373 K and 34. Sectioum 4. Note Ilnat tire predictions of all EQS approach tine experimental values quite closely within tine vaporisiusg regioum.767 11.51) II l’Ine cmmpmihility of EQS in predictiung the plmase volumnne of gas condensate sysmeumus. h’ience. I % in the predicted bubble point pressure.. is generally insferior. Note that the error in predicted phase volume ratio is the higimest in all the cases.3.007 ((. Smcim higln errors near critical conditions should not be surprisiumg as a snmnall prcssn.242 1.8.944 (1.014 ((. which dominale time lic umid fornmation.77 14. the predicted results in each cell provide the input data for time neiginbouring cells in the flow direction. Therefore. Note that errors of over 100% are qtiile conmsmnnoun. particularly witlnins tIme retrogrmsdc region.91 35. resulting in a large deviation in predicted phase volume ratio.918 1)830 0. 2.249 (1. 199 11. the overall error in a multiple contact sinnulation is expected tobe significantly higher than that in flash calculations of the original fluid.77 43. Table 9.11611 (1.18 11. conuporm.10 30.l)euns. Average absolute deviations of predicted volumes at equilibrium.01) 81 .19 10.481) 80(10 17.2.12 27.31 41. 6 (1.64 42. may be used to calculate the density of under-saturated liquids. I.9.742 nC 4 n(’ç unC.154 20.661 0.71 PR3 SW P1’ VPT 14. .58 MPa are shown in Table 9.462 ((.135 11.02 The error in predicting phase volume increases sharply when the critical point is approached.68 11.27 11. The results of first contact between Volatile Oil(A). generated in the critical region.81 25.77 27.292 3.117 1. with 1 tIne commnpositiomm givems in Figtmre 4.13 48. it resulted in a significant deviation of the predicted gas/oil volume ratio in the final stage.374 1.21 31.594 (1.54 24.~ nnCi 2 nnC 15 nC. has been found to be negligible [32]. EOS ZJRK SRK SRK3 PR PR3 SW Oil Vol.53 14.887 C C2 5 4.59 9. Time inmiprovement in predicting phase ratio.9 shows the deviation of predicted phase volume by various EOS at the front of a forward moving gas in a reservoir described by four cells. Note the severe usmass exchange between the pinmuses wlmere the oil/gas volume ratio of 4 prior to the contact changed to 0..g fl(’iq 0. Whereas tuning of EOS to experinmental data. by inclusion of the near critical density correction.50 33.Di (‘I 72.47 20.ce’ru’ojr Su’nmm.398 (1.47I (1. It).293 Mutniple Conumuct I.470 t).744 ZJRK 44.10.06 4)791) 1.1)75 4.84 29.90 5/dunn’ 0..54 8 (1.95 10. 4 nC~ 5 nnC.29 32. Mi~% .3310 ‘l’mmlrlc 9. Gas and Liquid Volumes The errors involved in predicting phase composition and density are couinhimmed to nmake tIne calculated phase volume in flash calculations as lime lcasl relimubic predicted imnfiu’nmnmntionm by almost all EOS.67 n(’ 5 ii Xytenc cC 5 usC.56 32.348 0.948 I). 26 28 31 27 25 26 P’f . Although VET was found to be reliable for the original oil.38 nC 17 nC.40 30.75 19. for examnnple mu I 00% error in predicted gas/liquid ratio could be equivalent to only an error of less than 0.59 46.25 41. with ahunrost no change in the total volume. nC.58 MPa.41 31.6. 11.64 44. its effect on the volume ratio is totally unacceplable.721) 2. can significantly improve the results. -118 -182 -152 -126 -126 -135 Gas Vail. Table 9. Figure 9. Such a beimaviour is expected a~tlme mmccuracy in munodlelhng the behaviour of heavy compounds. In compositional reservoir simulation.651 11.2 at equihibraim.325 11.53 9 VPT . where the reservoir is described by a number of equilibrium cells.266 811.627 Mcm CydI t’eumm (‘yet hex cC’.501 Equation SRK SRK3 PR Average Absoluie Devimutiiun % 37.1 aumd nrethanre at 373 K and 34.I~mlin.65 24. The deviations of predicted equilibriums voltnnmes by vumriotus leading EOS are shown in Table 9.05 36.84 21. l’ercenmtmmge error inn predicting pinase voluusmc by various EOS. Table 9.dunn’ 5 V~.49 16. EOS generally predict tine total volume more reliably than the volume of each phase at equilibrium. Whilst such an error in predicting the saturation pressure by EQS is highly encouraging. presented in Section 2..958 1)712 11.676 0.68 46.533 0.295 0.10.

. Tine optirmrunnn values of variables are obtaitned by nminuimnising time function A.20) 04 (-3 where cunchu elensmenmt of Ilse ol~ective fanunclion expresses tine weiglmted difference between tire prcclicled aund experinnmeuntmml vmslues. l. such as time critical point. temperature and pressure cain also have profound effects on lime convergence of EQS to a . mFIpreil mind ‘lft’xP. the various approumchmes are hmnsicahly siuinilmtr. are used to estimate tIne crilical properties of (lie carbon groups required for EQS calculations... often with signilncumntIy diverging restults mnmongst thenmselves. ( olnparisoiu of LOS 323 0 V E > 0 . wlmilst others may fail. as generally the nutnber of data points on the fluid saturation pressure is much fewer than tlnose of otiner properties. N. The pertinent comiditions of composition.322 20 9.n 9. -20 a ‘O ~4O o 0 S solutions. Hence.5W 0 o 0 7JRK PR) S 0 9. ‘The current approach in the industry to enmcounter tIne above deficiencies is to calibrate. none can he gtmmsranlied to scrlve tIne problem in all cases. mm Immrge nunnber of experinsmental data are often used in ttmning. 16 ~ E > 0 12 08 V (WNOn(X )—‘v~’ I ia C U ~0 C A= ~ wj~ ‘ (9. sucin as the consmposition of equilibrated phases. 0 10 15 20 25 30 35 Pressure.11 provides weighting factors as a rouglm gunide 133].~. Error in predicting phase ratio by variotus EQS at frount of Rich (imns mudvanscinmg in Black Oil (A) at 373 K and 20. TIne satuuration pressure is perimaps the most innportant property of a reservoir fluid for pimase behavioumr sludies. A nmodification of the Levetnberg-Marquardt nnethmod 1351 is often used to minimise the value of A in Eq. Gencrahised correlations. the converged equatiomss are not necessarily more reliable. Figure 9.Si. As the model is to prcchicl tine pimumse belnaviour and various fluid properties within wide ranges in conmsposilionnmml reservoir sinnnulumtion. EQS which locate time prevailing conditions away from the difficult conditions. 4 ppli( (ltiOii jul Resei’i’. than EQS characteristics. or ttnne. or preferably not rmsed at all. Real reservoir fluids.3 ‘l’UNIN(. defined as the sum of weiglmied squmarecl devmalionss. Time compositional analysis of these fluids mire not umiways very reliable mmmd tIne carbons groups are not fully defined. All cubic equations generally exhibit a similar convergence behaviour. Convergence problems may be observed unlso at conmclitions near Ihte rnumxinnsunm pressure and time nmnaximum tennpcrature of the plmase boundary.2.uuihuijo. Furthernmiore. w is the weighting factor and Nalalmu expresses Ilne mnuusnber of nsnemnsured data points t(n be fitted.(9. respectively. mm EOS nnodeh agmninrst experinncmmtmul dumla generated mit pertinent conditions for specific field sttmchies..20). t’lmmmsc hclumuvionnr nmiode’ Is bmmscd nun these cilumml iumnms nmmmmy predict Iniglnhy erroneous mestulls.8 MPa. should receive low weiglmtinmg factors. Robustness The robustness of a phase behaviour model in converging to a solution is more dependent on factors such as the matlmematical metinods of solving lhe governing eqtmuntions and inilial guesses tused in iterations. were (IeSCrihC(I in ‘Inmulster 4. The exercise is basically to rmnininsiise aim objective function. or applicable to that system. are described by a limssiled nuunrbcr of pure subslatnccs umn(I carbon groups. often converge.ii . 0 • vm’r -60 81) • .10. comniposcd of Ihousmtnmds of connnpounds.ess reliable data.2. Iligln weighting factors could also be assigned to more reliable experinnental data.()S. sommse uncertain values of input data to the phase behaviour tsnodel are adjusted In nsminimmnise tIne difference between tIne predicted and measured values. or converge to the trivial solution of equal partitioning of components between the phases. Ahtbmoungh time industry Imums not adapted a single standard method for tuning. they either canunot easily converge. All these factors further deteriorate predictiomis of EQS for real reservoir fluids. it needs a high weighting factor if it is to beconme effective. X~ designates tIme regression (Iunncdl) vmmriables. Comparison of predncted condensate/gas volutmietric ratio in a constant composition expansion test at 383 K by various EQS. at conditions close to the critical poinl. cvcnm for well clmunracterised nmodcl fluids uns shown in Scctiomn 9. lsmirlictmlmlrly for nmntnlticonnnponcnt nnixtures.9. The innportanmce of mm property is ensnplmasised by multiplying its deviation with a high weighting fumctor. puurlictuiumrly for unear cm it icmnl I Ituids. OF FA)S too • SKK3 0 2 4 Black Oil A/Rich Gas. MPa Figure 9. Altlmoughs various mmnethods [33-35] isave been suggested for solving multi-variable regression problems. Table 9. Mole Ratio 6 l’hc inmhucrcnnl deficiencies of F.

sen’pir Sinmuda. This can be due to the cancellation of errors at some conditions and should not be adopted. Property Bubble Point Density Volume Weighting Factor 40 20 10 9. App!iearion in R~. The swelling test with a rich gas. such as distillation. Tests unre genmerumily c. as described in Section 2. seidouin used in the tuning. provides useful information for miscible displacemeunt processes.2. the tuning simould unot be regarded purely as a mathematical regression problem. if required. Guidelines on time tntumber and selection of groups and the estimation of group properties were given in Section 9. Time type of experinsenlal data required for tuning has been addressed by several investigators [37. Tuniumg of [OS can be conducted with the fluid described by any nmunmber of conlmponennts.uilihrated phase are known In be genermmlly unreliable. certain equations may he preferable to others. Working in mass basis will retain the original compositional data. particularly covering conspositions around the critical point.2. excluding the near critical conditionms. the most reliable information on the relative concentration of light components is obtained by gas chromatography of the flashed gas. All reliable experirunensluml data should be used jun tumsing of EQS. msmolecular weiglnts. tuning EQS with a higlmerenmmpim~isison the liquid volume. [36] provide many examples. When the estimnation of produced fluid composition by gas cycling in a reservoir is the tnain target of the study. hence. particularly forgas condensate systems.3. The deviation between the predicted and experimental data is not only due to deficiencies of EOS. Tuning sinould not he comndiucted without considerations to capabilities of EOS. gas chromatography. Connipositiornal data onm eqn. but mostly due to the input data. rather than averaging the reported compositions. 7~ slnould be mmdcquate in most counpositional models. where the same fluid Inas been sent to diffeneust Imuhormllories for compositional analysis. llennce. high pressure analysis and mass spectromsretry. either by using the measured. Certain equations. (icumerumlly a severe tuning could indicate overlooked problems. For example. insproper characterisation. Fluid Characterisation The eharacterisation of single and tmmultiple carbon groups has a major innpaet on the results predicted by EOS. where a proper characterisation of real reservoir fluids has resulted in reliable predictions by phase beimmuviour ummodels without any tuning. and mill line discrele connspotmnds mis reported. The high pressure analysis also provides valuable infonnation for evaluating the reliability of the vapour to liquid ratio used in deriving tine overall composition by the flash method. is recomnnended.4. Aithougim usnost of tIme vami der Waumls type EQS are basically very siusnilar. kumown to be weak inn predicting tine liquid density. may be varied as atuning parameter. particularly the plus fraction. For example. Time parameters to he regressed need to be selected based on physical concepts and varied within reasonable limits. As tine measurement of dew point is quite subjective. whereas distillation provides reliable data on heavy components. Time nnolecular weight ofheavy fractions. Tuning ofLOS 325 Composition I Although the dew point is an important parameter and its accurate prediction is desirable. Experimental data should be generated at conditions closely sinnulating reservoir processes. may lemmd to serious problenms with prediclion of otimer data. depending on the grouping method.1. An additional tninor tuning of the new group properties.11. have revealed striking inforusmalion on tine dispmmrily of results. irowever. The high pressure compositional data on intermediates and lighter heavies are generally more rehimnble than those by other methods. seldommm cover all prevailing conditions. using tine quadrature tsmelhod. tIne luninmg process should primarily be conducted to evaluate and innprove tIne inrput (luila. Weighting factors of properties in tuning ofEQS. may be necessary. It is more logical to use proper characterisation and then attempt to improve other shortcomings. are available. Time eomunponetnts witlm their optimised properties could be grouped again to reduce their nuimrher. As reliable volumninetric data are also required in reservoir fluid studies. The concentration of components is alnmnost always measunred in munass (or volumnmre) basis in distillation and also in gas chromatograpimy. cotmid be considered annongst the first choices. particularly the plus fraction due to its low reliability. Pedersen et al. instead of the dew point. The capabilities of each method should be considered in driving the final analysis. to avoid loss of compounds in the flash (blow down) method. This is particularly valuable for gas condensate fluids. if gas injection is to be modelled by EQS. when questionable molecular weight data are adjusted. tunning of a two-paraumneler EOS. In genermul describing mine C with 4 groups. Section 2. assigning a high weighting factor to it may increase time deviation of predicted retrograde condensate volume. nnay lead to imigimly unreliable infommation at other conditions winere experinnental data is lacking. Matching tine dew poinl gencrumhly restmlts in over prediction of the liquid volume during the early depletioms stages for these fluids. The use of high pressure analysis techniques. which is often used in simulation of reservoir processes other tinan ‘simple pressure depletions.nnmducted at Ihe reservoir temperature to simulate reservoir Iii ~csses mmnd mmt lIne sepmurmulor tenumperature to sinunulate sunrface coumditions. such a treatment of compositional data will be . is preferred. would be tlme tnost appropriate choice. three-parameter EOS simould he selected in preference to the two-parameter equations. such as describing the heavy fraction witlm too few pseudo components. Selection of EOS Forcing EOS to match certain datms by excessive adjustnnent of its paranrmeters. or the generahised single carbon group. Many gas condensate samples show a liquid drop-out tail during depletion. to nnatch experimemn(aI density dlmmta. multiple contact test data are highly valuable for the tuning. For example. the data should cover the pertinent range of composition. pressure and teunnperumtture. or even lurtiner deterioratioun of predicted deunsity outside the raisge of available experiusnental (laIn. than relying on uncontrollable cancellation of errors. where tine flash mnetinod results in an analysis often leaner than the real fluid due to the loss of collected condensate. liney all should be used to determine the most probable composition of the fluid. Experinaental l)ata A proper analysis and characterisation of the reservoir fluid is tIme Inmost insnportanl step in successful application of a compositional model to determine the fluid belnaviour and properties.324 Table 9. which have consistently demonstrated their reliability. Furthermore. When compositional data generated by different metlmods. In general any leading EOS whicln predicts phase behaviour data reasonably well without tuning. ‘fine results are generally reported un immolc basis. Occasionally. Comparative studies. It is always advantageous to work with the compositional analysis in mass fractions. may lead to lower deviations of predicted results tinan timat of an appropriate method. The experinmental data. inmslcmud of modifying EOS parameters indiscriminately to mnmatch the experinnentuml data. Conventional PVT data may not be adequate generally for tuning of EQS. such as the Valderrama nnodifieation of Patel-Teja EQS. In general.38].ion 9.

properties of I)setn(lo-conmrponetsts. A cluamrge in sensitivity cmmn also be observed for tine EQS co-volume parameter. ‘rime scmnsitivily of predidtedl satinruntion pressure. had a profounusul effect on the results. An effective.3 where the liquid phase volummise nnscreumscd wutlm decreasinsg pressiure over a short pressure range below the oil bubble point. (Ire binary interaction paransmeter (HIP) wmms selected mis omne of tIme usnost effective paraumneters.3. ‘The deviation of any point fronm tine straigint line of ordinate+abscissa=i.4. Gani and Fredenslund (421 suggested a tumming procedure based on establishing the sensitivity of the prcdictedl resimlls. evaluated and improved prior to being used in tuning. however. . TIre critical properties mmmd tIme aceustric factor of pseudo components are probably tIme least mucctnrmmte inrput data. Clearly if suds data had been smoothed by time laboratory. inst their scussitivity to lIme spcciiic gravity.80). approach is to select and adjust those paranneters upon wlsich lime predicted properties are usnost Sensitive. rcsumltimmg ins adhjustutnent of critical properties calculated by the Twu msiellmod.2. tire nmrmuthnennruitical routinne mssay be designmed to rely onr adjusting the parmnnselers winich show high values of derivatives of time objective function relative to them.4 0. html usot mnecessuirily (lie unsost appropriate. however. by methods such as high pressure fluid analysis. or tlse nmolecular weight. such as the Hoffmann plot (40] or tlme modified Wilson equation plot. Deviations as high as ±6%for Ihe critical temperalure amid acentric factor and ±30%for the critical pressure of hydrocarbons may result frotns tlmese correlatiouss. In nnuili-variahle regressions. Section 4. Time critical properties are often estimated fromsm tIne specific grmmvity aund tine boiling poinnt. whereas systematic ones can be due to the error in nmemtsuring the aurnotumsls of phases. hiq. stucin mis iropcrties of lime pseudo colnnponents. Selection of Regression Variables line putrannelers thmrt uue ofteum used in humming are bitsary inmteraction parameters. nL+nv=nF (5.nulntjo. It is also very effective in cisanging the predicted results of [oS. Tine phase hehnavioinr was predicted using PR with the oil heavy end fraction described by otmly ouse pscudo-conssponent of C . In such eases. lime selection of BIt’ as a regressions varimmhle is mainly based on lime view that BIP is more of a hiltitng parannseter tlnuun mm pinysicmml property. equilibrated phase volumes and densities to the properties of psetudo coursponcumis in various processes. winich nunay unctually require innprovenmenl. wmus evaltumiled for mm wi(ie rmnmngc of flimidls [381. (Sr between all lime eornponennts. (‘omutrary to lIne connnnnnomm view. the specific gravity was found generally to be the usmost effeclive pmnranseter in tuniumg of [OS [38]. dmvcrt mittenlion from adjustinmg oIlier tnneerlain iunprml parumunnclers of [OS. Random deviations generally show errors in the conrposilnonal munumlysis. reliable compositional data.2 N (5.6 0. identifies the error associated wmthm tine measturcd rhata of tlnat component. the correctly predicted behaviour by EOS coumld have been regarded as a flaw. The predicted properties. ‘rime adjuslmmient of critical properties affect the predicted results linrough clnanginrg pmmrmmnnsetcrs of [OS. TIne accuiracy of repouled phsmnse conmlposition can be evaluated by comparing the number of moles of cads conmmpounerst nn tIne feed with the sum of those in the produced streams.2).u 9. can be presented grapimicahly (39] mis slnown in Figure 9. ‘line usmost connmnsoun approacls is to mndjtust BIt’ between tIne Iiglmtest componenl.0 0. ‘l’hse relmntive effectiveness of various paranmneters nmay depend nun tIne fluud type. such as swelling and multiple contact tests. Material balance calculations are the most popular method of evalrmatirig experinmmenlmn] data. Cenlammi plots.12. Applieatio.c.2./mole in feed Figure 9. specific gravity. The experimental data are given in ‘l’able 9. ‘b’.0 usiole in equi.u in Re.(4. particularly time critical properties and parameters of EOS. and lime heavy end fraction [33].2. Amongst line evumlumusted properties of pseudo commsponenls.rroir Sj.2. Smsnootlmitsg data may soumretimes mask certain ummcomnmusonm fealunres of mt pmmitncuimmr fluid. or 1 their cocfficieumts Umn mind ~ b. including time molecular weight. (lepcnding on tine fltmid amnd tIre prediction problem and selecting the most effcctive vumrimnhles for regression.2) The component balance equation. Imu a nnunnumher of tesled cases. that such calculations have not been previously iunmplensmented to smooth or even generate data by the laboratory. F(ir example.4. dlescruhc(l nun Sectioun 3. Eq.nF = x. can also be used to evaluate the internal consistency of comsnposutiommal datmm. it must be ensured. Ats exansple was givenn in Section 1 . nrsay he unsed in tinning. A direct regression of EQS parameters. or tIme lren(l reversed when it was increased by immore llmmmnn 3%.11 for the data reported in Table 9.. Tuning ofLOS 327 unjustifiable. 12—14 dcuuuonsslruulc lIme ci lcd of mmdjustimig time pmnrmnmuneters (sin deviations of predicted pr(ipertiCs in a nsnultiple forward coustmucl test of mm hlumck oil with nnsclliummne. however. Aguurwmml et unl. Note that changing the specific gravity of 6~ line pseudlo comnmponncnt. Sectioms 6. TIne tuning is then achieved with nninor clsmmnges imm origimmal himmrmunnnelers. (411 proposerl a nmmelhmod winere lIme nmmost effective paraimneters were selected (lynmmmsmicahiy frommm mm large set of paranneters dtmring tine regression process. Material balance plot of the compositional datum reported imm Table 9. umnay also be midjunstcd Iry regressiung tIme pmmmaunsctems of mm generalised correlation for BIt’. Figtnres 9.2 0. ‘l’luis unppromncln cmmun. time paramm’mcter ‘h’ can beconne more effective tinan tine mnttrumdtive ten-Inn parameter ‘a’ in pmcdidlimmg phrase behaviour of high pressure fluids. composilion mind parameters of [OS.8 1. should he generated.(5. present at a signnificamnt conmcenntrmnliotn in time mixture.1) and z. lsenrce.nL + y. of fractions using generalised correlations preseunted ims Section 6. The values of BIP bclwcemm tIme higlnlesl unmid lIne rest of cotnspomsenrts. Tine total and conmponenst hunlansce equmnlnons mine essentially those used in flash calculations. hunve also been suggested [33].n” i=l. U C U 0 ci cm > 0’ 5) C U 0 0. such as Eq.326 9. ‘lime adjustable parameters of the pseudo connuponrcmnts were varied in line rmuuige of -5% to +5% of tlreir original values to study their effects onn hsu’cdhictcdl plimnse hcluaviouur mmdl properties.11.

98 is) —0——— 50 ——— ~ . -—n-—-..91 0. - inC 4 i-C 5 nC.00 -6 -4 2 0 2 4 6 M S Adjusimenm% Figure 9. MPa Sat.nIc.. bin us u’nrnn.66 3. C 6 4 12..97 2. • in mmcm r~..79 Equni. dunn 77(14 99..se.58 374 17. Vol.6491 0.13.nn. glcm 0.96 1.1939 ~ui.31 1. I 2 Phase_________ Oil Gas Oil Gas 3 90. Tuning of LOS 329 Table 9. Effect of adjusting vunrious heavy end properties on deviation of predicted gas volume._.45 3. g/cm S (C~) M(C. cuun’ 36. ) 5 Pres. Effect of adjusting various heavy end properties on deviation of predicted liquid density.CuMr nfl 505 i’~.....6553 0.909 ii ——-— ~uw sir c in SOS -6 -4 -2 0 2 4 6 Adjusunuenu. Effect of adjusting various heavy end properties on deviation of predicted liquid volume.’.79 34. Dens.% IS Figure 9.42 1.694 0.’n(nr Sinuu!agion 9.00 Added Vol.79 MPa.80 3 84 94 117 126 140 153 165 180 197 209 Sat._.63 1..59 1.806 0.328 9. Appla’auiiuii inn Ru’.4 .45 8. Dens.12.843 0..) Forward-contact experimental d ata at 37 3 k and 20 . .14. ~ C 7 C~ C 9 C~ C~ Cm Cmi Cn4 C 0 C~. grannm/cm fin ‘fIne equnilmhratcd gas Iron the iirst smmuge was contacied wilh the frcsln oil in the second stage.6784 0.60 2.820 0.785 0. 2 2. Table 9.12 (Con.56 1..% Figure 9..16 m 0.6599 0. Pres.34 1.00 135.29 4..nct.1621 0.730 0..nwn i’ in i’._.00 90. ~1 10 —~‘0~~~ SC) 2% —‘—e’———— ~ —~—— ~~~~0~~ dOME —a—--— suw —s--—— muir’ i’nna..769 0.n.nnnncn SOS ni 0 a ~6 .01 137..838 194 3 Density.6896 0.36 11...nI~. MPa 20..754 0.844 0.799 0.64 2. Composition and properties of Black Oi 1(C).12.3.‘i) -2 0 2 4 6 > ~2 us 0’ Change in Propeumy.00 45. Component C 2 C 3 i-C MoIe% 34.

In tins method [431. l’unnning of LOS 331 Concentration of the plus fraction and its properties. Time results clearly denusonstrmnte that effective and probably unsore physically based tuniitmg.1. It camm be selecled as tIme tuning parameter. particularly of the plus fraclioun. reported previously. A powerful tuning parameter is tIme tennmpcralure coefficient of the attractive ternr in EQS.80). This will allow rapid flash calciulations in connrpositional reservoir simulation as described in Section 5. ‘t’Ise muccuracy of nmmeasured msmolecular weiglmt is mmsucls less tinmmui lhsmul ol lIne specnluc grunvity. Alllmormglm sinmullanseous mndjtnstnmment of regressed vmuriahles ussay lead to smitisfactory resmmlts. Pedersen Cl unl. K~w[(t. Tlse results of a ttmnimmg urmetlnodl usiung PR hut with no BIP.36). Kossack and Hagen [45] . along with heavy ernd properties. are hot very sensitive to themnm due to tineir low concentrations. can be achieved witlmorut uusinsg HiP. was used by several imnvestigators in a comparative Running exercise (391. they will be adjusted consistently when the specific gravity is varied to tune EQS. 9. As experirumeumlal data set covering all possible conditions witlminr a reservoir is not fortlsconming in nsiost cases. wlnere selected parannmeters are adjusted nut turn cmunm be unnore mippm’opriate.16. are preferable to adjusting a large nuummher of HIP vmulmmes aund shift paranseters. For exammnple.4. ±1%.330 9. when using a two-parameter EQS such as PR arid SRK. a highly effective tuning can be achieved.2% respectively.suuhntio.2) a > am iso F’. A connnlmimnmmtion of rchimmhie EQS mmmdl properly characlerised fluid data should lead to predicted results close to cxperiunmcnlal valuncs. The plus fractioum propeu’ties strongly affect predicted properties of condensing fluids. Specific gravity is one of time IrlosI effective parameter in adjusting the predicted results of EOS. > It is advisable to reduce tIme nunnber of variables in the regression to avoid nrnusscricmml problensis and innprove the searcin for time global nr’minrimum of tIne objective fiurnctiomm. ‘lucy all.3. 15. For exmmmsmple. swelling and nrumltiple countact vumpour-Iiqsuid phase equilibrium data. Applications mu Resc’s u’pur . boiling polunt mmmdl time specific gravity of pseudo components are about. pmmrticulumrly for lIme average hoihimng point. however.8T )~]/S 6 (6. msre unnucin wider f(ur the plt~mfm’act monu.Si. ilue mud mnslnnscnmt of the mmhove properties witiminm Ilneir error bmnnds. were described in Section 4. in 1985. The above critical properties are calculated from generahised correlations based nun tine specific gravity and normal boiling point temperature of carbon groups. I-lenncc. amid those of lIne volume shift eorrelatiomm. their adjustment us quite justified.1. lead to unrealistic values for the tuned paramelers. very little need for tuning. lime smut pmmrummsmeters oh carbons gromnps were also mndjuusted. however. It can be readily used as a tuning variable. line above hmmnnds. tIme unsuiltistage tuning. A cotnspreimermsive dmntmm set on a voluntile oil. as tine variation d)f linis factor is relatively small for carbon groups. whereas the trend should be opposite for tine critical pressure. Eq. Met hodology Although adjustment of BIt’ ium tunming of EQS is quite common. nnmmuy nuot be suit mc cml lii mis: Inmeve tIne required tuning. tIne specific gravity of time plus fraction and also its nsmeasured commceuntrmitioni. l’he critical tennpermmture. It is inmportaunt to mnaintmmin the consistency of regressed pmiramnetcrs whsenm usnorc Ilnams us single variable is used to tunme a phase behaviour model. used BIP as a tuning paranmeter. severe tuning should be avoided. ‘rIme deviatiouss of Iluese cori’cimilionss.cssuire. Sensitivity of tine prcdictedl results to artjrns(immg input data generally increases when the criticuul poimit is approundtscdh. MPa Figure 9. This coefficient and its adjustment for sumper-critical colmnponnents. iIsal cormld. are also shown in tlnese Figmures. Conmparisoun of relative vohuuumme in differential liberation experiment predicted by variomis lmnnned nniOdlels. by just adjusting the properties of carbon groups.u 9. All lIne participants used time Peumg Robinson EQS (PR). Wider linsnits for tuned parameters provide higher flexibility for matchrimmg expermnssentmml dlatmi. For example. Tise suitability of the nusetirod for guns condensate systems has uulso been demmnonnstratcul 1441. K~. however. Typical error hands for measrured molecular weigin. musing generahisedl property cou’relalionrs wlnicim introduce mmd(hitmonnmnl errors mlmlo [OS. hence. uncentric fmmctor and the boiling point temperature shotnld generally increase witim the molecular weiglnt or carbon number of pseudo components. can be regarded as the hitmsits for adjusting the properties. ±1%amid ±0. Eq. Limits of Tuned Parameters it is reasonable to adjust mneasured parameters within their error haunds in tumnimug. such as the density particularly at low pressures.(4. hence. regressing the parameters of time BIP correlustion. ‘[Inc nmmaium drunsvhack of rising onsly tIne properties of pseundo components. are probably lime icmmsl reliable immptut information.(4. applying different in-house tuning methodls. the results of tIne tuned unodels for some properties are shown in Figures 9. mis tIme lcmmst reliable comisposiliomnai inforunatioum. Tinen the volume shift fmmctors of pseudo connnponcnmts can be adjusted to match lime density dmmta.15 and 9.4 I)YNAMIC VALII)A’l’ION OF MODEL As all the critical properties and the acentric factor are calculated frorns time specific grunvily and boiling point data. As these experimental data are employed to calculate tine criticmnl properties of pseudo comniponents. wider adjustments are acceptable. constant equal to its original value. A phase behaviour nmsodcl wilh its input pumrmuumnetens umdjtmsted widely woumhd lead to unrealistic resmults at conditions otlner Ihmln tlrnse tested in tine ttmmsinrg. Pedersen 1361 suggested adjusting tine ismohecular weight by as inngin uns 0%. prior to goiung back to the otlscr regressedl pmirausmctcrs for fine tuning. the denrsnty data can be initially left oul of regression. is thmnt tine guns pmnase propertmes. Typical laboratory uncasuremneunts mused imm tuning include conventional PV’F data. without resorting to BIP. were unsed as time regression pmmrmmuuuelers. with the boiling point related to it by nsaintaimrimsg lise Watson cinaracterisation factor. (36] have reviewed the danger of tuning by considering various cases.

Figure 9. Two phase nsnixtures equihibrmuted at tine test tenrperature and pressure were prepared.25 4 5 6 7 8 9 50 Khazam et al. 1. 0-S 0.4 am 0. timerelore. The choice of an almost one-dinnensionmml flow mm ut properly designed tube displacement is reasonable. smmchn as rids gas injection. as time effects of dispersion.’ such as asphaltene deposition. an accurate prediction ofthe displacement can be expected froun a reliable phase behaviour model. at alunmost no nmiass transfer cotmriitions. Relative Permeability Function 0. which is to be used in a reservoir simulator to study gas injection. U Esp .4. A similar conclusion was reached also by Mansoori et al. Contacted Oil Volume! Iunj. Applmcaounm jim Reservoir Sinnulation 9. if necessary. includiumg real reservoir samples and concluded that a single set of relative permeability-saturation curves is adequate in describing the flow hehunviour of all fluid systems which lmave the same 1FF value. ‘Fhmesc paraummeters. the immobile oil left behind. Hence. They concluded that an EOS tuned to the static PVT data was not adequate for simulating fluid displacement.21) and V. The investIgators conducted displacemenmt tests. wimicln dctcrunnines tIne nummxlnnre cnmunilsumslmm(mnn. As tIne unmeasurenmemmt of relative pennieability in a slim tube at various 1FF values involves a major effort.vtnnr 0. Hence. using different fluids.35 Fqs. investigated tIme relative penmiemihility of gas-oil in a slim lube musing binary fluids. should be able to predict the fluid Tine slimnm tube was pumeked witlm tIne liquid and displaced with the eqmnilihrated gas. kk At’ (9.45 0. It is. gravity override and heterogeneity~ which are significant in a large three dimensional system. in simulating the gas-oil phase behaviour in slim tube displacement tests.8 (00. where miscibility is not achieved at the two leading and truuilinng edges of time transition zone. relative permeability correlations may be used instead. thmmt is approaching miscibility. ~t is the viscosity and k is lime tube absolute pernmmeahihity. It is evident that as 1FF approaches zeu’o. 1471. that is tuned to all the relevant static data. is the simplest apparatus that can be used to plmysically simulate compositional changes resulting from the conlinuuomms contact belween lime inmjection gas and the reservoir oil.332 9. Methane Vinlumnnc Figure 9.17. Generation of suncin data for soumme processes. APIL is tIne pressure gradient along tIre tube. which may not be evident in statistic tests. the interfacial tensions (1Ff) and velocity at the displacenment conditionss. I)y.u ofMode! 333 studied the capability of EOS.0 conditions in such a simple displacement. The flow of gas and oil in a slim tube is described by the L)arcy’s equation. ‘55. Therefore. tuned against static experimental data. 0. by checking its performance in predicting slim tube displacement data. after proper implementation of the above factors in a numerical sinmuimnlor. dcpenmds nmnu lhue relmilive peunnncmnlmilimy cormelmml moms emnpioyedl inn lIne sinumtnlationn mnsodcl mnnmul line viscosity of hot in plmmnses. these factors need to be carefully isolated and detennined.65 kk AP (9.22) 0.0 0 20 40 60 80 100 Oil Samuraumon. viscous fingering. however. it is advisable to further evaluate the phase behaviour model.04 mN/m. shnounldl be dcleu’mnmimncd relimihly inn uudvamnce. ‘fine test was conducted at different pressures over time iumterfacial tension range of 9. lime l)Imuusu’ hclnuuviotmr. decreases towards zero and tire relative permeabilities increase. kr is time relative penneahility wlmich depends on the fluid saturation. Imenuce.iquid • t~p .17.16. if the phase behaviour model is to be evaluated against displacement data. are minimised. further tune the phase behaviour model. The slim tube.2 1-22) clearly dennmonstrmnle tinmnl tIne ratio of lIne flowing pinumses. the residual oil saturation.i.manmic Va/ida. reasonable to expect that a reliable phase behaviour model. The flow parameters and numerical methods incorporated in the sirnumlation model can strongly affect the prediction. It has been demonstrated [47] that. is not practicable in static tests.(9. The test could also indicate unexpected phase changes.6 The experimental data used in tuning of EQS sinould cover the conmposilionunl range occurring in the displacement process. [46]. V is tine fluiul velocity.2.. It is. C0. the comparison of the displacement data with simulated results of a compositional model using the tuned EOS can be ennployed to evaluate and.2 0. Comparison of gas and oil density in a forward contact experiment predicted by various tuned models. therefore. Variation of gas and oil relative permeability with interfacial tension (tFT).55 —— ModelA Modetli Modei C NoBIP where.jo. described in Section 7. A different set of EQS parameters was required to match both PVT and displacement data. ‘[he results are shown in Figure 9. essential to .

The thirdi approacis uses the concept of residual viscosity. extendled In lnydrocarhron reservoir flmnids.k.l0I325) in order to obtumimi the viscosity un nstPmm. as imsrplcuncumleul buy I. 1581 extended lime mihove In nnnixtmmres. but with vokuunne replaced by viscosity. tine corresponding states methods. Section 2. particunlarly for gas injection processes.4. There is very little reasoning behind linus approunclm.. Hence. [531. where the redunced viscosity. mind P. by prusposing the Herning-Zipperer mixing mule (601 for lIne low pressure viscosity mind tIne mnmolunr mixing utile for other properties as foIlmiws. relative permeability. There is no useed..’ln’olemmmnn imudiustry. The correction factors adjust tine deviation of time predicted result by comparing it with the viscosity of one reference fluid. Du’nanuic Validation of Model 335 measure the relative pern’neabihities at a single high IFI’ condition (base curves) as lhsc starting input data. similar to van der Waals type equations. saturations approacim straight dIiagonal lines. Applscasuons so Re.3.u e. Cuuhic equnations.25) should be K and atm (MPa/0.. The increase of temperature.040758 a + a p + a p~+ a p~+ a p~ 1 2 1 1 4 5 (9. is insignificant. sunclm as tine reduced pressure and reduced temperature. the above approach predicts acceptable data in most cases. Although the viscosity is not a thernnoclynanmic state property. and rtreasuuring the production rate and the differential pressure across the tube.s (cp).olsrcnz-Bray-Clark (LBC) [58]. Jossm et al (59] nnsultiplicd tIne residual viscosity by ?~ to unmake it dimensionless and correlated it witim tine reduced density. It is required to use a single method to predict the viscosity of both plmases at such conditions.uumucsmlanly ins rescrvunnr smumnmmlmntiomn. lime nmnellnod is hasicunily tbnmil of Jossi et ~mi. to usseasure the change of relative permneabilities with lET extensively. whereas lIne viscosity (sf gmmses at low pressunre can he reliably deteruimined by time kinetic Iheory of gases. 55 h is the base IF]’ and mm depends on time porous usrediuuni type witlm mm dlcfmmmuit vmslue of 7 The value of k~ cams be assumed equal to tine phase satunruilion. tIne residuuul phmnse saturation values decrease towards zero umund line relative penumucuitumluty curves vs. provide all the reqmnim’ed data to detenusnine the relative permeability using a graphical method [48]. its effect on the evaluation of phase behaviour model.°” 1X l7. some correction factors are included in these correlations. X ‘F~M ‘i’~ (9.23).m° is line low pressure viscosity whicln cmmmm be determined as. methane [53-54]. may not be suitable for reservoir condiliotis.(9.olnrcnz Cl mml. however. + (I — F. except at nmear critical conditions. = ‘line knmnctme theory of guises slniuws thaI time viscosity is inversely proportioumal to. for pure connmpouncls as. which is defined as the difference between viscosity mst prevailiung coundilions aund linmil at low pressmnre whmere the viscosity depends unmshy on tIne Ilmerusnal cumergy. A nuunmbcr of correlmitions (47.’u’our Si. annul F is the scmnlmmsg functor between time bose 0 relative permmseabihity krb and the miscible relative permeability ~ F is a function of the interfacial tension. Altisouglu tisis simple interpolation approach.023364 2 a = 0. defined mis lime rmnlio of time fluid viscosity to that at the critical point.334 9. those correlations developed either for gas or for liquid.(9. iii Eq. )k. 0 F. The Coats correlation is based onr the commcepl lhsmml is tine interfmmcial tcursiimn between tIne two plmmsses appromicines zcn’o nmcmnr line critical point ( immiscible conmnhit ions). Ely and Hanley [54].58T l.(X)93324 5 amnd ~.058533 3 mu = -0. This mnpproach.67) /X 4 Tr 1. methane and decane [55].24) wisere mn = 0. One of the earliest atteusmpts to correlate gas-oil relmulive peu’msuemuhiility witim lET is that of Coats [50]. (9.25) F. =(~‘~b)” ~. One set of relustive pcrnsscmmhihity curves at a low 1Ff value and the base curves are sufficient to define tine parameters of a gemmeralised relative permeability correlation. as follows: [(p — ~u~’)x x + l0~ = (9. is relaled to two redunced sImile properties. P 1 = p/pt. l.23). 1591 for ptnre commupomiuuds. using slinmi tube dispiaceusient dumla.27) = Note that lime units of T. 57]. Pedersen et al. or time reduced teusiperature and reduced density.5 (9.usikuio. A nunmber of methods are applied to both gas and liquid in reservoir studies. At high pressures. fn°=34x10’ T.1023(1 1 mm = 0. lime behaviour of gas viscosity is more liquid-like (Figure 2.m I 9. have been proposed (56. which can be classified into three groups: First. Eq. will result in zerur rcsiduual oil mit mill 1Ff conditions...28) X =(txT~JtxM)~(txP J~ 5 (9. As reservoir fluids cannot be modelled accurately by the simple two parameter corresponding states principle.78X l0~(4. is mused widely in tine p. or two reference fluids. Displacing a binary oil with its equilibrated gas. I he suggestedl to cstiumnmulc tIme rclmulive pcmnnmcmuhihnty mit aumy 1FF vmnlue. 49—51] lsave been (IeVCl(ipcd to miccounusl for tine el fed of 1Ff our ‘lire second utpproacln is based on time analogy between viscosity-temperature and specific volume-temperature beimaviour. decreases the liquid viscosimy whilst it increases the gas viscosity at moderate and low pressures. especially when miscibility is approachedl and the properties of vmnlxmur and liquid become similar. by interpolation betwceun the base cmmrve dlelcrnnmincd mnt luigin lii’ mmmd tIne slraiglsl diagonal line. Viscosity Prediction The viscosity of a single phase reservoir fluid increases witin pressure.26) wisere (52].5 i’~>1.. apmmrt from the similarity of pressure-volume-temperature amud pressurevuscosity—lensspcrature plots. as described below. 4 a = 0.. N (1° = N ~x~p~’M? =1 / ~x~M? (9.29) .23) wincre kr is tlse relative pernneahihity to gas or oil. line rcsiduuml viscosity cmiii he related to tIre fluid density. p.

valune of X for immixluire is cmnlcnnlated fronmm Eq.701 29. C~=37.2 1.00210 0.8 > 0.6 v.05 10 nnPa. ‘total 0.4 I---- o2 to 20 Pressure.705 58.02150 Reduced Densimy xM°’ 2.04706 0.20900 18. respectively annd tine estimated 3 critical volume is in m lkgmol. It unray predict oil viscosity with deviations exceeding 100%.4 1.9 nC8 0.34629 5. 40 20 ?4~ 4’ . is shown in Figure 9. Hence it should be used only in consbination wills EOS winich are known to pmechict gas annul liquid density reliably. The liqmuid density at the above conditions is 3 0. as.4083x10’ M~. Ileisce.84583 ~ .~. where the measured and predicted viscosities have been matched only at the bubble point. + 4. 1 l3.417 15.47 74.(9. atm Cl 0. U 1.37519 2. cnm’/mnoh 98. as apparent mm Eq. It is common to tune the nmodel by adjusting the critical volmunnue of tine C + fractions to nimatch the measured data.97 3.368/29. g/gmunol ‘Ic. Applicalion in Reservoir Sinmnlatio.68 MPa.19.(9.2(1 -40 -60 A A A Prop.18 shows the deviation of predicted viscosity by Eq. mPa.231 568.7 24.Sc. A successful example of sucim practice.6 200 t~s -80 • • • n-Dusujcc.733)xi49. reduced density is cmilculated froums Eq.~ nu—Ikoanie n-Os’uminu’ n-I)crznune The properties of pmmre conmnpounenmts are read froun Tumble A.=(0.43 269. K Pc.3468 + 9.~ 0 0 ° £ U 52. with time critical pressure converted to atom (divided by 0. S(.24 molc% at 311 K mind 20.uict’. 28-30) 0 I 2 ‘ 3 4 Cl C3 nC8 0..1) where PM is the molar critical density and v is the critical molar volume.796 43.n I 9. the unnctlnod becomes unreliable for dense fluids witin reduced densities over 2.14=h .30. MPa . The amnthors used the 5 to back calculate and correlate tIme critical molar viscosity 0data of a number of reservoir fluids volume of C .29) to he 0.27).05052 0.00864 0. xvç 26.(9. The method of Lohrenz et ai.14 The ‘I’hc valume of 1” for nnmixlunre is c.101325) and their viscosity is calculated fronnm Eq.nuue uu’Peuuu.26) for pure connmpounds. (9.513 16.30) p.54 xM 9.83 41.5 [61]. a U a 0.1) 41) Figure 9.46 and nCg=3.28) to he 0. The above approach improves time predicted results 7 markedly in processes where the heavy fraction remains almost intact. is quite sensitive to the flumid density.01134 0.s (0. Example 9.31) 5 where M and S are the molecular weight and specific gravity. Conump. The mixture p. = v / v 5 52.63203 0.huuiolm: .03343 0.92 Figure 9.0() 138.368 g/enn .5.7265lS~.518 xP.4 C3 0.00605 given mn ‘Fine usnixtmnre properties are then calculated using the nnixing rules Eqs (9 .18.i us Appendix A.s.0096992 mPa.iuie n-Iiummnne un-Pcuuuan. Consmpmmrison of predicted viscosity by LBC nnctlmod with experimeuntumi dama of mm North Sea oil at 371 K. as.(9.26).84092 0.03 186 0. 1.75 149. I)ynuanuic Validaiimm ofModel 337 PM =(v )’ 5 5 =(u~XiVci)~~t . mns follows. Clearly the correlation loses its reliability for heavy compounds.3746 44.6 0.48752 xi’.733 0.05 hO cp).593 16.915 15.t)324 114.ilctulmnleil from Eq (9. 7 3 (v )~. Deviation of predicted viscosity of pure hydrocarbons by the method of Jossi et ai.(9.02693 0. Figure 9.096 369.s 0. (9.30). = 1.0377423. The nmeasured viscosity is 0. x M.043 191)56 45. Estimate the viscosity of a liquid Menlumnne Eilnannc mixture conmposed of Ci=59.4.iuue un-I Ieptmuutes’auue 486 T.4404XlO~”Mc — l.54686 ~t°.336 1 9.19.

‘I’Ine ltuused mrsodcl nnatchcd tine volumes of vapour and liquid phases in equilihriium tests wills an average absolute deviation of about 3%.9 1. cmmn be identified by conducting miscible liquid-liqumid displaceusmenl [471. . At conditions approaching ussnscihihnty.(9. the numerical dispersion can be conmsidered equnivumlenl to lIme plnysmcmul dispersion. For mummy nsununher of grid-blocks. of 311 K.s. more grid blocks are required due to sharp changes of fluid properties. tlu’uuce. with the composition and density reliably predicled. The use of these approximations introduces truncation errors and nmuusnerical dnspersion. along with nmeasunred relative pemnmeabihity curves and the optimum grid-time step sizing. p_~n=O. The Peng-Robinuson EOS was ttmned to tine vapour-liquid equilibrium experimental data of Sage and Berry (63] on the above ternary system and multiple forward contact test data (64].68 MPmu were mnlso qmuite reliable. Pore Volume injected (fraction) Figure 9.muunl/. whiclr yields the best nsatch between tine predicted and tIme experimental effluent profile.O 6 mPa. 100 grid blocks are generally needed to achieve a stable numerical solmution.20. (62] cumnn be used to determine the optinm’mum tinme step-grid block ~iIlmzero dispersions. Tine mtmltiple contact test at 20. In the slim tube displacement the pimysicunl dispersion is generuilly sinumull mnusd cams he mmssmutned zero in most cases for lnonmmogeneous sand pmmcks.79 MPa are shown in Figure 9.2 0.S’inuuulaiion 9.0 1.338 9.79 and 20.4. which resulted in a significminl deviuml ion betweeim tine predicted and nsieasured displacement data. Application in Rcse.21.(4 ] to a liquid nnmxture of CI/C3/nCl() displaced by methane in a slim tube at two pressures of 13. hremmk llsrougim mind prodtncing gums to onl ratio values.’u’oir . tine aunthors dclihcrumleiy usuistumned the model aguminst tIne static data. Memisured aund predicted displacenmnent data. Fraction Figunre 9. 7 The above approacis was applied by Khazam et ai. ‘I’o indicate lime sensitivity of disphumcennent results to tlne phase behaviour nruodel.26) results in. ‘I’Inc simnuhumled displacenssent resulls at 13. particularly the gas The degree of sImm tube packing homogeneity and time associated plnysical dmspcrsion. Tlmese paraunetcrs should be selected so tismul tine nunscrical dispersion becomes close to that of the physical dispersion in tIme lube. sensitive to (lie numusher of grid-blocks mnnd Imusme-step suz.5 2.1 1.68 MPa imndicated the mmclsicvcnrsent of umsiscihihily. Tine tuned plnmnse helmaviouur umnodel was inscorporated in a one-dinnmensional numerical unodel. iundlncmmled by low lET regions. at time test temperatture amid pressunre. Variation of simulated effluent conceustration profile witls Immune step size its a shun tube modelled by 100 grid blocks. so C 40 0 20 ‘0 Q0’i’i~0t’52.20.0 1 E a LC Li C 0 CI C) 5) 0 0 0 a C-) C 0) C LL~ mm 0. therefore. The simulation results are.68 MPa and tennnperature a 00 05 1. to predict tIre above. TIse umnetlnund proposed by I .8 t). uunstemudl of counduicting liquid-liquid displacement. demonstrating miscible (hisplaceunnent (64]. For a typical sliuss tube. lknanuic Validation of In’! ode! 339 4 Substituting the above values in Eq.s The predicted valume deviates by 8% from the measured vmscosmty.0 Pore Volume tnjecied. Time resunils mit 20.21.0 1.e usc(h to model the slim tube displacement. TIse unodel tuned In tIme static dala clearly is capable of predicting the dynamic experimental resunils. For the opluumsmscd grid size-time step. can be identified as shown in Figure 9. Implementation Most reservoir simulators available today obtain solutions to flunid flow equuatuomms (non-linear patlial differential equations) by replacing the derivatives with finite-difference mippmoxinmations.O37l 5 usnPa. the optimunu time step. 4 84 p=O.

The plot also denmonstrates that the dew point becomes less sensitive to the recombination ratio as tIne separator pressure increases.5 EVALUATION OF RESERVOIR FLUID SAMPLES in a saturated reservoir.2. the lack of seumsitivity affects line recomunhination ratio markedly mit Imigh pressures. as time two pimases nit Inigh pressumres mire more siuusilar than at lower pressures. The dew point pressure. If time separator pressure is equal to the saturation pressure. however. with properties significantly different to those of the reservoir fluid.4 Mole Liq. then. disturbing the produced gas to liquid ratio.’ 5) 32 31 3(1 Separamor Pies. Hence. Predicted dew point pressure of reconnbined separator gas and liquid samples.22. The authors conducted an extensive investigation of susmumpling Irons (lepheled reservoirs to determine the original reservoir flinid mmsinrg comumpositmonnmml smunmuimmlioun. Evaluation and improvement of a collected sample generally benefit from a combined experimental and numerical modelling effort. 9.. The swelling test. ‘I’he equilibrated gas and condensate plnumses were tlsen rccouumhinmed nil differcmmt rumlios at cads pressure.’ C 29 a cm.5. The collection of a sample that reliably represents the reservoir flmnid is essential ium any phase behaviour studies. Phase behavuoumr mmnodels cmtnm play an important role in helping the above task. or time dew poimnt of time gas samumple. represent the original reservoir fluid in oil and gas condensate reservoirs. covering both sides of the critical poinrt. They used a nnodified black oil simulator to produce from a low permeability lean gas condensate reservoir amud an EOS nmodel to simulate the recounhination of separator samples. As tine target dew point has a certain error hand. Processes occmmrrinmg witimumm lIme reservoir generally need to be modelled by a reservoir siumnulator. however. respectively. Some processes. the higimer is the difference between the two recombination ratios which resmult in tine same dew point..2 0. The bubble point pressure of oil is a unonotonic fumiction of the gas to liqmuid recombiumatious proportion. Pinuuse heinaviour nmodels are required to simulate more demanding equilibriummm tests. tine bubble poinnt pressure increases with increasiung gas to liquid ratio (GLR). They recommended a method to hack calcunlate the initial reservoir fluid composition by matching the initial reservour dew point pressure. will be higimly unseful to generate static data for miscible processes [12]. Souse of time key issumes and pitfalls in fluid sampling were described in Section 2.69 3. if tine condensate formed at the dew point is added to the saturated A main concern in surface sampling is the recombining proportion of the collected liquid and gas from the test separator. can be physically simulated by simple experinnents.’ Is (1. If these processes can be reasonably ideumtificd. such as a snmmgle equuilibriumnnm flash. However. . The equilibrated oil and gas phases. The results clearly show timat tine higlrer the separator pressure.1.340 9. resulting in changes of its properties. i.31 211 0)34 27 26 0.1 0. The authors showed that the dew point pressure of a wellstream (recombined sample) was lower than the initial dew point of reservoir. ~13 CI cm. be close the above value. Figumre 2. may increase. tIme saturation point of coexisting gas and oil phases should be equal to the reservoir temperature-pressure at the gas-oil contact. however. Applieatioin in ke. As time GLR-dew point pressure curve is dome-like shape in gas condensate nnixtmnres. Eu’aiiwtion ofReservoir Fluid Sanuples 34 I The slim tube displacement data are certainly valuable for evaluating a tuned phase belmaviour model which is to be used in reservoir simulation of gas injection. decreumse. neglecting time compositional grading in space. In practice. in immiscible displacement processes.94 MPa at 383 K. it may be possible to trace back the original fluid from the collected sample. ‘I’lney proposed experimental methods to obtain the original fluid fronnn collected sammnplcs. Figure 9. will be of little value inn studying that reservoir. MI’a C) cm. Therefore.s.nndaiirnu 9. The main source of error in sampling is the phase transition and collection of co-exitiung fluuids at an improper ratio. Theoretically. no condensate will form.79 20(’u( 0. ntis less likely to select the wrong reconnbination ratio at high pressures when mminning to matcim time dew point. Fevang and Whitson [66] extended the Reffstrup and Osien’s mnnethod to cover otlmer types of reservoirs. Reffstrup and Olsen [65] studied fluid conmrpositional clmanges during surface sampling under non-ideal sampling conditions. it may not have tine same composition and propertIes mis the ormgmnuuh reservoir fluid. the compositional variations with depth aund area are rarely negligible. ‘‘I 689 13. it is expected that the nreasured bubble point of the oil sample. in principle. based on their simulation results. Gas Figure 9. However. it is a reasonnahie practice to ignore time measured GLR during oil sampliumg aumd take oil and gas sanmples fronun time separalor and recombine timeun to achieve tine target bubble point. A key recommendation to obtain the original reservoir fluid in saturated reservoirs was to equilibrate the samples collected from the gas cap aurd the oil zone at the original reservoir gas-oil contact. Add/ Mole Sep. The collected sample may have gone through certain umnwanted processes. ~Flnebelmaviour of mm typical North Scum guns condensunte. tuning of the phase behaviour model to relevant stalic equilihriuumrn data should generally suffice and there is very little need for relatively tinme consuusnimmg displacenrnenmt tests. a model tuned to experinnental datum of a saunpie. pressure and temperature. with a dew point of 31.3 0. Any fluid produced from a reservoir should. provide vunlununhic muslomnnmunlion nun tIne reservoir fluid. Challenges in obtaining representative samples from gas condeunsalc mmmd volatile oul reservoirs have been well acknowledged by those involved. but higher than the bottom hole pressure. the effect of deviated gas to liquid ratio in recounhination on the total fluid composition and its behaviour is less significant at isigher pressures. imperfect sepmnration of the phases also causes either some liquid to be carried over witin the gas from nun upstream separator to the next (carryover) or some gas to be produced with the liquid (carry througin).1) . i-lensce. il is possible to obtain time saumme dew point pressumre wills two different Ci LR ‘s. After all. or remain almost uncimanged by increasiumg GLR. was simuimmted by flaslminmg it uml vmmrious pressuires. Any uncertainty in the measured gas to liquid rmtlio in the field directly affects the composition of recombined sample and its properties.e.’rn’oir Si.22 shows time predicted dew point of tine differenst recombined fluids.

App!ieaOon in Reservoir Si. I tencc collecting tire produced flunid can provide a reasonable representative sample of the original siumgle phumse gums. 20. 8’ a > a a aa 0 Recom. ‘lime overall connnpositioun of the produced fluid with time is simowmm in Table 9. the region should nol grow at all winich is not tine case. Ann nmdeqummmle volumunse of line rensnoved liquid is added back to the gas to mnatcln its dew point pressmure to the initimml reservoir valume. If lime rmute is decreased to reduce the draw down. Note tlsat tIme composition changes very littlc with time and it is almost the sane as that of the original reservoir fluid.22). as a lower condensate smmlumrmmtiOn is requmired to unmmuintmiin tine rcdunce(l condensate fractional flow. [lay tOO 000 point and the two phase region. Growtir of commdcnsmute rimmg witin linme for a typical North Sea producer.23. regardless of the phase ratio.u I 9. nun unpproximnsate quuasi steady sImile msmmmy bc eslmublisimed ins thuit regiour. Both actions may lead to mm smmnmnpie mssunciu richer thunun tIne original reservoir fluid. with a false GLR selected. is shown in Figure 9. The two plnumsc sulnnulslcs cuullccted at lime sumrfmmce mire rcconsbined at the nnicasured GLR to obtumin line welihmead stremmun.25 shows time growtlm of line two phase region by depletion as simulated numerically for a typical Nortln Scum produmcer. The rumain imnpcding factor in collecting a representative fluid sample is the pinase lrmunsitiomm due to pressure reduction aund the variable mobility of the phases witimin the reservoir. Figmire 9.24.uion to C 0 The predicted liquid drop out of tine mixtumres in the above exercise recoussbinned at time atmospheric pressure.24.22. Figure 9.5. in spite of the significantly extended condensate ring. as follows. A long flow period to slahilise the well and its drainage zone is often advocated. Predicted liqunid drop Out in constant composition test at 383 K for various reconnbined fluids.u ofReservoir Fluid Sample. Tisis results in amm increase of coundensale to Figmure 9. 17. Distaist~c 10’ • • Original a a CI 5)) 0) CI C 0) cm’ ‘a C a 0 Fignure 9.(9. thmnt for a gas con(lensate reservoir a representative sample may he obtained (luring nonsnmml operalioun if a quasi-steady State zone around the producer can be acinneved.13. if line above arguument was strictly valid lisrougluouut tine two plsasc regiusmi. html mnlso dunmrps sonsse conmdemmsatc into the well. ‘lIne usnixture is linen brougist to equilibrium at the average reservoir flowimrg pressmsre (or line imottonsn hole pressure) and temperature and the remaining liquid plnunsc is removed.342 9. Note that mmltinoungln tIme -3% error inn dew poinnt corresponds to a much higher deviation in the reconnhinmitioum rmulio at tine higImer pn’cssunre (Figure 9. . Figure 9. with the overall coumnpositioms of the ountflow beinng lIne sunmnse as timmmt tlowinrg imsto tIme region.23. grows into tIne reservoir hulk by continual production. Tire increase in condensate saturation increases time condensate relative permeushility mind decreases the relative permeability of tine gas.1. when the pressure falls below line dew U. tIme resullinsg pressure bdmiid-up not only vaporises the condensate iuslo lire gas plsase.2l-22).r 343 gas. Sauur. Tine collected sausuple cminn he innrprovcd fuurtlncr winenr line reservoir gas dew poinmt is known. Isowever. The condensate saturmnlionn at army locatiorn increuiscs due to the local reduction of pressure and the inflow of rich gas towards the proiluncer.7 MPa False GOR 6’ - 4 a. Gas-condensumle distribution arouuumd a producer. referred to as the condensate ring. line condensmule satuura(ion increases only to the value winch nnaintmsins (tie associated frmictiomumil flow. > (It to Time. The predicted results with -3% error its tine target dew point pressure are also simown. However.alima(no.’ : ~ is Pressunre. Pies. Tlse mumixtunre clearly lacks the true behaviour of the reservoir fluid. the results are more acceptable than those at Ilse lower pressure. it was noted. Eu. Tine condensate initially is formed around the weilbore.nulatio.25. gas fractional flow out of that region as described by Eqs. As tine condensate accumulation diminisises. it is a rcasonmahIe assunmption for practical purposes. Hence. Nevertlseless. similar to the nnnetlso(l used in oil smnmnsplirmg. MPa Figure 9. mnsiung lIme comnclumsiuimm ohtuummcd iun tIne mecombinuutionm exercise described in Figunre 9. Some recommendations to alleviate the above problem were given in Section 2. the gas composition remains unclnanged at Ihe dew point pressure.

764 3.246 0.. In this section the application of phase behaviour models in alleviating a number of impeding factors in fluid sampling was described. .438 0. which can be evaluated and rectified by applying phase beinavmour models. Koehler.377 (1. Applying the contact method.300 0. so 520 a 15 0 a 2 ma • Oriqinai Ihead ‘a a a. 100 days 1.854 0.286 9. Then the removed phase is added to a portion of the remaining phase to match the saturation pressure.532 1.400 1.534 0..396 C8 1.828 0.846 0.385 1.1(23 1. SPE J.C: “Lunmmped-Connmponent Characterisation of Crtude Oils for Compositional Siusnumlatioms”. 1984).384 0.533 0.13.528 0. -2% 0 5 tO 15 20 25 30 35 40 Pressure.379 0.405 1.024 1. R.655 7.759 1C4 0. Coats. 2% (‘oetaot C4eth. Variations of produced fluid cornp~tionwith Comp. Conf. Predicted liqumid drop-oumt (if various samples in constant composition expansion test at 383 K.029 2.105 C18 0. such as flunid conntamination [671. with time contact method affected less severely.l1. Omen adequate voluumne of it is mudded buick to time liquid to match the bubble point pressure. Application mum Reservoir Simulation 9. As expected it provides a leaner fluid compared with the original one.300 0. SPE/DOE 10691.846 0.306 1)072 0. described above. 1870-1886 (Oct.292 0. presented at time 3rd Joint Symposiunsn on FOR.389 1.221 0..395 1.388 0.090 75.306 9. Evaluation of Reservoir Fluid Samples 345 time. SPE 13119.306 0.160 0.441 0. -J “~%—Wet — -~- error OP (‘rotact nieth.088 2.092 CI9 0.6 REFERENCES I.535 Cli 0. K. In the contact nnetlmod for oil mill lIme remmmmuinminrg eqnilihriunn gas is removed at constant pressure.828 Cl 1. 535-50.359 0.760 3.837 0.373 0. of 59tlm Ann.846 ClO 0.296 0.089 CI 75. et al: “Experinnemntal and Theoretical Studies on the Fluid Properties Required for Sinmnulation of Tinermal Processes”.375 7. SI: “The Use of Semicontinuotus Description to Model the C Fraction in Equation of State Calculations”. ...379 0. 1984).307 0. K.362 0.095 0. the contunc unmethod is tine preferred option.26 shows the predicted liquid drop-out from flumids prepared by recombinming the collected separator gas and condensate after producing the reservoir for 10(X) days in the above example.373 C3 3. SPE/DOE 14925..608 0. JPT.759 0.105 0(192 1000 days 1. -2% —-“ Separator Seth.344 Table 9.211 0.396 1. when the dew point is accurately knownm. It should be mentioned that if the recombined sample remained single plnase at the contact pressure. mole % Original I day 10 days N2 1. P: “A New Lumping Scheme of Analytical Data for Composition Studies”. Tulsa (April. Scinlijpcr.156 0. Whitson.Separator Seth.541 0.754 0. 6. 5. Table 9.543 75. IIommg.326 0.652 C2 7. 1988). 216. the conntact pressure could be reduced to form two phases. 3.089 75. (Oct.089 with fluid sampling. Lee..156 0. 1983)..362 1C5 0..300 CIS 0.216 CI6 0.767 7.242 0.828 1. Montel. Cii: “Cisaraclerising Hydrocarbon Plus Fractionss”.611 C6 0.292 C13 0. The wellhead fluid refers to the recombination based on the measured producing GLR. Jacoby. ST.026 1.105 0.379 Ct2 0.242 0. 1981). most probably due to improper collected phase ratio at the surface.242 CI4 0.026 C02 2. R. 683-694 (Aug. (Sept.152 0. the Use of Pscudoconmmponents inn Eqsmmmtion of SImile Calcuulmitions”. AG: “Siuinuluntion of Conmmpositionnml Processes. i’roc.646 75. provides very reliable results..089 2. and Sandier.A. SPE J. U.373 7.108 0.078 0. 0% “A..J: “Effect of Consposition annd Temperatiure on Pimase Behaviour and Depletioum Performance of Rich Gas-Condensate Systenms”.216 0. Although matching the bubble point by adjusting the phase ratio dunring tIme reconmhination process is adequate o improve the oil sample in most cases.075 (1.13.C.Fl: “Sinrmumlalion of Gas Condensate Reservoir Performance”. Tulsa (1982). Ignoring the measured GLR during sampling and recombining the two phases at the low separator pressure conditions to match the dew point. .292 0.5. M1’a Figure 26. due to loss of condensate within the reservoir.440 NC5 0. presented at the Stim 70 Symposium on EOR.533 NC4 1. Behrcns.373 3.075 C20+ 0.832 0.363 1.439 0. ‘fsulsmn (April.237 0. 1986). 4.287 0. results in a sample which is inferior to the wellstreunun sample. and Berry. 406-411(1959)..216 0..156 C17 0. AIME.092 0. R. Figure 9. 0. F.611 0. One can easily identify other problems associated 2. presented at the SPFJDOF 4th Synsmposiummmm on EOR. mind Gouel.026 2.366 1.102 (i. particularly for volatile oils.535 0.389 C9 0. 0% —•— Cootact Seth.611 0. 8.293 0. Trans. St’E/DOE 12633.075 0.533 1. An error of 2% in dew point impairs the results for both adjusted fluids. 7.440 0.613 0.372 3.535 0.

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Temperature and Composition”. Todd.. Danesh. 62. 6. 0: “The Viscosity of Pure Substances in the Demmse Gaseoums mind Liquid Phases”. (Sep. paper SPE 20521 presented at 65th Annual Technical Conference and Exhibition of the SPE. and Heinemann. October 27-29.. JP’f. Wasserfach.H: “Relimmhle Tunmminsg of Equmumlion of State with No Binary Interaction Parameter”.65 2. paper SPE 14151 presented at tine ôOlln SPE Annual Technical Conference and Exhibition.. 1980). A.6. 39 1-401. E..X. 13. Gas U. Gani.L. (Jun. 1994). 38-49 (1991).052 mPa. mmnd Dennmhicki. K. S. Sd. L. A. T: “A Unified Viscosity Model for Hydrocarbon Gases and Liqunids Based on Transposed Patel-Tcja Equation of State”. Il: “ilow to Obtain Reservoir Fluid Properties frons an Oil Sanmple Contamtniunated witin Synthetic Drilliimg Mud”. Nghiem. and Todd. Presemmted at the 1997 SPE Annual Technical Conference and Exhibition. and Burgass. Coats..H: “An Equation of State Compositional Model”. New Orleans. and Hagen. (June 1982). Presented at the 7tin European improved Oil Recovery (IOR) Syusmposiumn in Moscow. 60. Gozalpour. SPE 38852. London . DII. 43. J. 63.5 K and 34.A. 323-332 (1981). SPE 28829.09 C3 5.sc Behaviour and Flow Models to Gas innjection and Gas Condenmsuite Recovery Processes”.. Kluwer Academic Press (1994).1 I.K. Jumne 19-20 (1996). and Hanley. Bette. and Tehrani. London. A: “An improved Correspondimng States Model for Prediction ofOil and Gas Viscosities and Thermal Conductivities”. J. Lusmrtz. ammd Olsen. Cl!: “Accurate Insitu Conmmpositions ins Petroleunn Reservoirs”. Eng... 54. SPE J. API 64. J. Danesh A. and Zippcrcr. Eng. Ind. English Edition. Dandekar.

4.91 4.10 9.6424 561 kg/mum’.756 0.03422 0.00467 cud.00511 0.06 1.92 1.798 0.60 0. (VfVsam) Liquid Vol.68 24.395 2.110411 0.132 1.0934 7.487 2.34 60.847 0.000 0.3948 17.10 52. are givemn in the following table.948 0. Pressure MF’a 34. Frac.60 5.s Compressibiliny Factor 1.54 32.0000 1. ‘t’lne predicted results by a phase behaviour model.831 0.16 C3 5. l’lnasc 100.01)456 0.85 162 75 187 201 218 229 243 260 419 0.92 31.5) 3.00 1.ilation 9.28 Oil 57.89 0.26 MPa.01) 86 64 38 25 4 1) 1. The reservoir oil in Exercise 9.839 0.554 2.24 21.45 7.1)0433 9.823 7.80 1.69 0.79 I 63.45 42.44 28.72 2.622 1.689 1. Constant composition expansion tests at 373.t)5t I 940 1.49 1.0872 35.79 1.01 nC5 1.862 0.54 C~ i.t6 30.27 0.79 MPa.01082 0. and consmpare the predictions of tuned and untuned models with the experimental results.916 0890 0.836 0.69 1.53 C2 10.06956 3.040 B .04 0.342 2.55 1.776 0.832 0.72 5. as given in Fxamnmple 9.076 3.5.83 i-C4 1.956 0.10 225 44 17 lIne slock Formnalion Voluuuie Separator Volume 1.927 0.73 10. Relative Tonal Volume 2.0079! 0.1 K per volume of stock tank oil.72 0.96 35._c3~ponenm C 1 C 2 83.57 4.787 3.65 .791 3.34 Oil 57.759 1.5)1 1.5 was flashed at the reservoir teunperature of 373.28748 0.1 K and 35.995 8 0.726 0. Component Moie% Molecular Weiglst Cl 57.907 0.22 nC4 2.350 9.9968 * Summuraled liquid wimtn a tcnsiuy 13.00481 0.81 286 1.004 Cl2 Ct3 Cl4 ClS C16 C17 Ct8 Ct9 C20÷ 1.79 0.0352 grams of condensate was collected Iromnu Ihe liberated gas at 288 K and 0.67 I 0.212 1.70 C6 1.71 3 Gas 72.1 12 13. ‘l’muse a pimase behaviour model to the measured data.818 0.368 Z.99 .9970 0.00 34.14 74.4)) t.00410 (1. Calculate the composition of equilibrated phases in terms of tlme original components.16 96 C8 2.813 0.92 MPa and 373.tS I 98 Gas 0.6 K. MPa 35.00639 Specific Gravity 0.66! 2. Apphcatron in Resen’oir Sinu. The oil was described by methane and two component gronmps.26641 Iraction=0.06 0.168 I .t)07 0.00406 33.13 27.03 .2470 1.21 2.62975 Gas 0.85 9. Gas 8 Formations Volume Factor 0.02 1. 9. unsing the above flumid description. Group/mole t’rac. Pressure Relative Vol.06 5.19 2.47 10.56 3t.01 Gas 71.1 K.83 0. Sepmmrator test at 293.571 0.79450 0.48 17.89 Gas 78. (3) Voluunc of oil at separalor pressure and meunperauure per volume ofstock tank oil.837 0.441 2.66 75. The following set of experimental data is avumi’)umhle on a volatile oil.168 121 286 258 23)) 203 177 138 lIt 2.89 lt).00 2.06 i-CS 1.781 0.777 27. LiberatedGa.854 1.55 1.31 of Differential liberatioum test at 373.99 0.25 Oil 56.78 0.55 104 C9 ClO Cli 2.446 I I 0. Compositional analysis of volatile oil.79 .82 % 09954 Iorwmmrd conntmmct cxperinmmemnlal datum witln mmncthanse at 373.01699 0.429 2.0 K and pressure of 20.839 0. 7 Exercises 351 1.903 ‘romal Densiuy of 0.342 2.46 8.767 4.963 1.15944 0.6) 35.3t) 24.57 17.377 1.03 9 fit) 5.00 0.22 1.C 4 nC 4 5.87 787 4.00k Oil 57.24 20.1 MPa of mercury pressure.764 mask oil at 288 K = 81)) kg/sun’ (I) Separamor flashed gas volunnne (sc) per virliunune of smock lank oil.329 I 252 1.92 R d Solution 5 Gas/Oil Ramin 405 356 0 .1 K.00 68. I (unmeulmane) II 111 Liquid mote 2.20083 0. Prcssure (his / Oil Ralio 5. tusing the equal zlnM metirod and molar averaged properties.9978 1.10 116 131 148 26.969 0.49 0.435 0.24 7. (2) Votunise of samurated oil an 34.3.34 13.220 t.1508 1.0394 1.40 85 C7 2.828 0.j Retamivc 0 Volunnc Oil Oil 0.039 1.

51 0.55 2.41 2.76 0.05 11. 0.50*9 40.74 0.95 1.23 1.39 0. I A.05 0.70 1.86 0.74 1.18 0.23 0.5 564.19 11.18 1.75 (1.04 1.11 1.36 1.16 0.9 * Volume of fresh oil contacted with a density of 563 kg/ni’.2 A.66 0.36 0.12 0.5 0.3 312.50* 3 67.33 4.27 2.26 MPa.352 i-C 5 nC 5 9.96 0.47 0.08 (1.96 11.58 0.82 0.74 0.61 0.36 0.57 20 3 V~d.0 580.76 2.5 Properlies of Ptmre Counspounds Properties of Sinmgle Carbon Nuumnber Groups Universal Gas Constarmt Binary Interactiomm Parameters Conversion Factors Page Nunmher 354 356 357 358 363 364 Appendix B: Critical Property Correlations in Field Units Appendix C: Eqtuatiomm of SLoe Expressuomms Appendix I): Equilibriumusm Rumlios 368 372 Equilibriums Ratio CInumrts at 501)0 psia (34.31 1.15 1)39 2t).99 1.8 358.98 43.55 4.71 34.41 1.10 0.87 Cns 1. Application in ReservoirSimulation 353 C C6 C7 8 C 2.95 1.68 1.90 0. 4.33 1.21 0.23 1.25 0.16 Cn2 1.75 1.47 MPa) Convergence Pressure (WA Copyrigtmt.56 19 0.08 1.69 1.0 Pc’ kg/rn 604.97 0.41 2.18 0.33 1.69 1.92 Cm6 0.32 2.76 Cmi 0.65 0.03 (1.98 0.02 1.24 0.36 1.00 22.59 0.42 1.42 2.22 (1.01 1.3 312.31 (1.82 0.26 2.17 C . .15 1)38 25.41 0.5 APPENDICES Appendix A: Tables A.26 4.85 1.65 C15 0.11 0.28 (1.01) 27.41) 11.64 11.67 0.20 0.52 0. cm 67.16 0. ** Volume of methane contacted at 35.19 9 Cno 1.13 0. cnn 90.4 A.77 0.39 3 61)4.24 0.66 Cnn 1.72 1.19 0.07 0.41 1.05 0.92 350.77 1.92 0.29 1.tR) 211.10 0.13 0.76 1.98 43.47 0.14 0.62 1.26 0.27 1)81 ~ 0.3 A.41 2.54 0.6.32 0.36 1.16 m).63 0.00* 22.92 1.69 1.09 Cns 1.11 1.71 Vequ).30 0.12 0.15 1)54 C 0. Reproduced willn permission from: “SI Lngineering E)ata Book” (1980).23 0.54 t).52~ 90.97 0.13 51)00* 48.27 2.58 2.

4130 0.32 0.2275 0.0852 0. K 190.71 118.3495 0.0986 0.5 3.5070 05629 0.258 142.27664 74.sane n.77 606.612 4(9.03 185.481) 0.6247 0.2694’ 0.1943 0.50)) 425.0218 0.1 (93.2568 0.161 84.2704 n-Butane i~Pcntanc Neopennane n-Penlane 2-Melhylpcnlanc n-Flexanc n-Ilepnane n-Ocuane n-Nonanc n.76 4.544 0.1770 0.580 1.13 430.3540 0.72 9 .37 4.6273 1.15 647.6111 0.2880 0.167 106 167 28.7 132.24322 0.8114 (1.99 460.019)1 0.2960 0.2126 0.2800 0.2199 0.3310 0.3053 0.7835 289.0940 0.6112 0.2262 (12235 0.3260 0.4435 I) 25456 (1.63 4.(l.27821 143.21500.8666 0.18) 269.3079 0.109 6(7 17 3.8743 292.3738 0.043 30.3996 0.2817 (1.4 801.71 136 61 366.2894 I 0.9069 0.67 282.9890 0.3 617.8694 0.34)) 1.8522 1)2158’ 813.17 3 5)6 .7633 (17722 (1 7772 0.0403 0.r values ire to he used only in Fq.6286 0.181 0.0995 (1.2705’ (1.2687 0.3946 28.6638 (1.1620 t).4 1.8 653.27044 0.177 100.28971 0.2320 0.160 1.055 0.8(8)4 0.7924 0.29 2.3791 0(191)1 0.419 489. Ellmylcyclohexaunc t’tcnicne ‘I’otmucne Hlmythenneenc cu-Xylcne nu-Xyleuuc s-Xylcnne Niun’gen Osvgeus Cambon Monoxide Carbon Dioside Hydrogen Sulptuide 70.740 39883 568.1)16 81.Pcntenc tuimns-2-Penmeune 2.2824 0.3259 0.79 4.6576 0.2701 0.26186 0..41 497.31997 Sulptucr Dioxide Ilydrogen Waler * * * 194.161 91) 18% 98.05 0.010 44.2350 0.28128 0.7527 282.2598 (1.3758 11.599 4.2717 (1.2 I 1.502 532.6683 0.371 0.312 n.7174 0.19 3 471 569.110 469.3158 (1.486 0.0827 0.1810 (1.27351 (1.33 0.114 92.161 98.2627 0.1523 0.1)8 309.2114 0.(8 .24692 0.210 1.53 0.3036 0.28966 (1.41) • Z.204 114.65 425.2303* (1.659 0.7015 210.215 78.Heneicosane 4.6174 1)6430 0.5000 0.37 3 714 617.648 272.123 1’.26729 -0.14 K 111.tlulaslicnuc l-l’cuuuene cis.527 1.49 1)1.3449 Yamada.392 212.2693 0.59 4.27275 82.8 180 0.657% 0.28476 85.1421 0.2744 t).4 810.0560 7.5764 (1.2535 0.08 37662 404.2.3562 0. irons II 151 excepl mtnose idenlitied by w)uicln are calculaued froun Inc 0.2653 t).3(158 0.500 268.810 511.043 0.2419 (1.2711 0.8 373.199 309.6 2.01)) 34.6563 0.1455 0.65 433.0663 0.0985 0.2038’ 981.50 0.2659 11.313 0.27331 0.96 0.775 17t).1867 0.55 n-Docosanc 310.331) aceintric Rackelt paraclmor factor Z .054 42.2l90 (1.231 128.010 341.3021 (1.35 417.7445 522.285 156.1424 0.13 22.11 261.11)7 56.2620’ 0.05 3.2190 (17697 0.2767 0.01)5 0.1596 0.43 n-Tetracosane 338.2725 0.0(1 0.2701 0. 1’~ Tumble A.26824 0.6882 359 13 0.065 54.2870’ 0.529 3..019 .3692 ((.6322 t).21431 0.107 40.78 3.08) 56.511 I 26.97 594.78 4(19.147 1.150 86.76 4.1964 0.7748 0.17 464.7070 39u) 57 0.26074 0.50 730.01) 216.2862 0.43 3.8829 252.29(1 447.2641 0.3036 0.54 4.2697’ (1.79 322.2639* t).19 212.2068’ 939.43 266.51 77.5210 0.2108 0.177 86.58 540.2685 0.7 3.17 3.26967 0.215)) 0.2667* 0.11) . 1.025 371.2767 0.114 70.17) 1. 0 3()0() Naunme Llhylenc Propylene I -Bulene cis~2-t’5ulcne urans-2-Bulenc Propadiene I 2lltnlaulicnc I 3.08 639 1.2559 0.040 562)6 4.2t).0931 7.1.680 (1.381 282.27130 Sp.).4500 0.7 2.096 58.473 1.060 0.2714 0.05 112.2611 0.2000 0.2686 0.2615* 0.0000 t’arachc.206 428.082 64.167 1(16.963 7.270 1.7617 0.362 (1.24698 (1.3 127 0.7921 210.2733 0.400 45(1.114 84.150 72.15 3. Name Methane Ethane Propane i-Bumane MW kg/kgmuul 16.2765 0.2742 0.95 254.1220 0.8744 08849 0.830 1.86 747 603.6524 0.3189 (1.tlepuadecane n-Ocmadecane n-Non~Jecane n-t2ico.2583 0.7540 247.9 276.4 344.2920 (1.9220 1)2(197* 897.428 0.2753 0. Properties of pure coummpotnnds.A Iroun 11.35 9(1.609 63(1.7820 Mcmtnytcyclopennane Cyclotuesanc Me0nylcycluuhexanc Lltuylcyctopenmane 1)7869 ().l3). acenlruc factor R.2182 0.2616 0.66 184. 0.2739 1)2002 0.56 305.141 11)6.107 56.90 229.28054 101.tlnslrvaoe n-Dcsiecane n.2455 0.101 1.365 198.2382 0.000 240.2594 0.382 8.6~ (1 7142 482.020 435.2703 0.2660’ 0.7 781.6005 0.96 153.1932 0.28962 61.32 369.446 1.Gunn correlation.27035 0.6 3.22811 296.7 2.898 591.2629 0.27570 (1.2637 0.2515 1)26853 0.889 1.370 333.7712 328.85 851.67 304.Gr.2670 0.7797 0.553 1.27212 0.4)8) 504113 3.3 291 2) 311.2340 0.6458 0.15 276.188 70.2509 0.79 3.83 408.26986 0.3021 465 3.2118 0.2294 0.3680 0.2030 0. ~~~rties of pure compounds. K 169.654 0.78 475.44 (1.15 5.s 355 Table Al.55 231.170 0.58 5.601) Z.12 0.18 * ~l 8.27569 0.05 758 616.784 551.64 1.93 3.53 263.680 664.338 184.2011’ 023.5303 (1.949 0.73 543.05 647.059 1.74 0.(8.93 768 629.95 353.134 7(1.065 2.58 412 27 411.6769 0.62 526.103 391.8094 1.87 374.l)nnicuuc 1-tlesenc I-HeplCume (‘yctopcnn~unmc MW kg/kgunol 28.151 except those idcnlitied by • whictu are calculated frousi lIne Yannada-Gunmn cou’rclanuon.75 21)39 33.27283 0.65 284 26874 ‘I’.3(17 0. I (Cont. 9 0.6598 475.7954 1)7981 0.070 44.37 236.2208 4 0.167 106.761)3 0.3(121 11.2726 0.2701 (1.03 238.570 0.198 0.7 641.92 3.2663’ 0.394 154.197 609.188 112.292(1 0.2168 (1.8014 1.2763 0.3130 0.3013 0.3745 0.490 423.470 444 4.1)14 31 999 101 Il 31(1.2666 1)2781 1)2662’ 0.654 0.uckcu ~ virmctnu ur SpUr.5997 0.253 0.150 72.0642 0.032 364.092 54(192 T.21)78 0.2199 0.3664 0.22917 771.2286 0.88 507.2630 0.26 3.2793 0.2948 0.9551) 11.24 383.2276’ 0.872 4.6861 (1.Tridecaune n-Tetradecane n-Penmadecane n-Hesadecane n.820 0.26355 0.26 0.5840 0.2061 1.25678 0.89 0.43 (u8%.2382 (1.499 0.2302 0.630 1.00 0.27286 (1.2790 0.2589 0.541 616.3 65% 675 1.36 5.4923 1)25)17.2843 0.Mentuyt-l-Buulcnc IMeslnyl I -l(uHcuue 2 MelIlyl 2.83 560.0734 0.884 1.2705* (1.1)15 373.Dccane 58.12 3.2715 0.5974 11.400 1)944 226.140 537.248 3.2793 0.! 3.2 2.252)) (1.3 563.2095 11.354 Appendux A l’able.796 300.610 n-Tricosane 324.075 572.2550 0.02 0.22 469.114 70 114 7)) I It 7)) I 14 84.2704’ 0.129l 0.47 508. K P~ v MPa m’/kgmol t).123 72.2620* 0.05 0.120 0.2690’ (1.2917 0.2465 (1.43 P v MPa umm’/kgnunot 0.2706’ 0. Eq.8025 Parachor values are no be used only ins Eq.2685’ 0.2406 0.87 274.52 3.2451 0.1.58 4.01 575.716 1.27 0. ‘ 693 708 723 736 589.2373 0.91 54.1) (.2329 0.24990 0.8 791.2276 0.47 225.2287 0.

181 0.310 0.897 1)944 (1.936 0.085 1.) + A (C.448 1.690 0. and not tlmose given iI~ Table A.826 0. ZEA.86714949 0.909 0.).997 1. 7.234 0.522269 7.831) 1.194 0.226 1.636 0.232 0.922 0.23% 0.603 627 P v Table A..815 0.393 1.389 1.836 0.179 11. Zc: Catculaied from Pcvc=ZcRTc Acenu.237 0.140 1.680 (1.31)9 0.314 1.920 0.3.0083144 10. Pc.732 Ic.-.864 1.ric factor: Calculated from the Lee-Kesler correlation.414341)8 [-3 8.--..53747 275.789 (1.502 0.38878 24.269 0.392 2.915 1.(t63 1.727 1.261 (1.247 11.215 0. 0.-..85.226 0.604 0.484 2.888 0.752 0. Acen.672 (1.2(17 1.8518106 — 1.974 1.187 (1.175 0. M 1’~ ‘R S Cu) T~.7(8)211 [..356 1.194 0.107 1.211 0.534 0.934 0.253 (1.1)74 (1.3 ((. Generalised single carbon number group properties.8675351 E-3 — 0.29926384 — 2.652 0.844 1. Pressur numb bar MPa psia I’.96% 0.3028779 El 1.917 0.197 0.323 1.2.177 0. Universal gas constani values.----—--.193 1.24(1 0.125279 — — — 0.~ ~&.727 390 416 439 461 482 501 520 539 557 573 586 598 612 624 637 648 659 671 681 691 701 0.927 1.187 (1.998 1.232 (1.) 2 4 5 where.481 0.0567 0.468.2 41.951 1.142 1.861 0. Calculated from the Yamada-Gunn correlation. ‘R — — 131. Tumble A.7117226 E3 4.196 (1.571 0.4663890 E-5 5.259 1.154 1.9-l0).55(1 0.749 0.19(1 0.931 0.224 1.114 1.229 0. Gulf Publishing Conmpany.49433118 E-8 1.856 0.610 (1.56275 5.896 1.1146 t.96156 50..929 0. P.189 0.230 1.933 (1.188 0.054 (1.~-L .927 0.11375 434.614 0.191 0.219 0.(6.265 0.172 1.50862704 3.940 I K 510 547 574 .532 2.356 Appendix A Table.905 0.584 2.165 (1.876 0.263 1.348 3.9(127283 2.4017952 E-2 ‘ Time correlation gives the calcunlated critical properties by Whitson using the Riazi-Daubert correlaliotm.312 0.223458 E-2 0.495 0.71)1 0.433 2.251 (l.199 0. * Ahmed.8709139 E-4 0.938 0.244 ((241 11.013 1.ft’/Ib 1 P.899 0.263 1)261) 11.185 (1. 14).071 0.17% 11. Eq.866 0.953 0.060 1.271 0.11(2 0.193 (1. SCN C6 C7 C8 C9 ClO CII CI2 CI3 CI4 C15 CI6 Cli C18 Cl9 C20 C2l C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 C41 C42 C43 C44 C45 MW 84 96 107 121 134 147 161 175 190 206 222 237 251 263 275 291 T.681 1.877 0.421 1.257 0.698 0. (1. 915.: Cuirhon grotip nmtnmnnher (1.749 -(1.421317 psia v .ml property (‘.233 0.214 0.180 11.296 1.361 1.256 0.198 1)196 0.804 0.077 1.1627984 1.IJ_~r~l2r~.877 1.2(19 0. 0: Any plsysic.221 0.905 1.874 1.231 0.9324432 E-5 . T: “Elydrocusrbon Phase Belnaviour”.124 1.732 0. Eqs.871 0.253 0. .964 1.843 0. Eq.191 (1.083144 0.217 (1.839627 [-5 — 1.429 11.896 0.941 1.8484814 E-5 —0.8452129 E-3 1.224 0.147 1.32575 —401.851 0.244 ((.91(5 1(11)8 1.4941184 E-3 7.203 0.467 (1.665 0.~ 4 K cuui’/guunuul K lil/gmot K m’/kgmol •R ft’/lbmol R 1(2.Gr.095 1.J.(6.034 1.164 1.) +A /( C.559 0.85651 1.902 0.174 - w itim connslusnmls as follows: ----~.815 (1.ncu.181 1.23-25).2(10 1.885 0.61)1 (IS (6 Ahrned’s ConTelation’: 2 1 0= A-m-A (C.777 1.180 4.635 2.793 0.1)82 1.__ .(6.185 11.892 0.039 1.191 (1.28() 0.11)5 1.22(1 0. - Rackelt Generalised siisgle carbon nunmber gromup properties. 649 670 689 708 727 743 758 770 781 793 804 815 825 834 844 853 862 870 877 885 1(93 901 300 312 324 337 349 360 372 382 394 709 719 728 737 745 753 404 415 426 437 445 456 46-4 475 484 495 502 512 521 531 539 907 914 920 926 932 938 943 950 954 959 964 970 974 760 768 774 782 788 796 801 807 813 821 826 MPamVkgrnol 3.733 0.110 1. Houston (1989).352 (1.0280657 E-3 2. and ye: Calculaned from Twu correlations.217 0.181 0.026 1.212 0.13).782 0.184 0.7547264 12-i 1.184 (1.s 357 Table A.( 1.224 1)221 0.207 (1.)+ A~(C.226 0.2(15 (1.759 0.188 (1.643 (1.83~L__.F’.21)1 0.841 11.446 1.229 0.768 0.583 0..480 0.341)79022 2.881 0.213 (1.251) 0.266 (1. Eqs.2 (Commt.925 0.2. K 337 366 Sp.247 0.679 0.251) (1.268 0..75861(59 12.235 0.200 11.915 0.912 0.

0001) .00(10 .0019 .0000 . . 1(1(11) .0022 .0301) .0140 .1)5(11) .0144 .0150 .0000 -.13)81 .2.11(8%) .0000 .1881)) .0230 . Aunmerucan Clnetniical Society.0100 .00(8) .0000 .0033 (8)00 .’t .0870 01(78 .1370 .0250 .0230 -.0000 (1111)1) (8)00 .0250 .0)1%) .0289 .0380 .0000 .035)) .0031) (8)111) .0204 -.111)01) 11)1%) .0(178 .0010 -.1900 .10(8) .0000 16 17 18 19 20 21 22 23 24 nC~ MelCycttCX ‘Toli.000(1 .0000 .1)00(1 1)300 .1)15)) .0601) .0040 .0000 . DC.0156 . R. 000 .0500 .0(11)1) .1870 1900 1900 1900 1900 1900 .11(118) .1)101) .0056 -.0000 .11)18) 1131(1) (XXI) .0230 .0000 .11(1%) .0411 .0190 .0001) .0001) .0000 .00(1 .0190 .4.1000 .0000 .006)) .0101) .0000 .0015 .I(1(l() .0(180 -.0200 .1000 .0(1)))) .0978 .00(1) 4 Pn)uylene .(8)0 ‘I’umhle A.0140 II 12 II 14 IS .0350 (111)1)) .0230 . Advances inn Cliemislry Series.0101) .0080 .0005 . : ‘Applications of a Generalized Equation of Slate In Penroleuun Reservoir Fluids’.0(88) . Ediled by K.11(8)1) 1)000 .1)170 .~4 (.0000 9 nC n( 9(11) .141))) 1(81)1 1001) 111)8) .11)00 1000 .0200 .00(8) .0000 ((1))))) .0280 1(1(10 .1819(1 .0000 .0000 .0040 .00(8) .011)0 .0000 .0030 .1600 . 1) and Eckcrsuiani R.0000 .0000 .0010 .0001) 31000 .0150 .01)01) .1501) 1500 ISO)) ISO)) I 51)1) 15(1(1 .0380 .1(1(1(1 ..0001) .11(11)0 .1)100 . L.-.1450 .0050 .quitihrua for Mixtures of Low Routing Substances”.00(1)) .11(81) ..0000 .0015 .0100 .03(10 .111)01) ..181(111 .0300 .111)00 .0050 .010 .0000 20 24 Fronn: Yarhorosmgh.0040 .0(11)0 .01)00 .0050 .0150 .0000 .008(1 .0000 1)200 .?n_of state.0001) .0000 .0050 .).0015 .1)101) .1240 .0(156 -.358 Appendix A TabIe. 182.01(8) ..l.1(1110 . .1)130 . I 30(1 .111)00 Ncopenlnmne n(y . _______________ 8 9 1(1-24 9 It) Propylene C 3 iC 4 nC.0000 I)) II 12 13 4 IS lb 7 8 19 21) 21 22 23 24 iC 5 .1200 .0000 .0050 .10(1) .0060 .0004 .0100 .0000 .0000 nCls-nCl9 nC Q-uiC24 2 Prouun’ Knapp.1)001) .1)1)11) .0900 -.0000 .0078 nCti Men (‘ye Penn (‘ye Hex .0(100 (1001) .0190 .00(1)) .0)01) .1)151) .0(11(1 .—. tserticns.02(8) .0944 .10(1)) toOl) . Chnuo auud Robinson.c 359 Table A.0000 .1900 .0(16(1 .0(1(10 (1)8%) .0078 .1(448 .0300 .0144 -.0300 .0044 .1)100 .00(11) .00)1) .0101) .0050 .040)) .0(8)0 -. _______ 10-24 3 4 5 6 7 8 C 2 .0050 .0763 .1(1)8) .0000 9 nC -nC .0700 .mene o-Xyleuue nC1( nsCq nCIO-n(’14 .03(8) .0010 (8)20 .1)374 .000(1 .0220 .0760 . Binary insteraclion paranseters for Zudkevitch-Joffe-Redlicls-Kwonsg c.0551) 1)600 1)650 .1(1(10 1(10(1 10(11) 1000 .0000 . 0(10 . .pu’uieuuu 5 6 7 (8)11(1 I N 2 (611)1) 011)1)1 2 ~ 1)278 111)7 0)11)0 3 ~l (((0(1 .0080 . C.0001) .1(1)81 .0450 111)11) .1811)1) .06610 (XXX) .0078 -.1)1(11) .0000 . : “Vapour-liquid F.1)1(10 .0407 .1900 .0000 .0001) 1)1(1)) .4 .0(1(111 S ~2 6 7 8 9 Propylene C 3 iC 4 nC 4 ((80)1 .1)0211 . — ~—.0100 . Washungmon.0005 .4.0005 .001)0 .02(10 (1201) .1(11)0 .0100 .1000 .000(1 (81(10 .1090 .0300 .01 70 .18)0(1 .0(8)0 .0(8%) nC 19(10 . L.0220 .0400 .0100 .0111 .1000 .1500 .01)01) .1163 -(8)78 ((026 .atmommof stu~c.1)418) .141)0 1400 . Equalions of Stale in Engineering.000(1 (1(3(1(1 .0(110 Binsary insteraction pumraummelCrs for_S~mvc~Rcdlnclm~Kwofl~e~Iuat~.0(11%) (101)0 .0000 .0131) .0000 .~.0330 .0100 .0005 (111)6 .01(10 .001))) .0230 . Eds(l)ceheunsa Chemusustry Data Ser.0200 .1(118) ((18’) . II and Dorimmg.0201) 1)100 .001(1 .04110 . R. page 385-435(1979).0100 .1000 . 2 3.11448 . 11)110 .11)111) .0050 .0120 .1)000 .1)040 .0030 .0000 .0241 .0100 .0010 .0300 . 3 ~.0867 .1)120 .1(11)0 .0000 .0050 .0025 .0400 .0011) .0)100 .0130 .03)17 .01)10 .0185 .1000 .0(8)0 .I6’)() 16(8) .035)) .0333.Binary System (1986). 1(1(1)) .0000 . .0900 . 6 ~ 8 I 2 N 2 (02 C 1 I2lhylcnc ((000 .101)0 .0200 .0270 . 1900 900 .0120 .0000 . Part I.1000 .0101) .01)1(3 .~ iC~ Neopent~ne nC 5 nC 6 Met Cyc Pent Cyc Hex nC 7 Met Cyc Flex Totumene o-Xytene nCg .1(1)10 .18)00 .1422 .0000 .0300 .00(X) 10~ 4 uuCIy-n(.onn.0005 .00(10 .0000 .0000 .0(88) .13(10 .011)0 (1067 .

1)00(1 .1500 .12811 .031)0 —. and Eckerman R.1450 .1550 .141)1) 1401) .0470 .1501)0 .111)1(1 .01)611 .0150 .0020 .001)1) .111)11(1 2 .1111(1(1 .1)141 .03(11) .0620 .00(11) .nC 9 (15511 .02()0 .0000 .0242 .1100(1 .0145 . .02 10 6 .1400 .0(8)2 .11930 .1)0(11) .035)) From: Knapp.00(1(1 0000 11005 .1400 . S.03(8) .0400 (XXX) (XXX) . R.0451) .0001) nC 1( .025(1 .0590 .0160 .0200 .03(11) .0300 .0010 -.0150 .).0040 .1100 .18)18) .0000 .0160 .01)33 .14(11) .11(81)) (81(11) .00(10 22 23 24 nClO.0(101) -.0320 .0352 .03))0 .0500 .01(8) .1)1 74 .01)00 .060(1 .128(1 .0600 .0401) .18(10 .1400 .00(11) . No.1111)8) (1(1111) .061)0 . 24 nC .0000 3 C .1111(1 .111)1)) .0400 .030(1 3)02(1 .021)0 .0400 .001)1) .()4(10 .0(11)0 . : “Vapor-Liquid Equilibria ftsr Mixtures oIl.1501) .1441 .0250 .0236 .0(100 .0060 ((004 .11(8)1) (8100 .1450 .0450 .1(401) .18)0(1 .0(11(t) .0700 .ow Rolling Subsuances”. 7 8 9 10-24 No.0056 (1)1(1)) .1)1 2() 0267 .1)1(1(1 .01St) .0000 .0(8%) .0000 .0270 ((561) .1)21(1 .0270 .18)78 .1)1 SIt .1)400 .0500 .0600 .1)0110 .0256 .1)4311 . Component 2 3 4 5 6 I N .0181) .nCl4 nCl5-nCl9 .100(1 .1(1 (Xi ((360 . I 270 3 4 5 6 7 S - 9 10-24 N 1 4 5 2 C 1 [tluylenne .0600 .001)0 .012(1 ..0000 .0150 . .04(10 .0(101) .0300 .0250 OIl)) (1111) (8)1)1) 11100 1150 .0026 (8)89 (11)00 2 6 7 8 9 10 II 12 I’) 14 Propylene ‘I’ahle A.0145 .1400 . (401) .0450 Mel (‘ye l’enn (‘ye lIes 012)) .0200 .0(100 nCi Met Cyc Hex loluene o-Xylene nC 1( nC9 17 I 8 19 20 21 22 23 .0133 -.0120 . and During.01)80 .1)141 .0141) .2(100 ..06)))) . Berhens.11111 .111)40 . 4(8) .074)) .11(811) .1)311) (((1(1(1 11080 .111)01) .0080 .0000 C’~ iC4 nC~ iC 5 Neopentane nC5 nC6 Mel Cyc Penn Cyc Hex .18)11) .1800 .1111(1) (XXX) .01111(1 .00(11) .00(11) . ((XX) .14(8) .1)080 .01)181 . Part I.1322 . l2ds(Dechema Chemistry Data Ser.1161(0 .14(8) .14181 IS 16 Ii IS 19 20 21 .0400 . AIChE J.11(811) .11001) .0056 .111118) (88)0 (XXX) .1)21(l) . 1) 1’ nnnd Tejnm.1)31(1 .0000 (1(8%) .0000 .0(8)0 .1)3(8) .18)8(1 .00(8) 2 2 C02 .1)140 .1251) .000(1 .1200 .1500 .11)1(11) .0000 .03(11) .0380 .0188) .0001) .181%) .3.0711 .0145 .0078 . Binary interactions parausseters for_Patcl-Teja equation of state.0145 . 32(12).0000 .1111(11) . A.011(1 .0000 .0171) (1171) .11242 .001)0 .0515 .0600 .0000 (XXX) (1811) 0 nC ).01)71) .0000 .0311 .0000 20 Fronni’ Willnnnmn.1241 .031(1 .0000 .011(8) .111)89 .1400 .0001) (811%) (XXX) nC -nC 14 .0100 .18)1111 .1)171) .0540 .1)11)) .1(100 1000 1496 150(1 . 1450 .0500 .1333 .00(1(1 .11371) 3)000 .111(8) .111)11 .16(X) .0260 .11(11) .0350 .4.1)14(1 .0(180 .0400 .0000 .1)150 .131)1) .0450 .1500 .0590 .0400 .11(8)0 .0000 .0800 .0300 ‘~0t11)) .0160 .1137(1 .0000 .11(11%) 1 un(’ -nC24 .0141) .0001) .1500 .0100 .0001) .0010 .0190 .0600 . .01)01) .1)11(0 .0300 .011)0 .030(1 nC2(XnC24 . Binary interaction parameters for Peng-Robinson equation of state.04511 .1000 .s .111)11) .1300 .000() (8)00 .0()06 .026(1 .11118) .0301) .0160 .01)10 -.019(1 .0001) .1)251) .0121) .0400 .0400 .1550 .0330 .0(11%) . Coumipoiucnt I .0(1(1(1 .0004) .1550 .111)10 -.1)12(1 .1)11)11 .0)80 .0096 .1)1)211 .1070 .0215 (88)0 5 C .00(111 .0401) .1)111 .I 350 .0474 .0450 .128)1 .0001) 7 8 9 10 II 12 3 14 IS lb Propylene C~ iC 4 i(’ 5 nC.1550 .11600 .0000 .1)25)) .1001) .1)1)1(1 (NtIS nC7 Met Cyc Hex l3uluemme o-Xylcne . H.0080 .0300 Nciupcnttanc n(’5 nil’ 6 .0371) .Binary System (1986).1450 .1)000 .0400 .0500 . : “Conminuouus Thermodynamics of Phase Equilibria Using a Multivarame Distrihuiion Funclinin nmuuul an Equation of Slunle”.1)400 .0500 .0400 .0501) .02(11) .1)000 .01)11) .1700 .0000 (1000 .4.0580 .4.0250 .0800 .11050 3)090 .360 Appendix A Tables 361 Table A.0000 1 4 Ethylene .0200 .0(100 -(11)4 -. 2067-2078 (1986).0470 .111111) .00(11) .1)422 .0050 .0001) .)t8t)0 .0000 .025(1 .0852 .1500 .0620 .11201) . D.11(8%) .1450 -.18)67 .0601) .

1(510 0. N2 and l-12S binaries for Valderrama-Patel-Teja equation of state.601 846 =kg/m mmml — =rn~ x 1.111) 58.I ueiniperaturc ulcpendeuiu: kpin=O 0278+11(1111(911 (‘I’ 271Y waler-uiietltasot us tcunperatunrc ulepettulcnu kiumw-0.91 11.6(1 0.1)2 [2÷00 CI) (ccnti poise) cSI (cenli Stoke) d (darcy) dyne dync/cnmi ft 1’t” II’ II ‘/bhl x x ‘C+273.047 0.111) 0(1)) Methanol Waler 1) 0000 64.86-89).5331 0.1)1:3 250* I .s = = = rntn’/s = = x x < x x x 9.56 7.081) 0 176 - Table AS.7908 0.28 17.095 0.(4.521(1 1.134 0.1 k(knlt)=l: + (1.2245 0.047 0.362 /tppendin . Eqs.8 (F + 12 .4)) 39.11 2174 0.4165 0.4974 (1.291) 304* 9.29 17 (1. SI nmetric conversion factors.2538 - Waler l~~ - 5 fI /]hmin 1’~~ 49.02 = bin’ nls’/m’ 1 =rn /kg = ‘C = Ethane Propane -Otitane 00(37 (1. 11(1 (1 ISO n-tleplane (1 I 0) (1.0779 0. Sulfide 0. inn” x 459.589 873 1.0440 (1.380’) 11(1)8))) 2.70 0.138 ((114 n-Penlanc (1.21 35. 2’t (1)1) ((.535 924 =kg 3 htmi/ft’ x 1.1403 0.070 u-Butane (1 I 26 1).0)) 45.581(0 0.6070 1.s lhnns x 4. —___________ Methanol Conuponenu (I) Methane k.5607 0.01) 0.036 .01) 17.13 E .290 304”’ E-0l 12 — 02 12 + 04 =rn = ma’ = Table A.0519 0.8 3.050 0.2484 00694 n-Octane Carbon dioxide Nitrogen Hydrogen sulfide 6.32)/1.047 0..6575 0.4792 0.869 233 1 0~ 1. 111(1 + 0.45( fi* 1 jun.088 (1.242 796 (“F-.4 lable.785412 E-03 12-02 E-04 12 — 05 12+00 12+03 E-0l 12+01 E-06 E-02 12-03 .61118 .7861 I 6885 1.1382 ** I~ 1.00(11115) ‘I’ 271) 1 =m >< 2W =rn =un~ ~< fi.5.894 757 = Pa. nsmm’/s Interaclmon paratnleters and coefficients of usnellnanol and water hiusarics for Vaklci’ratmta-Patel— ‘I’eja equation of state with non-randonn mixing rule.6.0* [2 1)4 = mnm’/s t ~SIt usml l’. ((.4.128 0.038 Propane 0.5525 (14577 ((.5465 (1.aImn(sld~ x ~ I .320’) ((.88 21.4870 1.5021) ((.333224 =MPa psi ~< 6.2528 n-lltutane n-Pentane n-llexane n’Hcptane 0. API .3901 0.22 33. (96S (1.448 222 =N hf.589 873 feAPI) 12 + 05 12 + 05 =~/cm” = Pa = Pa = nss’ bar hhl (US) hhl/I) Iliti “1’ x x 1.s exacl gal (US) i Is.894 757 ‘~~MPa =K x SI (s)oke) >< 1. x 1.67)/1.1(000 nietlian.72 3 I .1461 0.1233 ()l46S ((.0~ . Cornponentjfl~çarbonsDdcN~~ Metttane 0. I 34 n-Butane 0. Interaction parameters of C02.02 12 — (II 12.092 0. 142 Carbon Dioxide -0.54 27.0* nsmuisl Ig=torr x 1.035 Ethane (1.46 I 3.0* Os’/S kJ =K = umPa.050 0.cltxcs: nnn(uniullt)=E —0.141 (11)88 n-Hexane 0.4. s/rn’ x 6.1133 ((1)001) 0.4592 0.4 I 3S.1)1) ol propaneof 0.5200 0.781(17(5 6.5710 1.1)1)111) k 0.048k 9.0700 1.638 706 = mm hf x 4.57 23.30 17 4)) x >< l 0.j~~oen All hydrocarbon-hydrocarbon DIP=0 I-lydr.ious laclor u.1 M(nsnega)=13 + 06 * (“ouuvenu.831 685 1.7232 2.7319 0.00(1)) 0.055 056 12-01 12 -01 E + (8) 12+00 E +00 12.1)11)1) 1.0” m’ nmN =rnN/m 3.08)) 0.5863 0.17 36.l5 I 1)* 1.s 363 Table A.

2518 — 6875 IS..843693 —(1. and K~ is tIme Watson clnaracterismmlion faclor. a to f.67)’ +0. (15. in all the following equations.4679 s 10 ~ 3.095 x l0-~ Lee-Kesler Correlations I vIM) ‘l’~. + 1.5 — -2.67)—0.10834 5 — 459. InTb. calculated values are tlmems ad~usledfor petroleum using the difference between TIne tIne boilinsg point as lIne correlating parameter.1 -1.32712 x Ill ~(‘1’~ —459.6015 1..1 I74S)T~.67)— 0.4 where. Tb .2087611 l0~(Tb— 459. S 554.8 specific gravity of lIme hydrocarbon fraction and that of the tsormal paraffin with the same w = —7.5287 2.3O84 -026404 0(1 l0-~ 0.8(114 O.. + 8~359Tbr Nornnal Paraf/n.4244+ 0.67)~ — 0.657 x tO (1.51274 3 3.2623S) x~ /T 5 (vIM) M S M ‘l’~.007465K~. S.O /Tb.4721 Twu Correlations W=(lflPbr —S. 3 _________________ ‘I~Tt.81067 .S M l’.2..1(078 lO’~ -l .401673 -1. for Tb.204.69 psia.udit R (‘ritical l’ropertie.111)56 x lt)-~ 0. 888W + 36.8(1663 0.941211 I0 (Tb —459.19525V’ + 104.1939 x p~3 ((.ns: TIne properties of normal paral’lnmns are correlaled with the normal boiling poinl temperature.1395 xl0~ (T — 459.193W~)’ —0.15184 x I0 (T~.alu.0566/S —(0. < II IO~R) +(l. The specific gravity. S S ‘(71) < M < 30(1 0.47227/S’)x lO’Tb’ —(0.4 . 11(1(6. >0. Cavett Correlations T.24244+2. — 0.0.7134 (Tb — 459.21)28 It. = 8.1.1104811 I0 (T —459.23) s I ((.1352 K.505839w — I .969468 x 102 /(‘I~ /100)111 7 I0~ T ’ 5 —0. —13.67)’ API’ 3 5 logP~ = 2.5.904 + 0. psia.3036 543076x I))~ -9.0 1.3889 x 10 (T 768.)J0~O~ 1 1 I’ The units of temperature.97476 6. are constants for each property as follows: _________ _________________________________________________ 0 ~l ~2 a c d e 106443 - ~ 1.2(0711 -1.5309511 I0’(T~—459.131.361691V’ — 13749 wlnere tine subscript prefers to properties of norunal paraffimns and..53691 (1. is defined relative to water at 60 “F.67)’ API 5 9 —0.67)API + 0.67)2 11 7 +0.83354 + 1.58262 lnP. pressure and volume are Rankine. m’especlively.77857 -.8 ‘f = where Phr=Pb’Pc.984036 -4.6977/S’)x 1(1 927 4 6 9648 l + .071 + 1. and ft /Ihnmol.6164 I -4.6(112 x lO’~ (1.750(1 - 1.1 2 8624 W — 3.+ (0.2998 0.648/S + 0.67)’ 48 P~.67)’ API + 0.364 ~t.7 + 81 IS + (0..2).1 1857/5’) xIO ‘1~ 54(1< ‘l’~.67)API + 0.779681 x tt T + 0.408—o.= (3.162 x Itl~’ 4. +(l. ~ M S 6.0555 4.3047511 I0’ (Tb — 459. .4669— 3.5/S). TIne mellmod inilially con-elates the properties of fractiomms normal paraffins as the reference.67)API’ + 0.67)’API’ 5 = [i —(o. e. — 459. -4.169347T~~. C’orrelal.621(3 s ml)~ (‘.’i’e.829 + 0.89213 x I0’’(T~— 459.25288 5 l0’~ 0.3634— 0.544445995k I(t~ -((.42019+ l.53384 1.4844 0. x 1(12 581.+0. +d0 O. where API=(141. S 341. I9629ip~+ 3 .=T~/T~: ~b is the pressure at which Tb is nmeasured.01o63K~)/T~.3478 5 -0. —0.g. + 0.96 6.77409x1(f 2. w I—T 5 IT.s 365 CORRELATIONS IN FIELD UNITS FOR ESTIMATING CRITICAL PROPERTIES Riazi-Daubert Correlations 0=a [exp(b0 +cO.28437611 10 2 6 x I0 (Tb —459. The correlations in SI unit are given in Section 6. = 3’ 10633272 + (1191017 ~ I 0~1Tt.2898/5+ 0. the nomnal 1 boiling point at 14.4357T~) for Tbr 0.66436w’ —9481 S~ = 0.725 5 1(1.28862 lnTt.4827 x 10’(Tb — 459.~ 19869— 0.0846 1.4685÷ 3.)/ /Tb.

..0398285—0.328086/T.(%o(271)1)5’Fh)+ (I I.~ I 1 . /(11).0123420 0.362456/ T~4 0.orre’k.endi v I-I 1 (ru(ical !‘roperlues (.)j’ = ~ ~ / T +(— 0.0062 -a. 1 T =A. ) -- 2l’~) ~‘ The properties of any petroleum fraction are estiuim~ntedby adjusting line calculated properlies of the normal paraffin with tine same boiling point as.St’ —41.)/(l — 2f.71579 lnM~—0.7522 mM +35.1 22488/(ln Mp)’I —24. T 5 = 11) = ASp[12.366 .tions 367 The molecular weight of paraffins is given by the following imisplicil relation.4 .j.I955/7~_(t.om — 75691 + 0.r=CXPF6(Sv S)J — Critical Volume: Vc = v~pt(l+ 2f. = exp[4(S~ — s2)] — Critical Pressure: Pcp(Te/Tcp)(vcpIvc)~I+2fp)/(I_2rp)~ 2 .I40l1~+0.3l55(lnM)’ AS~ ex~10.~1(1 which can he solved iteratively rIsing the following itnilial guess.714l9+ 2.) Pptroleu.193168 /1~ )AS 0 I T~.8544/(lnM~)—0.1 AS.(X)23O535ThJ~Sp] exp[(5..182421 + 3. ~uu A5si~’I + (o.m Fractious. Critical Temperature: ‘F.948125/ T~ AST AS. Mv = ‘F.286590(ln Me)’ _39..1. 6( S~— S) Molccuular WcighI Iu~ M = (Imn M~.1(1 + 2fr)/(l —21) )I’ “I’ = 0. )I (I f 2 f.= expI5(S~ — S)j — AS.01721/ T~)AS ‘.4277+252.. 44 — I — 0.53262_46..

0=cos’t(J/~J_Ql) A..fD)t/~— a /3 1 If D<0.Ju2+4w2L 1 uu’ +4WW2 jln}I2Z+U_.3./h) A + takes the following dimensionless form: 2 Z~_(1.1 01 ~1 ~n . Q = (3a.T b[. 12). —27211 — 2a )/ 54 1 D=Q -fJ’ lIme eqtmation inas ounly one real moot: +(J — Z~ = (J + \/D) The expression forfugacity of a component in a mixture is: . RT and RT Solution of Cuhk Equation 1 Z -t-a Z’ +a. fl a /3 1 .W2 ‘l~(UZ_2W2)UU1 2 2 )(U +4W’) j = 2. II D>0. B~ .368 ~ (- flquazu’n of State E.anL . .4~B_U)Z’+(A_BU—U—W )Z—(AB—BW’-W’)=O where A~—~—. One equmaliomu Isas tinree meal roots.j___I2~x~a L U’ +4(w~ +4W’ /w)W’1 1/a (u /u)U’ 11 t — ~1 mi I 2Z + 1)— .~.T 1 Ut Id(nw)1 ~)un 1 in.F4W2j (Z’ + lIZ— W’)(U’ +4W ) 2 1 -j ~ RT W~!.. . ~RT v—b a v’+uv—w’ = ~ . — a~ >/9 J = (9aua.Z+a =0 1 1 The above equation results in the following expression for the fugacity coeJ/Ic:euut 0. where. the dimensionless derivatives ofEOS parameters are defined as. u = ~xu . ~ufl(iW I ~ in .. Eq.— .mpre.fU2+4W21 U’-)-4W’ L2~~+tj+’~4’~”i . =—iui(Z—B)+ — ‘ .~. b= ~ . E. ~‘./—Q cos(0/3 + 240°)—a /3 1 where. =2.1).. n.~ Z =2. B(b.cio~us Immmpiemnsemnling line raundom mmsiximsg mrules for the tnnixlure EOS parameters (Sectiotm 4.T 11 Jn. defined as. (RT)’ B~-~-.t. RT lnu~.f 1 1~ cos(O/3)—a I3 1 Z. tine equmatiomn Imas three real rools: ln4 =—In(Z—B)+-~’~--+ Z—B 1 A A.J—Qcos(0/3-l-120’)—at/3 (Z’+UZ—W AE2(2z+U)W. Jn.10 pure compound: ln4=(Z— I)— In(Z—B)— A VU2÷4W2 In 2Z+U+.T If D=0.JUc4W2 2Z÷U-TV’+4W’ Let. 369 EQUATION OF STATE EXPRESSIONS a The general cubic equation of state. i[~rmu>~ ut ~)n 1 . at least two of tlnern are equal: = 2J° 3 — with the total number of moles.f~3~+4W21 A[~(2z+U)(w /w)W’ +(UZ— 2W’)(u /u)U] I [2Z+ [I + ~JtJ2..(4. and w = we ohlaimm.

— = P(v2 ~2hv + 2P(v — b)(v+b) 2RT(v + b) + a h = a’ (v—(. I). result in. Eq.( . by multiplying it with in. and dividing the obtaiuned expression by the total number of moles..i 371 THERMODYNAMIC PROPERTIES USING PENG-ROBINSON FOS (PR) h. us. by n and differenlualimng tine obtained expression of the Iotal entlmalpy. we obtain. ~ Multiplying tine molar enthalpy. NN a’ = ~ xx. H = ç’í N P _T(~) }mv + PV + ~ Converlimig the molar volume in PR differentiating it. .(l — k.74) and (4.j~j)• using the randoumm mnnixuung wles. h~”=h —c P 1 1 Partial Molar Volume vcor=v~c Molar Enthalpy v’ = ~)v ~ The total enthalpy is calculated from the following tlnernnodynauinic relation.78).. (4.b) - a~a/[v(v+ h) + b(v - b)] wlnere v.27) 2~2h a’ a’ —)lnI h. Eqs.J~--l)b’ N —InI — ~+ Pv+~x.(4.4 1~ f~endInC l~. we obtaimn.U. and where the last term is the total internal energy at low presstmre and prevailing Ieulspcralure. is the partial molar volutsne.qt4ahiotu of State Expressuon. ~=[l +m(l 5 2 Tr° )1 (4.370 . tIme corrected partial molar enthalpy is given by. 10 total volume.\ (v—(~ _i)hJ + v —(~ — l)b v +(~+ i)b ]+ Pv 1 1 — 1 1 b ~v+(’f2+l)h v—(’/~—l)h v+(’12+I)b 1 + P = RT/(v . h”’ =Im—cP Partial Molar Enthalpy h. derived above. 2J2b ~v+(’f2+l)h) I where.P)(v’ + 2hv — 1 ________________________________________________ — h’) h’) + [2h RT —2~x~a —2h P(v I 11 1 ___________________________________________________________________________ — — h)}v — b) + b~a Applying the Peng-Rohinson equation of state to calculate ~.31) When using the volume shift. and it is determined by summing the internal energy of individual pure comnnponents. N (RT+ h.~’’ + x~ 1 12 43 When usitng the voiutnne shift concept to correct tIme predicted minolar volumne by PR. the corrected molar enthalpy is given by.r n.23) (4. h. ~ an. ~i)r. )a~’’mm~’[mT.

~ I ~ I[17—”——. .00 .00= .-.* .o. a.L I I -~ J~’~! ~ I ~-:Th-~ a S S I“on I //: ~/H 30.47 -- ‘-~ ~~±Jo ~ —305 :~—~ ~ 0% —‘00 0 00 210 300 ~O 300 300 ‘00 0% 000 Figure Dl.-~ 4 -~i~’._ l40 _‘~ -. 00=0 -~ ~-. Convergence pressure of hydrocarbon mixtures for use with GPA equilibrium ratio charts.0 2~ nOn -2 •~ ‘~ ‘~ 010 20 000 3~ ‘20 . -~ .1 \-u.nfl.-3 53 ——3 _. •. :1 ~ /~ .° P “?~-.1 ___________ .~ C 30000 ‘ 100=0 30=0 30000 ..

~ —.. . ~_i . ~a. ... —~ _‘ ~‘ . .. ... I S . _ . .. ~ ..~i. ~ ‘Ii c~ . ‘ II 0 ‘Jv ~ . ~ . . I ~ . ~it~ i~ . .a) co..:.orc I) 4 t~q. ‘ ‘ (“1” ‘ ):i:I5~.. . ‘ . kPa Fig.. ~ ... . I 0 ..— 0 . -- i~:~ l.. ~~I ~ F’ ~~ . . !. . . . 00 .. .. .. _— _ 6 4:i~-’•_ 1 ~‘.01 oSno .I 1~~ ‘ . to I ~ ~ ~ K =Y/ 5 ~ 0 ~ ~ -~----:-~-:‘. .. 0 0%~ .=. -‘ ... p ....o- 0 ~ 00 ~ ~ ~ ~ ~ ~~~-Hl .‘ lili ‘ t~ ‘4 ~ _~ : .—.~ . -~i~‘~ ..~. .(‘ . 3 ~ ~ 4-....hr. loom Pressiure.. 0 ~ . -. . ~ .. .. ii ~ I~ _ ~ ~“o-~ ~ ~ I .ul.. .-_- . .. .. . ~ ~‘ap..~ is 00 ~ . .. 00 . I. U.... .~Tt .’ :iia~~ . Sam ~I:. . . ...um ral.g. :~ :.1 375 I i. . ..374 PRESSURE. V~ ~. ‘~: ... . - . PSIA Y~ .~~rtIso:iij~.I~. ~ .‘ ~ ~ . kI a 115 14 47 ~tll’. . .. 3 1’ ~ ..- ~ ~ .I . IL— .-.. -:: .c~ “~‘r’n’~’ ’ . n . . am 34..oiI. o• ~0 ‘ ~ ~._ ~ _ — — C’~ K =Y/x . PSIA 0 t •~I 1. ~ ~ ‘~‘. ~ .. .-. ~ . I .~ .-~. 4 ~ i~: ::.47 MPa (5(XX) ps.—~‘~-EH~~ —..s ‘. I ... ~-= _~ _ ~ ~ ~ . . .:..nvcrseoce prescore ~-‘L’~ ~1 - . ~ It 3 ~_. -. . .. . . 3. . .~ — —— ‘ . 4 :. ./n.o) c.:. . it.It” . ~ :.ver~cnce pressure. 0+ Equilibrium mau.orn.lr. ._.. .v. ~ . ~ ..- ~ — 3 v’~~i~ ~o -0~ ~-‘. . ~. :0:. ~ .. ~ 0 ~ .. ~ ‘ ~ .- ~ . .. -’3 0 0~ PROPANE I ressure.. ‘ ‘ ‘°~ — — 0 ‘ ‘ . . ~ .f.-. ‘ : . ~ ‘~v : . 30 .t ‘ 3 ~5.I .:fuji..~ ~. I..~0 100 PRESSURE.th~ 0 ~1 ‘ j: . ....~ ~~. ~ ~1t. ~~ ~ ::I~5. .‘:c ~— — ‘~~i1:~’’~. . ..):. — . .. ...: ~ .~ ~ ..: P ‘~:vv-( ‘ 0 .-~ .I ))) r~.C’ ~ ~ .~: .. Fq. .-~ —_:~:a.. . _i :. Eq.t_ : ~‘. ~ . . . ~ ~ .0I ‘:.~ m3~~io . ~.‘:. 0 0 — -- 0 .~ 3.. ~ . I ..~ (It — • . -. . 4 .. . 0—. ~( .~ ..:::s(~ ~ ~. ~ ..

47 NI Pa I515)1) psit~).0 !~..i..~ . 377 Pressure. Oqiii)~I’riut.I.uvergeucepress.r:~.3pt koathi Ij.. kP:m i’.376 PRESSURE.!.:i. at 34.0. Equilibrium raujo at 34..g.1.5.~ Riot.47 MPa (501)0 psia) convergence pressure.~0...0i/i/~~ jti.... kPa Figure 0. I’ressrmre. PS1A 300 ~ .Ie. - BUTANE ..ore i) (.

0....oto. ~ • _ ‘i50~) . ..‘. 10 . 3 S 0 .. ~— I ~.i . . ~ ‘ ..l... ~ ~ •~~~-:‘• .h.goiI. : ~ . _ ~ — . “?(~‘ .’ . ~‘ : . .r. — . — .5:. -:.o.. 3. ~ ~ . -. ~ ..~I./ .‘ .4 7 r~i t’a ( 5(55) psia) co~nvergcncep3cssoome.’r.~ ~ . ~ mu ~ ~ ~ . - J’rcssume. Ii~4~ = . . .:: .. 2 3 1’ mm Pressure.. )S)$1() u’~. .~o ~ . at 74.ii.)’ri~or. ‘ n’it~ ~ I ‘ . Ru(.— .t.r ~ ....~ ~ . .j~ ~ 2’ ~ ~ II ~ : ‘ :1 L ~ I :~ . . I.....iu. .~ ...: ~ _ . ~: . :: c.. - —— . ~ .: 0 8 K.. .tOO!!1100 u 05 .I. ‘ .:.. --. ~‘e ~ ~ I ~ : .?...‘... . . e .4.~ 5..) 1. ..--~~- . .11 Ptll’.. . _~4 0 ~ .... “a..st •i... ~ ~ I’ ~ 30) r... ~ ~? _5 .. ..378 00 I0~ ~ ~ 3 3 PRESSURE. ~. 5 ~ ~_ ... .. ri) .) c~’ns~-t)’..~.. . PSIA 500 m. . PSIA moo aoo . ~ 10 : I I ... .i..1. kP:u I tgure I) 7 PEN’rANE II-PENTANE i 3 .. kPa I~ I ) I) l~.l.. ~.. ..~ Iq. . ~ a.. _ . ~‘4AI ~2 I‘ I. .00~/o)’3o~o~~J R.3 I ..I’... 379 PRESSURE.. j~~ &4~ : ~ ~ 0 fli.si). I.

.I.. kPa Figure 13.3i~0. at 34.Riot.. 0.qoi..9...rtutit rat...o/..o F~.380 PRESSURE. i.t....47 MPa (5000 psia) convergence pressure. kPa Figure I).I. Pressure..47 Mt’a (5)))))) psia) convergence pressure IIEPTANE . Rmi..- - PRESSURE.. PSIA Iti)~Ill~)... Equilibrium ratio at 34. PSIA u 181 S I ‘~‘ 3 Pressure.

P.4 I ro.t. Corp.r.~ 3.. PSIA so m I PRESSURE. Uuio.o.) 47 MPa (5)5)0 psoa) convengenuc pR’ssi~re ... 0 *907 .o~ n. Euiro nntnt.’o#o0o.hr. )947 1flb0i0~i000.5..5~ of 302.ow... kPa Figure 1) I) - OCTANE l.I. at~.o 8.I) 2 l..a) 54 Pretsrure. I I ~ Pressure.. of G.0..on...u 947 1. ~ Pt.j.oi(ihriu..ceprcssoorc NONANE l-qu.un.382 E.nto....u~ 3 54.. (5)HH) pun) c~inverget.d nod 3.0(0 ~ Rut.PSIA 383 3. Un.. rat.ot. I 00..0. PRESSURE.d d~u’-n~j -- o . uf 0 P..aso I . of Uiuf.bootn~iuo. a) 5. kPa I/ Mt’.o~.. -~1~.t.g.1o1).. E..o.

. ~ 01 __ r.....lecuolar wciglsl boundaries. h..rrelalio. I 54. ~i •.‘ ) “ ‘ ~ ~ ~ jL~fl.. . : )) L2. 2t ut I) ~‘ t ..a ‘-4n ‘ . — .._. tO. ~ .’II:1~-. see also earhouu group clmaracterisatiomo lactonr. —.4::_. PSIA ~ ~ I 1q~o..:(”. 327. .ir Ihoitls.. 237 g000uoma prohahiliuy disirihumion 236..iling poi sm.t.... 173 corretamiorms. see also nninimmnlun mniscmhulimy pressure Darcy’s equalion. j~.. 2111 Ilterustiol gradient. .0. ~ ~‘4 ~ 4~ (t~/’~. . 75.. ~ ~s . 319 Siandiung and Ksoi.13 Equilibrium ratioat 34. ~. 4-)(’~’’.‘..nvergeuce prcvsure l~ickwarol uunuliiple clunusucl. ~ ~.’~’. . 222 Frlmusmer corrclalj). . See Gibbs phase nile density prcducm ion Alanu and Kennedy e(luaii.lt’Cllon... 199. 192-195 Kreglewski and Kay unmeihod. o~I :~ _~.~:Hf .O . ~I~~~ I m.-=i.‘ 0 ~-:. 39 co’inup. 149. 193 v. ~ “: u• ~~ . ~~‘O’. 3. 3. 353-354 sungte carbon groups.—~F5a . 73. ..ut r. 1’~.p 130 . 211 nsotlecular weiglut.) evaluaui..200-201 non equitibrittin . 2(11 Commup. 131 Slarlummg modification. bj~ Tb.n lactor clseun coil poiemiui:il.tuuracfivc lenin.nentual dislrihumioin. _c’-i—=— ~.~: . 38 carbenes. 38 hto. ~ H ..lume 194 critical tie tone.“ ‘—._. 331.( .. . . _ — .t. 2. : ~ . 268.d .n. 4 mruc. — . su’e abai ef. 9. l98.~ P’on.. condensing gas drive. .R ~ —. 222..n ~957 ‘gon of 385 INDEX 0 : I I . ‘ °i0. ‘~0.. .n reirievtnt. . corresponding slates.74 . l.i. ml .~ ‘. 239 norunsal ho. 200 cla.. 199 sigutilicance.000 .. 38. 221-227. 222. 143 calculation..uattn.usflto.’. - ~-.otj.. 211) Benedici. 256-26(1. — . . ~‘7. 119 criiteal mnnolar volume. 332 degrees of freedom. .0. ‘ ~ ~ ‘d1~~ E ‘~~3h :~. .5.n . . 213 Caveti eorrelatuon. 2(12 heal of Iransport.. 2 ads. 26(1. 13.‘. ~: . ‘ -— ‘~‘.r..Y ‘~io. 197 gradieni.~‘Ic K~/x I ~T=—-— ::. .o. see also carbon grottip exp.. .. .Iohr. ‘ t 5 . DECANE 100 30) ° 500 ‘ ° ‘ 0. 73 aru.. 18. c . ..n oI rescrv.)’..l . -.. 2.atv. valuramed pure compoion.. 73 appareni liqiuid rlensily onFnatural gtis. see ills)) oil lesls bubble p00mm pressure. .~i I~I i~ ~ . (~. 23 apparcni oil densimy. Ill. ~ 3 I :~ . ~ ~ . ‘5 5: ~ i)~’ H~ ~.. See aI~t..~c. .. . gas injection iests hum ling point. ((17—11)8.. 17 . ~ I~ l~’~ ~ ‘‘ ~ to ..156-157 Caveim corretamion.w-down 39 (Jal. 5. ~ ..opuOoOod ond 4.ns 223 Riajj-[)auhcru coru-elalions 222 properuics by runiximug.~‘) ~ S Atano and Kennedy equatittn.. 4. .~ Pressure. see also gas condensate critical cu’unpressmhiliuy factor.. 8 uuieuloosj.29 composilional grading. : -= .. see inverse grmuping comiipre. . — -. 2 API gravily.. _ ‘“— ~ ~: ~= __ . ~ 1 ~ ~ h ~~ t . kPa Figure 13.un 222 I_cc. -I. 241 critical properuies hmnsrfes.~ : . 1 .’ ~ ~ Ii .sl.. — -— -‘ii —.‘ (22) r’’ l~ 1 1 (~o1 . 221.__ -. U” ~ ‘y of E. 183... ~ . 2 ....Rootot. 28-29 corrctamiorms. t . ~ . (11. ~( L’.. see gas commpressihilimy factor coniinu.mfe ~ Ii’ 1 T . . 132. ( 410.’.t. U ~ 0~ .b LI. 195-203 aro.tfi Iinu.’ ° (~) soot ‘ .- . see also critical properties criiical pu~inm.’. 86 conlculamion..Wehh-Ruhjn EOS..osotional analysis. cf. see also gas injecuion..uis descripiion crotucal propermy correlaliuns.itoau cs.. .. - 300 . 213. (.. . ~.. 64. 134.~I .. (55. 213 msno. see also density alkanes. ~ mu ~. acentrtc factor. _~ .273.. 2 carbon group criiical properties. .. _~:I:. ~iy’~ . . . . . . ~ 60 ~ )... : ~ I.. 68 (‘7 j. ..’’. .. ItP~ ~‘ It. 2 carboids..unatic effecm. 152.. .ssthlluly facio. ‘~=- ~o ~ “e~ C— — . 257-258.-: . 0_I _ .o S i S..~..osoi .. 75 FOS. 947 ob.7~E((~i/..non. 5f~ 1.. . 214 aspltaliemnes. 131 binary interacuion pimraunelcr.ons. sec also gas in. ~~ 8 40’. see tulsjt mmsmxing rules black oil. .n 126 (toll s)rcauts (olirs’cu 1 sauuspli nip. 42-52.. 241.‘ ..2 rE.. ~ _5_ — - r 4 ~ -) = 2 c’e~ 19 — — is’t~s-’j~.J ‘iiI 12 i~’~u ~ U’!F ... 31)8-31)9 single carbon muuuimhcr grotomp.e0~.)j)~((~ I 5 I ~ (~ .Io.eflocient Ill . . . 169.. u ~ _ _ I~ ~ I~ jt ~ ~: . 21 3 specific gravimy... II. 67-79 le.001 ~‘‘~ .Kesler (‘tim cat eorrel..~. 352-357 actuvuty c. see Walson characuerisaui. .. ~ see ntso.clisoracmerj. 10 Cot charl..4((5s tj~g 16. . . I . see also vapour pressure crico. minimum miscihiliiy pressure conndensiitg/vaporisung gas drive. ~ 0 ‘ .us description 234. 272. ~— - (‘ii ~. ~ ~. noruunal. 22.ndentfnei-nm IS. =~. 181).tts..~ ‘~0 — -.201 ()unsager relati. . . ~.sis.— Ii U ..-:’~. ~ . see also equilibrium rami~.t. see also riuuuluunnummo miscihilily pressure cross over lie hines. .. — ~ ~ ..:. ‘~ sot 8. 0~ . 22 I peruurhinliotmu expansoon c. 336 eapullary condensation.. Co..rhcnj untuleritml .‘ .‘.384 I ~ 0 I I S PR ESSU RE..—~. ‘ - .. . . 355-356.0. i ~ I .oo.uit.. C’ _~-1. 100 .. Os 0 5’o~n.ssi licai. ~ ~ ~.~im ion. ...~i1:5 .246.000 ‘ ..—ac’ C’ 51 ~ ) 1~~ . 259.47 MPa (5000 psia) c... ..-~ -~~t ‘ = ~ r I ~ . mmnimusum miscibility presaure convergence pressure. see also critical poini pure connpounds..Is.. . ~ ~ ~b... 194 Li’s mixing rule.

... 70 t. 142-161 tnvarmance condimi. 109. 347.d.k’rWaals PUS.uip lest. see ats. 1(4. 320 saturation pressure. 243. 256. 149 Peneloux ci at.214 (oil compressibility. 260. 5 iutiscihility couucepts. 314 equilibrium ratio.26(1 espcrttonental studies. 129. 148. 46. 283-284 pendant (Imp. 169 forward multiple coniacl. 302-307 Wlnius. 346 rohtostness.. 185 rules Kay’. 255 flash calculations. 52-65 constant cotssposo)uon expansioon. 112 equtlihrn..ns Lee and Cinieti. 40 deal gas vo. 175 irivial solution..cclteclnier and Gui.uI.Kesler vapour pressure eorm-etati. see Viscosity oil tests cotnohunalion ofdam.. Ill) Dratuclnuk and Ahou.. 217 comparison wo lIt distil lati.0(3 coutopulatiuinal I floe. 176 gas to oil ratiu. 340 gas viscosity. 304. 106.171. 172. 23. 314. IS gas condensate. 1(19 fugacity co’efficicunt. 346. 23 olefmns. 118 intermediate pressures. 321. 303. 49-52 (lofferentual liberalion 45 differential vaponisamjon 45 separator.. 272 Jensen and Michelsen 273 Ku.rrelatf. 332. 274.uos 221.rrclation. see carbon group Gibbs energy clnange.. 114. Grahoski and Daubert rosodification. 291 Weonaug and Kati. see als.cvsky..Kesler crulical pru~periy ci. fugacity limiting tie liune. 86 gas injeclion leSis backward tutultiple contact. 159 iuoiioiuitntui miscibility enrichment. 2o. rising bubble apparatus. 175 definition.in flash calculations 68.Iex Index 387 . 9 10 PNA. 121 Mollersop equaloon. 161 pseudo crimjcal values. 339. 25.rret. 3 14-323 general van . 273. 172.io 306 1 equal weight (iunass).. 305 selection. 347.n 159. 273.Ier Waals iype. 105-110 I . 258-260 mixung rules. 83 stability. 114.lunons.olutttns. 268. see viscosity local composition 159 non’random 159-161 polar. mixing mixtures.itat forisiatjinio voilujme factor. 1(16 miuiinisation. gas hydrates. I 91. sec also equi libriutti ral iii loytlrates. see als.le Iuacli.to. 314. 215. 316 volumes.el PUS.114 selection .in 13.. 343. 123 Wilson eqtoation. 160 raisdom usiising rules. 293 salts in Water. tiiscihility Ititui. 16I. see equilibrium flash calculations formation water. sec ols. 56. 26 inulticotsiponent mixture. 50-SI gas recycling. 156.ce.nslant vottoinne depletion. 141. 141 Starling.ui 1 4S see’ its. 276 utiunlecular weight cottdensame 79 measuremeunl.. see also dew point gas cycling. 136 gamnsa probability distribution. Pray-Clark ri.tunen.258. see also continuous description gas density.olsio carho.n willn density olilference. 176 definilion. 147. I pressoure btoilil. 288 .bocpmane.. 116. 257 mununsum muscibility pressure. 111-125.. 13$. 294 waler nonssal octa. 310 estimation 116-125 PUS. 1(6 unlerfacial tension dislillalion. 314. 325. 190. 306.314 Dtune. 314. 71.rrclati.. see also carbon group phase uliaprauui etluauoe.ontact. 325.i. 73 oil c. 138.. 267-268. 274. 348. 24 Edrntoer correlation.Kassetto c. 141 Jhaveri and Youngren.ns 223.lti energy. 10.. 21 5 non-eluted fraction. see gas injectioto tests gas soluhility in water Krucl. 1711. 69 314.sli Ct al. 276. 124. see also.l-liqooid displacement. 217 packed c. see also carbon group enuhalpy consuanu flash.ilar inieracijon coefltcienus.Rohjnson POS. 2. 254.on 302 I ce . 175.s tuotsing rule. 267-268.Iuoiooe.Redliclt-Kwong.lsydrocmj-. 56. 276 Peclrood 274. 178. 143. 220 pseudo critical condilions. 71—72 sisciisiiy.. rclatoi.ee. 19 pure substance. vtscirsiy iiielioing point . see also gas injection real reservoir fluids. 80 H2S and C02 effect. 277 first coniact rriiscihiliiy. 53 cu. sinaI. gas soluhility I bit luiitiosn plol.s law. tuning I . 2 13. 215 Henham ci al..ewis rule. see gas compressibility factor formation volume factor.tn gioutop I leliiil.. 54 dew point. 143 near critical poinl. 265 swelling. injecluon tests naplnilsenc. see also gas formation volume factor.... 276 Iliodgins el al. 327 Soave. see tuning Valderrama-Patel-Teja PUS. 245 rich gas. 317 OPA K-value. 124 split meth.. 42 utnuttiple contact tests.Robinson PUS.oc. 309. see also gas condensate calculation. 214. 53 colour change. sec . 148 l’eng. 147. 260-269.. 142 Zoudkevilch -Joffe PUS. See alkenes paraff’uns. 132. 271. 241. carbon group l. see also equamion of stale Peng. 4 Grouping. 37. 3)15. 182 root selection.221 capillary c. 266 single Contact. 116. 19. 152.Benedict-Wchb-Rubin. 256-257 prediction methods gas chromatography. 322 Schmidt and Wcts. 338 gas in solution. see swellung slim tube. 156. 222. 221. 146. 326. 70 usollicrunnal conuunpressihility coeffmcjenu. 223 Pamel-Teja EOS.. 289 preoliction metlt(xJ br lnydrocarl.ot i. 192-194 . 151. 140. 64.49 oil specubmc gravity. 212 tuneasurennenl 282-255 Inlerface curvaloore. 17 pseudo reduced properties. 3)8 Redlicls-Kwong. 43 oil densily. 273. 275 Firroozahadi and A~iz. 310 optimum number.ewus nile. see also equation of slate perturhaluon expansion critical properuy courrelati. 3(14 eo ioal iioo.. ject 000 uonaterial hala.. 273 carbon dioxide. 106 equaloon of state comparison.f. 212. 329.386 dew point 1.45 clnart. 82 gas condensate. 2. see viscosity generalised single carbon group. 174 pure substance. 59. 267-268. 171 first Contact miscibility. 307. 182. 68 viscosity. see also sapoour pressture Lce-JKesler critical property correlati. 141.. 338. 86-94 gas compressthility factor. It 6 llenrys law. 305. 339 predocooin reloahility phase composition. 325 sensitivity. 243 inverse grouping. 314. 286 water. 314.lecular weight.t. 329.on iuietlnane.. 46. 122 internal consistency. -263 forward multiple c. 17’)— 152 negatis’e flash. 292. 79 specific gravity.. stability invariance condition l59.p. 285 scaling law. I toi. see als. 2 1(1-215 dry gas.n incubi . 109. 260-265. 59. 17 I. see Gibbs phase rule. 270 (ilasii.ns. 282-283 tuning. 135 l’a)el Feja. 31(1-311 Newley and Merrill.Kasarnovsky colioatton. 293 inoruuosuc stability. 307 Gaussian quadrature. I 89 robustness. 157.~. see oils. 341. see als. 130-131 voolume shtfi. 193 I lenry. 17. 131 also gas injection tesis fugacity.waler 292 predic) i.n bubble poini. 3(12. 156. 160 van .’ gas it. 236.27 gas condensate tests. 155. 288 Macleod-Sugden. gas cycling. 63 gas foonation volume facttir.

341 sample collection. 340-345 gas condensate. 131 Starling modification. 335. 77-78 water. 47 vented at stock tank. correlation. 334 gas. 314. 92 content of lnydro. 335 . see also coniinuous description Rackett compressibility factor. 254 triple point. 131 virial coefficients. see also oil tests residual viscosity.sn phase. 324 grid-time step suing. 36-38 surface sampling. 330.. see also critical compressibility factinr Zudkevitch -Joffe EOS. 314. see relative volume volume shift. l54. see also equation of state Benetlict-Wehh~RuhinFOS. 266. 69. 43. 19 Riazi-Daubert correlations. 65. 35 recombination. 92 hydroicarhon solluhility in water. 68 stability analysis . 342 evaluation of reservoir fluid samples. 325 fluid characierisation. 34 Schmidt and Wenzel EOS. 88 density. 324 Valdenrama-Patel-Teja POS. 4 Lee-Kesler correlation.bouooe factuir. 334 relation with IFT.ipperer. 336 volatile oil. 354-356. 87 viscosity. see als. 150 super critical hydrocarbon components. 327 weighting factors. 43-46. 335 Loltren. 91 formation vo. 140. 323-331 consistency of regressed parameters. see also gnssoluhility in water vapour pressure. see also gas injection. see also equation of state - oil correlations oil. 14. 314.83 I-lerning-7. 89 conteuni of tiquid hydrocarlsuons. see also gas injection tests temperature dependency parameter. 331-340 . 25 Wils. see also equation of state residual oil. 334 Ely and Manley. 222. see also black oil correlations repulsive term. 122. 47 sublimation curve.sn equation. 68. 330 dynamic. see also equalion of iso-kinetic sampling. 156. 142 Rackets equation. see also carbon group viscosity prediclion sampling condensate ring. 87 Vasquez-Beggs correlations. 187 Standing oil correlations. see also gas condensate retrograde vaporisation. 14. 153 Twu et al. 5 tuning. 46. see also oil testing Yainada-Gunn correlati. see also viscosity resins. 69. 183-192 limil. 346. 27. 90-91. 255-256. 14$. 13$. see alson equilibrium ratio Y functiois. 155. 314. see also black siock tank state water conspressihiliiy.n equation of slate van der Wa~bs EOS. 138. 93 tuning. 2 retrograde condensation.carh. 254 tie line. 36 minimum gas well flow. 146. 335 low pressure viscosity. 340 corresponding states. uniniussum miscibility pressure vapour pressure Cox chart. 141. 14 Raoult’s law. 1(12 Redlich-Kwong EOS. see also equation of state Soave-Redlich-Kwong. 19. see alson equatioit of stile vaporisong gas drive. 45.sn. 132. II Index experimental data. 13 water. 212-214. 67. 16(1. 340 well preparation.oil. 346. 87.388 quadrature points.tlray-Clark. 314. see also equation of state solution gas to oil ratio. 5 swelling test. 339 limits of paramoeters regression variables. l30. 36. 136 Mathias and Copennan correlation.. 333 miscible. 330 wet gas. 151 ternary diagram. 93 Watson characterisation factor. 321. see also black oil correlations virial EOS. 189-190 Michelsen method. 154 relativepermeability. 67. 243-244. see also equation of state reduced properties. see also oil volume factor. 334 relativevolume.

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