GAS CONDITIONING AND PROCESSING Volume 1: The Basic Principles By: John M. Campbell In Collaboration With: — Robert A. Hubbard, Chapter 9 Robert N. Maddox, Equilibrium and Energy Data ‘©Copyright 1984 by Campbell Petroleum Series, This book is sold for personal or library use, oF for regulatly scheduled university clases only; use as reference or manual for adult taining programs is specifically reserved for John M. Campbell and Co, No part ofthe text or original figures may be reproduced in any form without written permission of dhe publisher. All translation rights are likewise reserved.GAS CONDITIONING AND PROCESSING VOLUME 1 SEVENTH EDITION Library of Congress Catalog Card No.: 76-157183 First Printing July 1992 Printed and Bound in U.S.A. Published by: _ Campbell Petroleum Series 1215 Crossroads Blvd. Norman, Oklahoma 73072 Phone: (405) 321-1383 Fax: (405) 321-4533 Telex: 9108306520 CGX NormTABLE OF CONTENTS Chapter # 1 INTRODUCTION. ‘The Fundamental Technology. BASIC TERMINOLOGY Elements and Atoms. ‘Chemical Compounds and Molecules, Physical Compounds... : Relative Atomic Mass (Weight) Relative Molecular Mass (Weigh... ‘The Mol. Valence Mixture. 3 BASIC HYDROCARBON NOMENCLATURE 5 Paraffin Series Formula: CaHl2e.. 3 Oiefin or Bihylene Series (Alkenes) For 6 Acetylenic or Alkyne Series Formula: Cablzn-2 i Diolefins Formula: CoHan2. 1 Aromatic (Benzene) Series Formula CpH3n-6vern nner i Saoa: 8 8 8 9 9 9 i az CoH. Naphthene Series Formula: Calon. PARAFFIN HYDROCARBON COMPOUNDS... Radicals Alcohols Mercaptans. (Other Carbon-Sulfar Compounds ‘Organic Nitrogen Compounds + AMINES sosnrnesn eter eee tae eee eee, Gryeols ss 10 ACIDS, BASES AND SALTS. 10 ANALYSIS OF MIXTURES. Wi BASIC UNITS OF MEASUREMENT B Presenting Numbers..csesennnsnsnantnsnseannnsn ae 15 Mass, Force and Weight. 15 Length, Area and Volume. : 16 Density a 16 Pressure 7 Temperate arenes ee eee 18 Work and Power 18 Heat Energy i 18 VisCOSILY a snsnnnnnnnnoranns 18 ‘VOLUMETRIC-MASS CONVERSIONS.... sn sens 19 REFERENCES. semen 20 APPENDIX IA: Definition of St Base and Supplementary Units 7 . 21 22 APPENDIX IB: Definition of SI Derived Units having Special Names. APPENDIX IC: Summary of Basic Conversion Factors ...0a- 2 PLANNING THE SYSTEM. ‘THE BASIC SYSTEM. ‘Constrainis of the Basic System. ‘THE DECISION MODULES, ‘The Reservoir Module ‘The Separation Module... (Crude Oil Treating Module. TABLE OF CONTENTS iProduced Water Treating Module 29 Ges Processing Module 30 Process Selestion and Design Basis. 34 CONTRACT TERMS, 34 Gas Contes. 35 Liquid Contacts 38 HE PROJECT PLAN 40 SUMMARY sess dl REFERENCES sone Al 3 PHYSICAL PROPERTIES OF HYDROCARBON SYSTENS...... EQUATIONS OF STATE... ‘Nonideal P-V-T Equations. ‘Corresponding States Concept ‘Third Parameters... Mixture Combination Rules GAS DENSITY. Katz Conelaion and Kay's Rule. Application of Figure 3.2 to Gases Containing H2S and CO>.... Approximate correlation for T’ and P’ Other Correlations for 2 : LIQUID PHYSICAL PROPERTIES Distillaion Characteristics. ‘Watson Characterization Factor LIQUID DENSITY...... Units of Density ennnsemnnmannnnn API Gravity, API Barrel General Correlations. vt Relative Density Versus Molecular Weight General Nomogeaphs.... Corresponding States Methods... Effect of Methane and Ethane. Summary of Liquid Density Correlations. VISCOSITY... Units of Viscosity GAS VISCOSITY. LIQUID VISCOSITY . SURFACE TENSION... 7 GENERAL PREDICTION OF FLUID PROPERTIES. USEFUL CONVERSION FACTORS FOR CHAPTER 3 REFERENCES... : 4 QUALITATIVE PHASE BEHAVIOR... SINGLE COMPONENT SYSTEMS PT Plot for a Pure Substance... MULTI-COMPONENT SYSTEMS. Erfect of Composition Effect of Cr+ Characterization. Effect of lmputites. APPLICATION OF PHASE ENVELOPES Reservoir Behavior : a oo se : Pumping Liquids... eee ror 89 High Pressure Pipelines. ai VOLUME 1: THE BASIC PRINCIPLESRefrigeration Processes. Operation Near the Critical REgIOM wnwmnmrnmnsnnnnirannnn rensnne Practical Suggestions, z # 91 GIBBS PHASE RULE. . . hon a1 PREDICTION OF PHASE ENVELOPE. oe eee teens. CCricondentherm and Cricondenber'T and P. 93 Critical Pressure and Temperature 93 REFERENCES. wn 95 5 VAPOR-LIQUID EQUILIBRIUM BEHAVIOR... eanennerannnesnne ST EQUILIBRIUM VAPORIZATION RATIO. : Partial Prossure Concept nner Fugacity Derived K Values ‘Computer Solutions for K. K Value Plots. Convergence Pressure Concept. K Values for Heaviest Fraction APPLICATION OF K VALUES... Bubblepoint Determination Dewpoint Determination Flash Caleulation Determination of Phase Stage Separation. SOME CONVERSION CALCULATIONS. ‘Composition Expressed as Liquid, Mol or Weight % Composite Stream Analysis Conversion of Flash Results for Actual Flow Rates... Basic Conversion Factors ACCURACY OF EQUILIBRIUM CALCULATIONS PRODUCT SPECIFICATION Reid Vapor Pressure. PRELIMINARY PRODUCT SPLITS STORAGE OF LIQUIDS. Pressure Storage. Crude Oil Storage: Aviomatic Custody Transfer (ACT). REFERENCES APPENDIX 5A: K Value Charts for COs, HS, and Paraffin Hydrocarbons... 127 APPENDIX 5B: Composite K Values for Reservoir Fluids. 6 | WATER-HYDROCARBON PHASE BEHAVIOR.. WATER CONTENT OF GASES Partial Pressure and Fugacity Empirical Plo. a WATER CONTENT OF SOUR GASES 'SRK Sour Gas Comtlation nnn ‘Another Equation of Slate Approach. Effect of Nitrogen and Heavy Ends. Saturated Water Content in Equilibrium with Hydrates WATER MONITORS. WATER CONTENT APPLICATIONS. GAS HYDRATES HYDRATE EQUILIBRIUM sn HYDRATE PREDICTION CORRELATIONS TABLE OF CONTENTS iii7 8 9 ‘Vapor-Solid Equilibrium Constants a 165 Trekell-Campbell Method oe se 170 MeLeod-Campbell Method... tee ee 178 Equation of State Calculations. 179 APPLICATION OF HYDRATE CALCULATIONS... a : 179 HYDRATE INHIBITION .. i Inhibitor Losses tothe Hydrocarbon Phase. Calculation Summary Cmaliatan (rein of Giycols, Giycol Losses... REFERENCES, BASIC THERMODYNAMIC CONCEPTS .. The Accounting Principle. stem and Surroundings Basic Thermodynamic Accounting. Accounting for Mass Energy Balance, ee Specific Applications ‘The Second Law of Thermodynamics ~ Entropy Relationship Between Thermodynamic Properties and with P-V Special Case for Ideal Gases. Special Case for Incompressible Liquids... Solution of Equations 7.15 and 7.17. Effect of Pressure on Cp. General Effect of PVT Relationships .. APPLICATIONS OF THERMODYNAMICS CALCULATION OF SYSTEM ENERGY CHANGES CHOICE OF SYSTEM. UNITS OF MEASUREMENTS 00 Flow Rates EFFECT OF PHASE CONDITION... ws ENTHALPY CALCULATION ALTERNATIVES SENSIBLE HEAT CHANGES... HEAT CAPACITY CORRELATIONS. MIKES emer LATENT HEAT... Pure Substances, Mixtures ENTHALPY CALCULATIONS FOR PURE SUBSTANCES. ENTHALPY CALCULATIONS FOR MIXTURES. General Correlations. PVT Equations of State... ENTROPY AND INTERNAL ENERGY CALCULATIONS REFERENCES. 2 APPENDIX 8A; Enthalpy Charts PROCESS CONTROL AND INSTRUMENTATION. sn DEFINITION OF TERMS CONTROL OBJECTIVES AND CONCEPTS... Feedback Control Systems... CONTROL MODES. Conteollers VOLUME 1: THE BASIC PRINCIPLESconor. Proportional Control Reset Derivative, PROCESS CONTROL SYSTEM DEVELOPMENT CASCADE AND FEEDFORWARD CONTROL... CONTROL VALVES. : Valve Sizing. Actuators Valve Positioners. PRINCIPLES OF PNEUMATIC CONTROLLERS... LEVEL MEASUREMENT AND CONTROL. Other Level Devices non PRESSURE REGULATION AND CONTROL... Pressure Controller Specification... ae ‘TEMPERATURE MEASUREMENT AND CONTROL. ‘Temperature Measurement ‘Thermometers Filled Systems. ‘Thermocouples. Resistance Temperature Detectors (RTD's) Radiation Pyrometers, ‘Some Temperature Control Applications Direct Fired Heaters conn Indirect Heating Medium FLOW MEASUREMENT AND CONTROL... Flow Measurement Pitot (Impact) Tube. Rotary Meter Sliding Vane Meter. Rotating Vane Meter : Reciprocating Piston Meter Rotameter ons Rotary Piston Meters ‘Venturi Meter. Vortex Shedding ... CCentitugal (Elbow) Meters Segmental Orif1C€8 nmr ea Eccentric Orif€28 wns nnn Flow Nozales Sonic Meters ‘Turbine Meters. ORIFICE METERS Heating Value. Wobbe Index... ‘Two-Phase Flow Measurement. ALARM AND SHUTDOWN SYSTEMS... Pressure Switches Flow Switches. e : ‘Temperature Switches Level Switches. Vibration Switches... oe PRESSURE RELIEF SYSTEMS. Sizing... 1296, TABLE OF CONTENTS vInstallation NOISE CONTROL ween Equipment Noise Summary. REFERENCES. APPENDIX 9A: Some Standard Control Symbols... APPENDIX 9B: Various Orifice Meter Factors. APPENDIX A: SAMPLING. SAMPLING TIME... Barly Reservoir Fluid Samples. ‘Stable Reservoir Fluid Samples... Plant and System Fluid Samples. ‘TWO-PHASE SAMPLING APPROACH... Stinger ‘Separation Vessels... METHOD OF SAMPLING. SAMPLE CONTAINER CONSTRUCTION. ‘SAMPLE CONTAINER CLEANING... MECHANICS OF SAMPLING... Ga... Liquid Gas-Oil Ratio. ‘SPECIAL CONSIDER: Storage Tanks. APPENDIX B: General Conversion Factors... APPENDIX C: Thermodynamic Data INDEX... rONS. Variations in Composition... Cold and Hot Sample... sesasnientanesnnnesrearinenene DES Volume 2 of "Gas Conditioning and Processing" is a continuation of this Volume I. These two volumes really are a single book published in (wo parts TABLE OF CONTENTS Volume 2 Flow of Fluids ‘Separation Equipment Fundamentals of Rate Processes Heat Transfer Pumps ‘Compressors Refrigeration Systems Fractionation and Absorption Fundamentals Glycol Dehydration Adsorption Dehydration and Sweetenin VOLUME 1: THE BASIC PRINCIPLESLIST OF FIGURES Figure # 11 Chromatogram of Condensed Liquid . ter 2 Relationship between SI Metric Units. 2.1 Schematic View of a Total Production Processing System..anumennn 25 2.2. Refrigeration-Type Liquids Recovery Module. 27 23. Simple Flow Diagram for an NGL Extraction Plant 30 3.1 Vapor Pressure (a) and Reduced Vapor Pressure (b) of Methane and Propane 89 3.2. Katz Compressibility Factor Chart ses 7 52 3.3. Correction Factor Chart for Sour Gases. 53 3.4 Approximate Pseudo-critical Properties of Natural Casa 055 3.5 Some Representative TBP Distillation Curves 57 3,6. Liquid Density for TBP Distillation Cuts from Three Different Oil8.....» 38 3.7 Correlations Relating Various Characterization Variables and Liquid Properties 59 3.8 Relationship Between Refractive Index, Characterization Factor, and Boiling Point... 60 3.9 Approximate Correlation between Molecular Weight and Relative Density for Hydrocarbon Liquids .....62 3.10 Density - Temperature Correlation for Liquids. 3.11 _ Relative Density of Hydrocarbon Mixtures sm 312 _ Relative Density of Hydrocazton Mixtures at their Bubble Point Pressure 3.13 Effect of Temperature and Pressure on the Density of Hydrocarbon Ligui 3.14 ‘Temperature Correction for Relative Density in Figure 3.16. vs : vt 3.15 Relative Density of Liquids Containing Methane and Ethane at Atmospheric Pressure and 15°F 69 3.16 Pressure Correction for Relative Density in Figure 3.1 7 3117 Viscoiy of Paratfin Hydrocarbon Gases at Atmospheric Pressure. 3.18 Pressure Correction for Viscosity from Figure 3.17. 3.19 Viscosity of Pure Paraffin Hydrocarbons... 4,1 P-V-T Diagram for a Single Component System. 42 P-T Diagram for a Single Component System... 43 Vapor Pressure Chart for Paraffin Hydrocarbons... : 44 Vapor Pressure Chart for Normal Paraffin Hydrocarbons Based on ‘Normal Boling Point. son 3 4.5 Typical Phase Diagram for Multi-Component Mixture... i 84 4.6 Effect of Composition on Phase Envelope, Methane-Propane Binary 85 47 Location of Critical Loci for Several Binary Systems. 85 48 Effect of Cet Characterization on Phase Envelope for Non-Associated Gas .. ron 86 49 Effect of Og, HyS, and Nz on Natural Gas Phase Envelope nnn sue 87 4.10 Use of Phase Envelopes in Reservoir Prediction .n..onnes : “ 88. 4.11 Characteristic Phase Envelopes for Four Reservoirs... 7 o son 88 4.12 Phase Diagrams and Pumping von 89 4.13 High Pressure Pipelines. 7 renee 89 {L1G Effect of Pressure on Dewpoint Conol Processing Temperate. 90, 4.15 Refrigeration Processes. a1 3.1 Effect of Composition on K Values. ae 101 5.2. Estimation of Convergence Pressure from Heptanes Plus. 101 53. Plotof Loz K ws. 72. “ 103 LIST OF FIGURES vii54° Volatility Exponent for Use in Finding the K of Cr+ 5.5 Another Comelation for Estimating Hydrocarbon Boiling Point 56 Constant "A" vs, Pseudo-Density of Feed at T=80. 5.7 Reid Vapor Pressure vs. Temperature for Typical NGL Liquids... 5.7 Vapor Pressures vs. Temperatures. i 58 Reid Vapor Pressure vs. True Vapor Pressure for Crude Oils 59 Mechanism of Tank Breathing Loss 5.10 Various Types of ACT Systems. 6.1 Water Content of Sweet, Lean Natural Gas, 6.1(a) Water Content of Sweet, Lean Natural Gas.. o 62. Effective Water Content of CO, in Saturated Natural Gas Mixtures. 63 Effective Water Content of HS in Saturated Natural Gas Mixtures. 64 — Water Content Contribution of CO3... 64(a)_ Water Content Contribution of CO3. 65 Water Content Contribution of HS... 6.5{a) Water Content Contribution of HS 66 Another Correlation for Sour Natural Gases: 67 Constant ‘k" as a Function of Pressure and Temperature 68 Water Fugacity as a Function of Pressure and Temperature 69 — General Fugacity Coefficient Chant, 6.10 Water Content of 5.31% C3 - 94.69% Cy Gas 6.11 Schematic of Natural Gas Hydrate Lattice. 6.12 Hydrate Forming Conditions for Natural Gas Components 6.13 General Hydrate Formation Characteristics of a Gas Mixture 6.14 Vapor-Solid K Values for Methane and Ethane wonssnn 6.15 Vapor-Solid K Values for Propane. 6.16 Vapor-Solid K Values for iso-Butane 6.17 Vapor-Solid K Values for CO and H3S 6.18 — Vapor-Solid Equilibrium Constants for n-Butane... 6.19 Hydrate Prediction Comrlations at 6.9 MP8... 6.19(a) Hydrate Prediction Correlations at 13.8 MPa 620 Hydrate Prediction Correlations at 20.7 MPa 6.20(a) Hydrate Prediction Correlations at 27.6 MPa. 6.21 Hydrate Prediction Correlations at 34.5 MPa... 6.21(a) Hydrate Prediction Correlations at 41.4 MPa. 6.22 Hydrate Prediction Correlations for Non-Hydrate Formers 6.23 Vapor-Liquid Equilibrium of Methanol over Water. 6.24 Freezing Points of Glycol-Water Solutions. Equilibrium with Hydrate 81 82 peer 83 Heat Capacity of 0.65-0.75 Relative Density Natural G88...ouim 84° Correlation for Estimating Latent Heat 85° Pressure-Enthalpy Diagram for Propane. 8.5(a) Pressure-Enthalpy Diagram for Propane... 9.1 Simple Level Control System... 92 Block Diagram for Level Control System.. 9.3 Performance of Valve Trim wit VOLUME 1: THE BASIC PRINCIPLES94 Schematic View of Two Fisher Pilots. 95 Schematic View of Fisher Dislacement Type Levet Controller 9.6 Schematic View of Low Pressure DP Controller Al Use of a "Stinger" for Sampling... A2 Recommended Separator Hookup. se 210 0D 24 313 313, LIST OF FIGURESLIST OF TABLES LL Fluid Analysis . on 1.2 Summary of $I Metric Prefixes. 1.3 Force and Mass Units 3.1 Physical Constants. 3.24) Properties of Paraffin Hydrocarbons - SI Units 3.2(b) Properties of Paraffin Hydrocarbons - English Units 5.1 Properties of Paraffin Hydrocarbon Liquids - Metric Units. 5.1(@) Properties of Paraffin Hydrocarbon Liquids - English Units 5.2 Comparison of Experimental and Predicted Liquefaction... 8.1 The Properties of Saturated and Superheated Propane - SI Units. 8.1(@) The Properties of Saturated and Superheated Propane - English Units 9.1 Some Different Types of Control Valves... 92 Composition and Temperature Range of Common Thermocouples... x VOLUME 1: THE BASIC PRINCIPLESCIS CAMPBELL PETROLEUM SERIES BOOKS... This book is one of a series in the area of petroleum production/processing. Each uses a CPS format designed to provide direct, concise explanations of the system involved for convenient use as a desk refer- ‘The same approach is used in a second series of books covering the area of financial analysis and planning — and petroleum project and property evaluation — for both petroleum and financial specialists. ‘These too have served as the standard references in the petroleum area for the past quarter century. ‘A description and price list for all books is available upon request. Adult training courses using these books also are available exclusively through John M. Campbell and Company. COMPUTER SOFTWAR! ‘The key equations and correlations in Volumes 1 and 2 of Gas Conditioning and Processing have been programmed for use with microcomputers. The books serve as your manuals. The computer will give the same result as manual calculations. No longer does one have to calculate "blindly" or to undergo the frustration of uying to make the program work, The program follows the sequence in the book. Example problems in the book can be used to check your procedure. ‘As personal computers become more common these programs become a part of your “desk refer- ences," along with the companion books. They enhance the time efficiency of the professional. Program disks are available in both English and SI Metric units Prices and other details are available upon request, CAMPBELL PETROLEUM SERIES. xiACKNOWLEDGMENT ‘This Seventh Edition represents a substantial rewrite and reorganization of the previous edition. This ‘was done to reflect what I regard as necessary basic knowledge to function effectively in the subject area now and in the 1990's. About thirteen revisions have occurred since this book had its birth as an adult training manual in 1960. Scores of folks have contributed to these changes by their formal or informal comments, Where possible, these have been cited. The source of some changes has been lost. I both apologize for this and thank these unknown persons for their contribution. Special thanks are due Bob Hubbard, Larry Lilly, John Morgan, and Bob Maddox for their contribu- tions in the preparation and review of the technical material. Sharon Antram is responsible for much of the new word processing and artwork, Joy Garrison (retired) is remembered for the many hours dedicated since 1968 to this and previous editions. Danny Stowe deserves special recognition for countless hours of layout and editing work. His efforts pulled this manuscript together as a book. Thank you all for your help. Dr. John M. Campbell ‘Norman, Oklahoma July 1992 xii VOLUME 1: THE BASIC PRINCIPLES1 Tee INTRODUCTION Knowledge of the basic fundamentals is the required foundation for successful professional practice." Tis new Seventh Edition of "Gas Conditioning end Processing” has been edited to reflect continuing changes in our technology and the manner in which itis practiced, Most engineering calculations are per- formed on a computer and there often is litle opportunity for the user to become very proficient in all arcas for which he or she is responsible. The only practical answer is to understand the relatively few fundamen tals which govern the multitude of applications For them. As noted in the Campbell Rules of Engineering which follow, it is impossible to use a computer intelligently unless the user understands the principles governing the system in question. It is desirable to also have first-hand experience with that system, but that is not always feasible, ‘We continue to modify, delete, or add to the technical content, but the goal remains constant — pro ing reliable, credible basic information to enhance the ability of the individual professional. The emphasis is (on relatively simple calculations and correlations that will give reliable answers for the applications involved, ‘Companion computer programs are even available to make the book calculations less of a chore. You may be somewhat surprised to find that some of these simple appearing approaches actually give more realistic results than some of the more complex simulation programs now available. This is not an accident or mere coincidence. Nothing goes into this book until it has been tested against the actual perform: ance of the equipment or system involved, within the limit of conditions specified. For this reason, a primary Use of these two volumes is to check the credibility of simulation calculations, Another common use is to provide @ “quickic” calculation for use in the early feasibility and planning Of a project. Or, to troubleshoot and/or improve operating efficiency, Simplicity has its virtues but it also imposes limitations, One should not extrapolate the correlations beyond their stated limits without concer for the increased uncertainty involved. Some of the factors affect. ing this are discussed throughout the book. ‘There are many figures and tables throughout this book that simply illustrate the relationship between the variables. They serve 2 kind of educational function to better understand how a piece of equipment works and to serve as a basis for the effective use of judgment ~ always a necessary ingredient in the engineering process. Before adéressing the details, I must admonish you to always remember that the professional decision Process depends on factors that are not quantitative or calculable, These include economic, political, cultural, CHAPTER I 1Ber INTRODUCTION legal, and moral issues that may tum out to have more effect on the final decision than the technical aspects, ‘We must always remember that engineering cannot be practiced in @ vacuum. ‘The remainder of this chapter summarizes some of the terms and nomenclature that will be used throughout the book. One complication in this area is the inconsistency of numerical systems used through- out the world, Itis interesting how otherwise perfectly rational persons will wax emotional about any devia- tion from the system they learned in school. So ... dual units are used in the hope that most users will be reasonably happy (even though not totally satisfied). SOME. CAMPBELL LAWS OF ENGINEERING “The utility of a computer calculation is limited by the user's real knowledge of the physical system involved and not by computer capability.” © “The time spent on a calculation tends to fully occupy the time available." ‘= “One cannot calculate reliably what one cannot measure reliably." « "There is a tendency to concentrate effort on those calculations one knows how to make, using equations that happen to fit the data available and which yield explicit answers - not necessarily those that are ‘mportant." © "Many calculations have as their primary purpose the justification of pre-conceived opinions or positions (biases) rather than to obtain knowledge. "The true precision and/or accuracy of an answer can be no better than that of the worst input dats; using = large number of significant figures cannot make a wrong answer right.” "The use of statistics to handle uncertainty is @ sound too! if used wisely but remember that statisties are like a bikini, what they reveal is interesting but that concealed may be vital.” ‘« "Engineering calculations are somewhat like sex. They ate important and give the practitioner varying amounts of pleasure, but there are other important factors to be considered in the (otal scheme of things.” ‘© Conventional wisdom can never be more than a partial truth because it is based on the past and assumes ‘no change in the interim.” “« "There is no such thing as a single equation or computer program that is equally valid for all mixtures in the full range of conditions under which they may exis.” the validity and usefulness of a computation is not necessarily proportional t0 its complexity." ‘The Fundamental Technology [All of the systems discussed in these two volumes are governed by a small group of fundamental laws and concepts. Understanding these, and their nomenclature, is critical. The most important are «© The physical properties of the fluids and solids. (A fluid is anything that flows ~ Hquid andlor gas.) «The vapor-liquid-solid behavior of @ substance as a function of pressure, temperature, and ‘composition. # The concept of equilibrium. «# The use of P-V-T equations of state to predict the behavior and properties of systems. ‘« ‘The use of combination rules for the prediction of mixture behavior from that of individual ‘molecular species present in the mixture, 2 VOLUME 1: THE BASIC PRINCIPLES:BASIC TERMINOLOGY ‘* Thermodynamic concepts that govern the conservation of mass and energy, and the calcla- tion of the energy level under given conditions, Rate equations which describe the rate of something happening in terms of stated driving and resisting forces, the area through which the transfer takes place, the configuration of the system, and a proportionality constant which covers all variables not specifically designated in the equation. This constant is most often called a “coefficient” with some adjective like hheat or mass to designate the system itis used with * The molecular theory of substance behavior (indirectly). In addition, it is required that the practitioner have reasonable literacy in the mathematical, chemical, and physical sciences, Chapters 3-8 in Volume I and Chapter 12 in Volume 2 discuss the above in detail. Please note the discussions at the beginning of each of these chapters. ‘The remainder of the chapters are applications of the aforesaid fundamentals. Chapter 2 is a brief summary of system planning, oftentimes the most important aspect of the entire ‘engineering effort. Each project is unique to some degree. When you decide to simply clone an existing system that is part of company standards or one with which you are familiar, without thorough review of the qualitative differences, you can be certain that atleast a small mistake has been made. Merely turning this phase over to an engineering company for a “feasibility study” also does not satisfy the need automatically. From their perspective, they will concentrate on simply modifying a process or system they know how to do or which they are licensed to use. Don’t expect them to suggest you buy something that does not give them a competitive advantage. As an employee of the customer you have an ethical requirement that cannot be transferred (to another party ~ or a computer). ‘With these thoughts in mind, let us begin our journey through the book. BASIC TERMINOLOGY ‘Throughout this book we will be using some basic chemistry and physics terminology. This is re- viewed briefly Elements and Atoms ‘All matter in the universe is composed of elements which cannot be broken down or subdivided into smaller entities by ordinary means, Over 100 materials have been found (or created) which are classed as elements. ‘These include carbon, hydrogen, sulfur, oxygen, nitrogen and helium — all materials occurring in petroleum systems. ‘The atom is the basi to form a compound. unit of each element that can combine with itself or the atoms of other elements Chemical Compounds and Molecules A true compound is a substance composed of more than one atom that satisfies both of the following conditions. 1. The atoms have combined chemically 2. The compound formed possesses properties different from the atoms of which itis composed. Chemical compounds are formed by the union of atoms in the simplest possible numerical proportions. ‘The molecule isthe unit of a compound. A molecule of water is HzO, two atoms of hydrogen combined with ‘one atom of oxygen. (CHAPTER 1 3INTRODUCTION ‘A diatomic molecule is formed by the combination of two atoms of the same element. Nitrogen (Nz) and oxygen (02) are the most common examples. Physical Compounds A type of physical compound, called a clathrate, may be formed. A gas hydrate is one example of a clathrate. These compounds are relatively unstable, Relative Atomic Mass (Weight) In forming @ compound, elements always combine according to fixed mass ratios. It is convenient to use relative atomic weight, the relative mass of the atoms of different elements, to express these ratios. The ‘word "relative means that the number used is a relative one. Currently, Carbon-12 is used as the standard, ‘being assigned the relative atomic weight of 12. On this basis, the relative atomic weights of common oil and gas components are shown below (to the nearest whole number) Hydrogen Carbon Nitrogen Oxygen Sulfur ‘A relative atomic weight of one element contains about the same number of atoms as a relative atomic weight of any other element. One gram of hydrogen and 12 grams of carbon each contain about 6 x 107° atoms. Since relative weights represent a fixed number of atoms, they may be substituted for atoms in calculations. Relative Molecular Mass (Weight) ‘The relative molecular weight of a molecule is the sum of the relative atomic weights of the atoms combining to produce the molecule. Water has a relative molecular weight of 18 (H;0 = 2+ 16 = 18). A diatomic molecule like oxygen (O2) has a molecular weight of 32. The Mol ‘The term "mot" is the historical abbreviation of the words “gram molecule.” The current definition of the mol is: "The mol is the amount of substance of a system which contains as many elementary entities as there are atoms in 0.012 kilogram of Carbon-12." ‘These elementary entities must be specified but include atoms, molecules, ions, electrons, etc. ‘The quantity 0,012 kg is 12 g, the relative atomic weight of carbon. Thus, the mol can be defined for engineering usage as that mass in grams equal numerically to the sum of the relative atomic weights of the atoms in the molecule of that substance. By virtue of the definition, whenever the mol is used as a mass quantity without a prefix, @ mass in ‘grams is implied. If a relative molecular or atomic weight is expressed in pounds mass or kilogram, we will use the terms b-mol and kmol, respectively, to denote this is not a standard mol. A kilomol (kmol) is simply 1000 mol Lkmol = 1000 mol = 2.205 1b—mol I Ib-mot = 454 mol 4 VOLUME 1: THE BASIC PRINCIPLESHOSES SST SS TT TTT TT BASIC HYDROCARBON NOMENCLATURE, Throughout this book the mo! will be used in many cases as a mass term in those processes where n0 chemical changes occur. It is particularly useful for gas calculations. AL a given pressure and temmperature equal volumes of different gas contain the same number of molecules. At O°C (32°F) and 101.325 KPa [147 Psia] 4 mol of any gas contains about 6 x 10%? molecules and occupies a volume of 22 liters. The mol is thus @ useful conversion factor from volume to mass, for the number of mols per unit volume is independent of gas composition. Valence Valence is a measure of the ability of atoms to form molecules by filling the electron shells of the atoms involved. ‘The valence number is plus or minus, denoting the number of excess or shortage of elec. trons needed to fill its outer shell ‘The question of atomic bonding is a complex subject involving many factors, as discussed in standard chemistry references. The concept is mentioned ofly to point out thatthe number of bonds or linkages used in the structural formulas that foliow inthe next section reflect the valence ofthe atoms in these compounds Mixture A mixture is a combination of elements and compounds which may be separated by physical means The properties of the mixture are a reflection of the properties of the constituents, Natural gos and crude oil are mixtures. They are analyzed by separating the mixture into its compo nent parts and identifying each by its properties BASIC HYDROCARBON NOMENCLATURE By definition, a hydrocarbon is any compound composed solely of carbon and hydrogen atoms, ‘These avons can combine in a number of ways to satisfy valence requirements. For convenience, these are sepa. rated into "families" or homologous series, each of which is given a name. ‘The carbon atoms can link together to form “chains” or “rings.” Crude oil and natural gas mixtures consist primarily of "straight chain” hydrocarbon molecules, the bulk of which are paraffins. ¢ CoHan42 Hydrocarbons in this series ate saturated compounds — all four carbon bonds are connected either to ‘another carbon atom or a hydrogen atom, with one such atom for cach bond Paraffin Series Formul: HOW H H to 144 H—C—C—H | H—-C—c—c—H tot Tea HOH HoH OW Methane Ethane Propane Notice that all names end in -ane, the ending used for the paraffin series. In each case, the number of hydrogen atoms is two times the number of carbon atoms plus two more for the ends of the chain The paraffin hydrocarbons are the most stable of the lot because all valence bonds are fully satisfied as indicated by the single line linkage. Most reactions involve the replacement of hydrogen atoms with other atoms; the carbon linkage remains stable, CHAPTER 1 5eee ee INTRODUCTION Each successive molecule in the paraffin series is created by adding a carbon and two hydrogens to the previous molecule. The incremental change in relative molecular weight is thus fourteen. Long chains con- taining scores of carbon atoms in series may be formed. However, the only ones normally identified by name contain ten or less carbons. Jn referring to a given paraffin hydrocarbon, the abbreviation C; for propane, Ca for butane, etc. may be used. Statements like "propanes plus fraction (C3+)" refer to a mixture composed of propane and larger atoms. Paraffin Isomers. When the paraffin series molecule contains four or more carbon atoms there are