PNGE 332 Lecture Notes

PNGE 332 - Spring 2010
Petroleum Property /Phase Behavior

Prerequisite: ENGL 102, CHEM 116, PNGE 200

PNGE 332 - Spring 2010

Petroleum Property /Phase Behavior

Lecture #1

Introduction to Properties of Petroleum Fluids and Alkanes

Petroleum

What is petroleum? --liquid/gas

-Petroleurn fluids: organic chemicals

-Srnall molecules

-Larqer molecules

Cf :f)'\'IA·kl,l~, I)'~ C:'t, C't) ~, • '~ .. Irll hlio,-v!"'() (,om fOV}elll +s

Table 1-1
Composition of typical petroleum
gases
Natural Gas
Hydrocarbon 7Q..-S8%C1
Methane
Ethane 1-10%c..~ r
Propane trace--5% ,,",, __ to '3
Butanes traoo-2% - L.Lt
Pentanes traoo-1%,_ -,
Hexanes traOO-:h% ____ \.....9,)
Heptanes -i- trace-%%-----2;;
Nonhydrocarbon ~.f
Nitrogen trace-15%
Careon dioxide' trace-S%
Hydrogen sulfide' traoo-3%
Helium up to 5%, usually trace or none Table 1-1 (con.) Composition of typical solution gases

Gas from a well which also is producing petroleum Liquid P

Hydrocarbon Methane Ethane Propane Butanes Pentanes Hexanes Heptanes+

Nonhydrooarbon Nitrogen

Carbon dioxide Hydrogen sulfide Helium

45-92% 4-21% i-1'5% \1;-7% trace-S% trace-2% none-1~%

trace-up to 10%, trace-4"/o none-trace--6"I" none

Structure Theory

·Atomic structure ·Chemical bonds -Ionic bond

-Covalent bonds

Composition of typical crude oil

BoDing Approximate

Crude point, "F chemical

fraetfon ffl9~l1:o=m=POIS:;:.Iti::.:o",n--=U:.::;se::::s'-- --l

Hydrocarbon gas C,-C. Fuel gas

to 100 C:rC. Bottled fuel gas, solvent

100-350 c"c" Motor fuel, solvenl

35(l.-.4S0 Cl1-C'2 Jet fuel, cracking stock

450-580 C,,,c17 Diesel fuel, furnace tuel

580-750 C,,,c,,,, Lubricating oil, bunker

tue'

C..-c.. Lubricating oil, paraffin

wax, petroleum jelly Tars, roofing compounds, paving asphalts, coke, wood oreservatives

Gasoline Kerns""e Light gas oil Heavy gas oil

Lubricants and

750-950 (100) 950+ (200+ )

waxes Residuum

C,.+

Atomic Structure

·AII matter consists of tiny particles ·Nucleus and electrons

·Electrons in shells around nucleus

Carbon atom

http://IN'vVW.hk-phy.org/articles/laser/laser_e.html

Atomic Structure

-First three shells can accommodate maximum number of electrons:

'Greatest stability can be reached 'Atoms tend to achieve stable configuration

Chemical Bonds ·Ionic bond

-By transfer of electrons from one atom to another

atoms

po sitlve neqetlve

ion ion

Electrostatic attraction between oppositely charged ions

htlp:flWVV'<N.accessexcelience.orgfRCNUGGJecb/covalent_ionic_bonds.html

Structure Theory

·Atomic structure 'Chemical bonds -Ionic bond

-Covalent bond

Chemical Bonds 'Covalent bond

-Outer shells become complete by sharing electrons

atoms

molecule

Electrostatic attraction between electrons and nuclei

http://w..v.N.accessexcelience.org/RCNUGG/ecb/cQvalent_ionic_bonds.htm!

r:;. i-rw,y\ e, :

Ii it\

,I!-.~ Itt ~

i-I: c_- (_~ H

" ~ CD

H '-\

Covalent Bonds

'Tetravalent carbon atom with four covalent bonds

-Single bond:

H3C- CH3

Ethane

-Double bond:

H2C== CH2

Ethene

-Triple bond:

HC-CH

Ethyne

Alkanes

<;. 'R .J

'Bond >-.nlf\(tik.;)oi/\'U,

'General formula: Ln 14b-.\')'+'1. 'Other names: saturated hydrocarbons or paraffins

'Naming: IUPAC Rules

'J." '{l~eYYlc;hovkd 0\ f..l.~. ClVld. l\:-ro ked C.h:.m'i )..\-( a

f ~ ~11\ ~ ()uw,\ I>or cJ Co-fb.)If), l.t \-0 N'I')

Hydrocarbon Families (Homologous Series)

Homologous series: a group of molecules which have similar structures and graded physical properties

Naming Alkanes

'Combination of prefix and suffix

'Alkyl group: an alkane with one hydrogen missing

Naming Alkanes

·Structural isomers: n-, iso-, and neo-

n-pentane

Methyl gro~

IUPAC Rules

·Substituent numbering: from carbon attached to framework

·Substituent ordering: in alphabetical / increasing complex

IUPAC Rules International Union of Pure and Applied Chemistry

·Framework: longest continuous chainparent chain

..--- substituents

·Numbering: lowest sum of numbers of substituents

·Positioning: ali substituents

Alkanes

Properties

-Physical properties: boiling point, melting point, and specific gravity

-Chemical properties: unreactive

..,'t

.~J<':--i-- ... ':;~:;__f--+--+--I'.' ill

I-+-JrT----J?4---r-r~p"l." i

Properties increase with increase in the number of carbon atoms

PNGE 332 Petroleum Property /Phase Behavior

Lecture #2 Alkenes and Alkynes

Naming Alkanes

·Combination of prefix (number of carbon atoms) and suffix (-ane)

·Alkyl group: an alkane with one hydrogen missing

Re-Cap of Lecture 1

·Petroleum ·Chemical bonds -Ionic bond

-Covalent bonds: single, double, triple

·Hydrocarbon families (homologous series)

IUPAC Rules

International Union of Pure and Applied Chemistry

·Framework: longest continuous chainparent chain

·Numbering: lowest sum of numbers of substituents

·Positioning: all substituents

1

IUPAC Rules

-Substituent numbering: from carbon attached to framework

-subsntuent ordering: in alphabetical / increasing complex

4-ethyl-3-methylheptane

Exercise



Alkanes

Properties

-Physical properties: boiling point, melting point, and specific gravity

-Chemical properties: unreactive

Properties increase with increase in the number of carbon atoms

Alkenes

-Bond: lo!(bo(\~·

-General formula:

L,l"

·Other names: unsaturated hydrocarbons or olefins

·Naming alkenes

2

Naming Alkenes

·Combination of prefix (number of carbon atoms) and suffix (-ene)

·Structural isomers: structural isomerism

IUPAC Rules

·Framework: longest continuous chain containing double bond-parent chain

·Numbering: from end nearest double bond ·Positioning: indicate position of double bond in name

Naming Alkenes

·Stereoisomers: geometric isomerism

n n

)=<:'¢7~

cis-2- butene

Alkenes

·Bond: ·General formula: ·Other names: unsaturated hydrocarbons or olefins

·Naming alkenes ·Properties

-Physical properties < -"7

-Chemical properties

L)

II

(\ iK0~

3

Compounds with Two or More Double Bonds

-Alkadienes (diolefins/dienes): two double bonds

-Alkatrienes (triolefins): three double bonds

Alkynes

-Bond:

-General formula:

-Naminq alkynes: same rules as for

alkenes

-Suffix: -yne

-Properties

-Physical properties 1 Yv,

-Chemical properties

)-:, Ai

1/,

o

,

-\0 S Of'c-t::_



e'lC\ b '7 +tir-le

:1

4


Lecture #3 Cycloaliphatics, Aromatics and Nonhydrocarbon Compounds

Cycloaliphatic Hydrocarbons

·Cyclic compounds 'Structure feature: C~,f 'Prefix: cyclo-Cycloalkanes

-Cycloalkenes



Cycloalkanes

'Other names: naphthenes / cycloparaffins / alicyclic hydrocarbons

'Formula:

'Naming cycloalkanes

-Prefix: cyclo- to name of corresponding alkanes

1

Cycloalkanes

-Substituents: numbered and positioned with least sum

cyclohexane cyclopentane 1,2-dimethylcyclopentane

Cycloalkenes

·Structure feature:

• Naming cycloalkenes

-Prefix: cyclo- to name of alkenes

-Numbering: closest to double bond

·Cycloalkadienes: ring with two double bonds

Cycloalkanes

'Properties

- Physical properties: regular change

-Chemical properties: different

reactivities

'Condensed rings: rings sharing carbon atoms



2

Aromatics (arenes) ·Aromatic compounds

-Benzene and compounds resembling benzene

·Benzene

·Hexagonal ring

o

-Probably, six identical bonds (hybrid bonds)

Property

·Physical properties

-Pleasant odor but quite toxic, avoiding inhalation of aromatic hydrocarbon vapors

·Chemical properties -Quite stable

-benzene ring retained in reaction

product

I

o

Naming Aromatics

-Benzene ring containing substituents

Name of substituent + Benzene

-Benzene ring considered to be substituent

-Benzene ring - phenyl group

Non-hydrocarbon Components of Petroleum

-Most common non-hydrocarbons

-N2' co2, H2S

-Cornpounds formed by sulfur, oxygen and nitrogen

-Sulfur compounds

-Oxygen compounds

-Nitrogen compounds

3

Resins and Asphaltenes

·Similarities

-Large molecules with sulfur, oxygen or nitrogen atoms

-Basic structure composed of rings, primarily aromatic

-Non-hydrocarbon atoms on rings or links

-Formed by oxidation of polycyclic

aromatics

-Reduced to hydrocarbons by hydrogenation

·Convertibility

-Resins can be converted to asphaltenes by oxidation

Resins and Asphaltenes

·Differences

-Resins readily dissolve in petroleum, but asphaltenes do not

-Pure resins are heavy liquid or sticky solid, volatile and red, while pure asphaltenes are solid, dry, nonvolatile and black powder

-Color of distillates depends on presence of resins, while color of residuum is mainly determined asphaltenes

4


Lecture #4 Phase BehaviorPure Substances

Phase

·A portion of system which has homogeneous intensive properties and physically bounding surface

-Three phases: ice, liquid water, water vapor ·Intensive properties: independent of quantity of matter

-Density and specific volume ·Extensive properties: dependent of quantity of matter

-Mass and volume

Re-Cap of Lecture 3

·Petroleum -Hydrocarbons

-Non-hydrocarbons N2, CO2, H2S

Phase Diagram

·Types of phase diagrams (pure substances)

-Pressure vs. temperature

-Pressure vs. specific volume

-Density vs. temperature

·Show conditions of pressure and temperature under which different phases exist.

1

Pressure vs. Temperature (Pure substances)

Temperature


·Vapor-pressure line (two phases) ·Critical point

JV,t.Triple point (three phases)

·Sublimation-pressure line (two phases) ·Melting point line (two phases) ·Single-phase regions


Temperature

Vapor pressure

Boiling point

Phase change

at constant temperature (T<Tc)

A

B

9g~d !K!~lclwntM

ISr.~~llr~ ~'l"<lt; "~P'" "' .. *'" .....

mMt""AM ItnUtl<.ll!tp'~~t

~IIU<ll''''*<Wi,j# 'i'NW< IM"'~"'''

o

.II!~ V:tl:lO'IUQ~ elll!Ml()tgu

W .. JII .... ~~_ ,,_,.....s.s1ll'.

2

Use of Phase Diagram ·Process of moving from liquid phase to gas phase

-Process: 1-2-3

Calculation of Vapor Pressure

-Frorn the ideal gas law

RT

P V = RT c:::::::=> Vmg =-

v mg Pv

R: universal gas constant

-By substituting Vm9, we obtain ClausiusClapeyron Eq.

dpv = p L;

dT RT2

-If assuming l.; a constant, we integrate


·Vapor pressure line: relationship between pvand T

·Derivation of equation of vapor pressure line

-Clapeyron equation

dp; Lv

dT T(Vmg - Vml)

dpv=~ dT rr;


-and get

t; (1 J C

lnp =-- - +

v R T

-Equation indicates a linear relationship of In p; vs. 11T

Slope=-L/R, intercept=C

-Two assumptions oLv=constant

·Vml is negligible

3

Cox Chart

A straight line graph of logarithm of the vapor pressure plotted against a non-uniform temperature scale

Pressure-Volume

Volume', Pressure, ·Segment 2-2: Vaporization Pb=Pd",Py

·Segment 2-3: Gas expansion Volume', 'iVI(

Pressure:

f)2 ........ }~

~~ n...;o,W'

,

Exercise 1

What is the temperature at the normal boiling point of n-pentane?

Exercise 2

A cell is maintained at a temperature of 150 oF. The vol of n-pentane is increased until a few bubbles of gas are present. What is the pressure in cell? If the vol is changed until the cell is almost full of gas n-pentane, what is the pressure in cell?

-",_ -J (,

"'.'/ ,

4

Pressure-Volume ·Pressure-volume plots at various temperatures

-Saturation envelope .,>

-Two phase region

-Critical point

-Critical isotherm:

,5

Density- Temperature

-Densities of liquid and gas at

two phase region

-Densities of liquid and gas are identical at point C -Average densities: a straight line passing through point C

5


Lecture #5

Phase Behavior - Two Component Mixtures

Phase Diagram-Binary Mixtures

L') ii ,Cole

-Types of Phase Diagram

-Pressure-temperature

-Pressure-volume

-Pressure-composition

- T em peratu re-com position

Re-Cap of Lecture 4

·Phase diagrams for pure substances

oP vs. T

oP vs. Vs

op VS. T

Pressure-Temperature Diagram ·Features

-Two-phase region

Saturation/phase envelop -Bubble-point line and dew-point line

-Bubble-point pressure: Pb

- liquid volume percent of total

-Critical point (C)

~----------~.--~

Pressure-Temperature Diagram 'Envelop between vapor pressure lines - r, L Lkr:>

- Pc E~(P( r)c[~LPC

'CricondenMerm and cncondenbar

- Cricondentherm:

- Cricondenbar:

Cricondenbar

............. (: ...

U<Juld \

1\\ I I I

~~u~1 II

f I J ,

100/ I }

/ } f

J I I } ,"7. I /

,t/ / / ,Ii / t., 1i';1 50 I:

/ / ,

/ / i

/ 25 Q

'-:0

G"

Pressure-Temperature Diagram

'Retrograde condensation

-Process 4 - 5: gas change to liquid with decrease in pressure -Upper dew-point; lower dew-point

-Between Tc and cricondenthejm

Exercise 1

Use Fig. 2-15 to determine the temperatures and pressures for the mixture with 70 mole-% methane.

1. Pb

2. Tc

3.

T

@ pd=500 psia

4.

5.

T @ pb=800 psia v

6.

Cricondentherm

7.

Cricondenbar ;c

8.

Pd @ T=-20 of z:

Pressure-Volume Diagram

·Difference (from pure substance) -Pressure decreases from bubble point to dew point

-Line is not horizontal. and unnecessarily straight

Major Definition of Hydrocarbon Composition

·Hydrocarbon composition may be expressed on a molar basis or a weight basis

• On a molar basis

-Moles - the number of mole: n

n, =!'!_;__ = mass of component i

I M, Molecular weight of component i


·Mole fraction of liquid in total mixture is symbolized with ft, and mole fraction of gas in total mixture is symbolized with fg

where

Major Definition of Hydrocarbon

Composition

·Liquid composition (mole fraction) is symbolized with x and gas composition (mole fraction) is symbolized with y

·For a binary system

nil

XI = --- n.; moles of component 1 in liquid

nil +n12

YI = ngl + ng2 ng1: moles of component 1 in gas


·Overall mole fraction of component i in total mixture is symbolized with Zi'

Or

where

Then

Pressure-Composition Diagram

-Three areas: liquid, gas and two-phase

-Two lines

-Bubble point line:

-Dew point line:

-Equilibrium tie line

"

ComPCIIltlon, mot_ % component A


Locus of critical point


Calculation of quantities For liquid

For gas

Temperature-Composition Diagram

Bubble point line

Dew point line

Exercise 2

Determine the compositions and quantities of gas and liquid when 1 Ib mole of a mixture of 60 mole % methane and 40 mole % ethane is brought to equilibrium at 500 psia and -40 of.

Q,

\b' (,!p\ v\


Lecture #6

Phase Behavior - Three- and Multi-component Mixtures

Compositional Phase Diagrams for Three Component Mixture

·Ternary diagram: equilateral triangle

Re-Cap of Lecture 5

Phase diagrams for two component mixture

oP vs. T

oP vs. v

oP vs. composition o T vs. composition

Ternary Phase Diagram

·Compositional Diagram for three components at constant pressure and temperature

·Equilateral triangle

-Each vertex: a pure component

-Top vertex: lightest component

·Left vertex: heaviest component ·Right vertex: intermediate component

-Each side: a binary mixture

-Points within triangle: three component

mixtures

Ternary Phase Diagrams

·Point A: ?I);( ·Point B: b

-Compcnent js: 1() ~~

·Point C: ;1\)

·Component 2: ·Component 3:

.e .9

Component 2

Tie Lines in Ternary Phase Diagrams

·Equilibrium tie line: straight line which connects dew- and bubble-point

·Determine composition of equilibrium liquidbubble point line

·Determine composition of equilibrium gasdew point line

Methane


·Line B-A: a process ·AII mixtures

-Ratio of compositions (components 1 and 3) ·Point D

·Component 1: ·Component 2: ·Component 3:

Component 2


Calculation of molar fractions 1

For liquid

For gas

Methane


All mixtures whose overall composition (z;) is along a tie line have the same compositions of equilibrium gas (Yi) and liquid (x;), but molar fraction of gas and liquid (fg and ~) change linearly

Met".ne

Use of Ternary Phase Diagram

·Ternary diagrams may approximate phase behavior of multicomponent mixture by grouping them into three pseudo-components

-Heavy: C7+

-Intermediate: C2-CS

-Light: C1, CO2, N2-C1, CO2-C2, .

·Ternary diagrams are used for analysis of phase behavior during miscible displacement -- EOR


At pressure: 1500 psia

·Bubble and dew points join at critical point

Methane

Use of Ternary Phase Diagram

Miscible recovery process

Solvent2

Exercise

Find overall composition of mixture made with 100 moles oil "0· + 10 moles of mixture "A",

V\

, J

Multi-component Mixture


-Features on pressure and temperature diagram

·Separation between bubble point and dew point lines becomes greater

·Separation between critical T and cricondentherm is large

A ~r) r~jJ.;\r(·Separation between critical p and

A I . r cricondenbar is large for lighter

hydrocarbon mixtures


~)t 100

'ilJl'f"r.:i!I'I,'!

I~

j~1



Lecture #7

Chapter 3 - Equations of State (EOS) Ideal Gas Law

Behavior of Real Gases

Equations of State (EOS)

The Ideal Gas

• Three properties

-Volume of gas molecules is negligible comparing with gas volume

-Forces of attraction and repulsion between molecules and between molecules and walls of container are zero

-There is no loss of internal energy due to collision

Re-Cap of Lecture 6

·Ternary diagram: equilateral triangle -Each vertex: a pure component

-Each side: binary mixtures

-Points within triangle: three component

mixtures

Boyle's law

-For a given mass of gas,

Or

1 Voc-

p

At fixed T

pV = constant

At fixed T

Charles' law

-For a given mass of gas,

VocT

At fixed p

Or

v

- = constant

T

At fixed p

Avogadro's law

·At the same temperature and pressure, equal volume of all ideal gases contain the same number of molecules

·There are 2.731*1026 molecules/lb mole of ideal gas

Equations of State for Ideal Gas

·Two steps

-Step 1: at constant T = T1

1. PIVI = P2Vx

-Step 2: at constant P = P2

Vx V2

t; T2

2.

·Eliminate Vx

3.

T~

V1 v,

Volume


·Equations of state for ideal gas can be developed by combing Boyle, Charles and Avogadro laws

A given mass of gas,

·State 1 (Pi, T1, Vi)

·State 2 (P2, 72, V2)

Volume


·Universal gas constant

PIV; = P2VZ = constant

t; T2

3.

-With molar volume,

4.

P VM --=R T

V M: molar volume-volume of one mole of gas

Equations of State for Ideal Gas (EOS)

·EOS of ideal gas: general gas law/ideal gas law

1. P VM =RT

2. P V =nRT

V: volume of n moles of gas

-Others

m

P V=-RT M

MpV

m=--

RT

m Mp p= V = RT

Dalton's law

·Total pressure of gas mixture equals sum of pressures exerted by each of components if it were alone (with same volume and temperature)

P=PA+PB+PC+···

-Assumption: mixture and each of component act like ideal gas

Or

Ratio of partial pressure of componentj (p) to total pressure (P) is

P n _!_=_.l_=y

P "n j L. .I

U"UwL~_-v> Pi = YiP

Use of EOS of Ideal Gas

·Give description of behavior of most real gases at low pressure

·Provide a starting point for development of EOS for real gases at higher pressure

Mixtures of Ideal Gases

·Laws governing behavior of mixtures of ideal gases

-Dalton's law of partial pressure

-Amagat's law of partial volume

·Apparent molecular weight of gas mixtures

·Specific gravity of a gas

Amagat's law

-Total volume of gas mixture equals sum of volumes occupied by each of components (at the same pressure and temperature)

-Assumption: mixture and each of component act like ideal gas

Or

RT RT RT RT

V =nA-+nB-+nC-"'=-Ln

P P P P j J

Ratio of partial vol~me of componentj (v) to total volume (v) IS

V n _!_=_.l_=y

V Lnj .I


·Apparent molecular weight of gas mixtures

Where

Ma is apparent molecular weight

~ is molecular weight of componentj Yj is mole fraction of componentj

Behavior of Real Gases

·The compressibility equation of state ·The law of corresponding states

·The compressibility equation of state for gas mixtures

·Pseudocritical properties of heptanes plus ·Pseudocritical properties of gas when composition is unknown

·Effect of non hydrocarbon components


·Specific gravity of a gas (Yg): ratio of density of gas (Pg) to density of air (Pair) measured at the same pressure and temperature

Pg Yg =-_

Pair

For ideal gas and ideal air,

and

Thus M M

Y = -g_ = __I(_

g Mail' 29

The compressibility equation of state

·EOS for ideal gas

p V =nRT -Ideal gas equation (law)

·EOS for real gases: real gas equation (law) / compressibility equation

p V =znRT

z: compressibility factor! deviation factor! z-factor

V: volume

Or

P VM =zRT

zRT Or p V=--

M

VM: molar volume, volume per mole of gas

v: specific volume, volume per unit mass of gas

m Mp P=-v= zRT

Or

Density of real gas

z- factor

oForrealgas P.VM,real

HI

-For ideal gas

p··· -. VM·d I

..... ,I ea = 1

RT

Z

VM real --'-=Z

VM,ideal

-z is the ratio of "real molar volume" to "ideal molar volume" of a gas measured at the same pressure and temperature

-Ideal gas has z-factor of 1

z- factor

-z-factor varies with changes in substance, pressure and temperature

-At very low pressure, z-factor approaches 1, indicating gas acting like ideal gas

-At moderate pressure, z-factor is less than 1, indicating that real gas volume will be less than ideal volume at the same P and T

-At higher pressure, z-factor is larger than 1, indicating that real gas volume will be larger than ideal gas volume at the same P and T

z- factor

Not constant but change with substance, P,T

.... _. ·:__-----i------

In low pr ••• ure ranga, actuat At higher {,Ir&ssures.

V I ••• then tde .. V actual V greater than

Id$aI V

o .".,~-.,-.--- .. , .... - ... -,---.----'

o Pr ••• u( •• p

z- factor (methane)


Lecture #8

Chapter 3 - Equations of State (EOS) Behavior of Real Gases

z- factor (methane)

Re-Cap of Lecture 7

·Equations of State (EOS) -Ideal gas law

p V =nRT

-Mixtures of Ideal Gases

-Dalton's law Pi = YjP

·Amagat's law VJ = y,V ·Apparent molecular weight

u, = Ly}Mj

.. j. M, Mg

-Specific gravity r g = Mal' = 29

-Real gas law

p V =znRT

The law of corresponding states

·A new pair of parameters: reduced pressure and reduced temperature

T

• The law of corresponding states: all pure gases have the same z-factor at the same p, and T,

Generalized z- factor with Pr and T,

The compressibility equation of state

for gas mixtures

-z-factors are correlated with pseudoreduced properties

·Pseudoreduced properties -Pseudoreduced pressure P

Ppr=-

e;

-Pseudoreduced temperature T

Tpr =-

i;

·Pseudocritical properties: Kay's mixture rule

T = "y T

pc ~ j c]

j

Yi mole fraction of componentj

Pei critical pressure of componentj

Te/ critical temperature of componentj

Example 1

·Given: p=918 psia, T=117 OF for ethane ·Find: (1) z- factor using p, and T"

(2) specific volume of ethane ·Solution:

(1) From Table A-1 in Appendix A

,qC1 a=:

Pc= psia, t, = 0/' Jel OF

Pr = .i: = ~ril--loG):"; ~ L 30

Pc

1',. =I_=~49.1 -z: 1.05 1',. r \?':l

From fig, '3-6, z =t). 3QO

V zRT

V=-=--

m Mp

M=30.07 Ib/lb mole

(2)

Specific volume of real ethane gas is

times of specific volume of ideal ethane gas

[2; or +9:::# ('-( GO')

-~

z- factor with Ppr and Tpr for gas mixtures

Example 2

·Given: p=9,300 psia, T=290 of, gas mixture is contained in 43,560 cf.

·Find: mass in Ib moles

·Solution:

Critical Critical

Mole temperature. pressure.

fraetton, "R pele

C()mpo~~_. __ y_, ~_. __ :?i__.~_,_, , !:! ~_YJ~~_

0.850 343.3 291,8 666.4 566.4

0.090 549.9 495 706.5 83.6

0.040 666.1 26.6 616,0 24.6

0.020 765,6 15,3 550.6 1 1.0

... !.'m_~.""" ~:~:.B J5';L~' 665.6 psia

T pc Co" 383~R, Pr<o 666 psta

= _p__ = 9300 = 14

PI" 666

Ppc

T =~=290+459.7 =196

In' Tpc 383 .

From figure 3-7, z= L

n = pV =""'Ib moles

zRT -z ., r. i

v +/16U Ik fMie'>

Pseudocritical properties of gas when composition is unknown

·Pseudocritical properties

'Correlation of Ppc and gas specific gravity 'Correlation of Tpc and gas specific gravity

Pseudocritical properties of

heptanes plus

·Heptanes plus: all components heavier than hexane are lumped together

·Pseudocritical properties of heptanes plus are determined

-Correlation of Tpc and Ppc with molecular weight and specific gravity

Specific gravity (C7+) =0.758

Molecular weight (C7+) =128 lb/lb mole

Tpc =1 082 OR Ppc =372 psia

Effect of nonhydrocarbon components

oN2 has no important effect on z-factor oH2S and CO2 cause large errors in zfactor without adjustment

-Equations for adjustment of pseudocritical properties

8: adjustment factor

YH2s: mole fraction of H2S

H2S and CO2 adjustment factor for pseudocritical properties

Table
Cumulative
Pressure, production,
Time P Gp Ppr Tpr pi'
Months PSI<l MMOO psia
1.00 1675 21.149
2.00 1623 41.625
3.00 1572 61.443
4.00 1523 80.616
5.00 1475 99.160
6.00 1428 117.086 i 1500 ,;

e, '000

......... , ...... .. , ...... , ......
-, y=-33 x+20774
0'
<, ~
~
"~
o ~~ 100 200 300 400 500 600 700 800 Cumula!ive production, Gp,MMscf

Use of z-factor in dry gas reservoir

p

Gl' 'I

1---

G)

z

P!z@originalpressm'e

Cip=G@P=O

Gp Estimate gas in place (G)

Exercise

A container has a volume of 0.5 cu ft and contains a gas at a pressure of 2000 psia and at a temperature of 120 oF. The pressure drops to 1000 psia after 0.0923 Ib moles of gas are removed. The temperature is constant. The z-factorwas 0.90 at 2000

psia. What is the z-factor at 1000 psia? ,

'7&--, ({if ~/J~) ~t

~.,.


Lecture #9

Chapter 5 - Five Reservoir Fluids

Identification of fluid type

·Indicated by production information -Initial producing gas-oil ratio

-Stock-tank liquid gravity (OAPI) ,

-Stock-tank liquid color ·Confirmed by laboratory test

-Phase change in reservoir

-Heptanes plus

-Oil formation volume factor (FVF) at bobble

point (valid only for black oil and volatile oil)

i

Petroleum reservoir fluids

·Reservoir fluids: numerous components ·Shape of phase diagram (P & T)

• Visualize production path of petroleum fluid from reservoir to surface

·Classify types of reservoir fluid

·Behavior of reservoir fluids: shape of phase diagram and position of critical point

·Five types of reservoir fluids

-Black oil, volatile oil, retrograde gas, wet gas and dry gas

Identification of fluid type

·Indicators

Ughllymlnra<l

- ~----- -ruLE2.:EiPEcmiReSuLTsoP LABOfIATORY ANALVSISOFlHEflllEFLUJD TYPES1?

BlackOU VoI.:l!il"OiI Re!~.rJ", WotIG..,. O<yGas I'

==.~"''''r ~2()~ B~~ O:7~n! M:I~.ci"'A~ Noph=7~hange

0iIf'VFa1bubb~"'OI <.2.0 ;,2_0 _ _ _.

Exercise

The following notices were taken from the Sunday Business Sections of the Houston Chronic, on November 30, 1986 and December 7, 1986. All of the wells were reported to have been completed in the Glenrose Formation of the Alabama Ferry Field in Leon County, Texas. Make an estimate of the type of reservoir fluid in the Alabama Ferry Field.

a. Flowing 150 barrels of 35 °API oil per day plus 100,000 CF of casinghead gas, the No.4 Largent Heirs has been finalized in the Alabama Ferry Field about 12 miles southeast of Centerville. Houstonbased Mitchell Energy Inc. is the operator. The well probed to a total depth of 10,752 feet. After plug back to 10,478 feet, it was perforated to produce from the Glenrose at 10,228 to 10,290 feet into the wellbore. Flowing tubing pressure came in at 450 PSI.

Exercise (Con.)

c. Majestic Resources Inc. has posted first production data for the No. 1 Maude Wakefield, a new producer in the Alabama Ferry Field, Leon County, seven miles southeast of Centerville. The well produced at 160 barrels of 500 API oil per day plus 600,000 CF gas. Potential was gauged on an 18/64 choke. Flowing tubing pressure registered 425 PSI. Majestic took the hole to a 9,557-feet bottom and perforated the Glenrose for production at 9,381 to 9,400 feet.

50

Exercise (Con.)

b. Murphy H. Baxter, independent operator from Houston, has filed first production figures for the No. 4 Frank Leathers Unit in the Alabama Ferry Field, Leon County, 10.5 miles southeast of Centerville. Bottomed at 10,350 feet, the well will produce from a set of Glenrose perforations at 9,801 to 9,860 feet into the wellbore. It showed potential to flow 95 barrels of 410 API oil per day plus 200,000 CF casinghead gas on a quarter-inch choke.

Black oil

-Production process (line 123)

-P res decreases at constant Tres

-Unsaturated oil: above Pb

·Oil could dissolve more gas if more gas existed -Saturated oil: at & below Pb

·Oil reaches its maximum capacity to hold gas -Oil shrinkage: from reservoir to surface

Pressure and temperature of separator at surface

Volatile oil


Wet gas


Retrograde gas


Dry gas


T Technology

Today Series

Heavy Components Control Reservoir Fluid Behavior

William D. McCain Jr., SPE, S.A. Holditch & Assocs. Inc.

The five reservoir fluids (black oils, volatile oils, retrograde gascondensates, wet gases, and dry gases) are defined because production of each fluid requires different engineering techniques.l-l The fluid type must be determined very early in the life of a reservoir (often before sampling or initial production) because fluid type is the critical factor in many of the decisions that must be made about producing the fluid from the reservoir. 1

Introduction

Reservoir fluid type can be confirmed only by observing a representative fluid sample in the laboratory. However, "rules of thumb" based on initial producing GOR, stock-tank liquid gravity, and stock-tank liquid color usually will indicate fluid type. Initial producing GOR is the most important of these indicators; nevertheless, both stock-tank liquid gravity and color are useful in validating the fluid type inferred from the GOR.2,3 Darker colors are associated with the largest, heaviest molecules in the petroleum mixtures.

Black oils are mixtures of thousands of different chemical species ranging from methane to large, heavy, virtually nonvolatile molecules. Volatile oils contain fewer of the heavier molecules. Retrograde gases have even fewer of the heavy ends, wet gases still fewer, and dry gases are essentially pure methane. These differences in composition cause the five fluids to have different phase diagrams, which cause differences in behavior in the reservoir and at surface conditions. 1

The heavy components in the petroleum mixtures have the strongest effect on fluid characteristics. Normally, laboratory tests combine the heavy components as a "heptanes-plus" fraction. Fig. 1 illustrates the effect of this heavy fraction on the most important of the fluid-type indicators: the initial producing GOR.4 Black oils, represented at the lower right end of the graph, have the lowest initial GOR's and the highest concentrations of heavy components. Dry gases are located at the upper left of the graph. The other fluids exist in a continuum between these two. The GOR's in Fig. I are not normalized to any standard surface facilities or standard operating conditions; nonetheless, the graph is an aid in understanding the differences among the five fluids,

Black Oils and Volatile Oils

Black oils and volatile oils both are liquids in the reservoir, both exhibit bubblepoints as reservoir pressure is decreased during production, and both release fas in the reservoir pore space at pressures below the bubblepoint. ,5,6 However, there is a good reason for classifying them separately. The "oil material-balance equations,"

Copyright 1 W4 600iGty 01 Petroleum Engin""",

This paper is SPE 26214. Technology Today SerI ... articles provida useful summary information on both classic and emerging concepts In petroleum engineering. Purpose: To provide the general readar wnh a basic understanding of a significant concept. technique. or davelopment wtthin a speclfic area of technology.

746

which are used for black oils, will give incorrect results for volatile oils; the behavior of volatile oils does not fit the assumptions inherent in derivation of these equations."

The gas that comes out of solution in the reservoir from a black oil below its bubblepoint is usually a dry gas. 5 As this free gas is produced, it remains a gas as pressure and temperature are reduced to separator conditions. As reservoir pressure decreases, the gas leaving solution becomes richer in intermediate components, and the gas could become a wet gas. However, this occurs late in the life of the reservoir and has little effect on ultimate production.

The gas that comes out of solution in the reservoir from a volatile oil is normally a retrograde gas.5 This free gas will exhibit retrograde behavior in the reservoir and when produced will release a large amount of condensate at surface conditions. The quantity of condensate released from the free gas associated with a volatile oil is significant; often more than one-half the stock-tank liquid produced during the life of a volatile oil reservoir left the reservoir as free gas.

Thus, the important difference between black oils and volatile oils is that the solution gases from black oils remain solely in the gas phase as they move through the reservoir, the tubulars, and the separator; the solution gases from volatile oils are rich and lose condensate in the separator.P One assumption inherent in the derivation of classic material-balance equations is that the free gas in the reservoir remains as gas through the separator."

The material-balance equations treat a multicomponent black-oil mixture as a two-component mixture: gas and oil. Reservoir engineering calculations for volatile oils must treat the mixture as a multicomponent mixture so that the total composition of the production stream is known and separator calculations (which require knowledge of composition) can be performed to determine the amounts of liquid and gas at the surface.5,8

Special laboratory procedures can predict the recovery of volatile oils under depletion drive; however, these are somewhat difficult to analyze.? Above the bubblepoint, the undersaturated-black-oil material-balance equation can be used for volatile oils. Below the bubblepoint, compositional material-balance calculations normally are required, either with K factors or equations-of-state (EOS). The special laboratory procedures mentioned above help in deriving the K factors or "tuning" the EOS.l,9,IO

Examination of hundreds of laboratory studies indicates that one should suspect the presence of a volatile oil whenever the initial producing GOR exceeds about 1,750 scf/STB, especially if the stocktank oil gravity is high. Another indicator of volatile oil is a stocktank oil gravity exceeding 40° API with some color: brown, reddish, orange, even green. 1 ,2 If the oil FVF at the bubblepoint is measured in the laboratory, a value of 2.0 RB/STB or greater is expected for a volatile oil. 2

The data in Fig. 2 (a subset of the data in Fig. 1) illustrate the differences in composition between volatile oils and black oils. An

September 1994· JPJ.'

100.000

00.000

\:'=- ,_ j + _ .. _ _

10

20

30

Fig. 1-Relatlonship between initial producing GOR and heptanes-plus concentration.4

,

o I a-(dewpoint£)

~J.~iJs (bubble ~~~~ _ ..•..

3000 1- _ - _._ _ .. __ .. o.~..... . 0 :.~.-.~

•

2000

.... , .

.

~----------4--------.---.~~~-~----_-

i • •••• ..

• • • ••

I .j

•

1000

7.5

12.5

J7.S

Fig. 2-Relatlonshlp between initial producing GOR, phase in reservoir, and heptanes-plus concentration.11

initial producing GOR of 1.750 scflSTB corresponds to values of heptanes-plus concentration between about 18 and 22 mol%. So we take 20 mol% as a reasonable, but not necessarily sharply defined, transition point between volatile oils and black oils.

As reservoir pressure decreases in a volatile oil reservoir, the flow stream in the reservoir becomes virtually all gas." However, this gas is a retrograde gas and is rich enough to release large quantities of condensate at surface conditions. Thus, early in the life of a volatile oil reservoir, the stock-tank liquid comes from the oil phase in the reservoir, and late in the life of the reservoir, the stock-tank liquid is condensate from the reservoir gas. The increasing amount of condensate in the production stream causes the stock-tank oil gravity to increase steadily during the life of the reservoir (see Fig. 3).

The stock-tank oil gravity of a black oil changes in the opposite way. The large amount of dry gas produced with the black oil apparently strips some of the lighter components from the oil during the trip to the surface. Thus, the stock -tank oil gravity of a black oil

748

gradually decreases during most of the life of the reservoir. Late in the life of the reservoir, when the gas leaving solution is rich enough to be a wet gas, the stock-tank oil gravity will increase because of mixing with the condensate from the produced wet gas. These changes in the gravity of the stock-tank liquids during production often help in differentiating between black oils and volatile oils.

Of course, black oils are not necessarily black. These are very dark, often black, sometimes with a greenish cast, or brown, indicating the presence of heavy hydrocarbons.t The stock-tank oil gravities of black oils are expected to be less than 45° API. 2

Producing GOR's are constant for oils as long as reservoir pressures are above bubblepoint pressure. Both oils exhibit increasing producing GOR's when two phases exist in the reservoir. This increase results from the existence of free gas in the reservoir that has a much lower viscosity than the oil and. therefore, moves more easily to the wellbore. Of course, as reservoir pressure declines further, the amount of gas in the reservoir increases; this causes an increase in the effective permeability to gas and a decrease in the effective permeability to oil. As a result, the ratio of gas to oil in the reservoir flow stream increases (see Fig. 3). Black oils typically have higher surface GOR's than volatile oils during most of the producing time because the gases produced with volatile oils are diminished in volume owing to the loss of condensate in the separators.> Notice the decrease in producing GOR's for both oils late at the end of the production period. This turndown results primarily from the severe increase in gas FVF at low reservoir pressures.

50

Volatile Oil and Retrograde Gases

At reservoir conditions volatile oils exhibit bubblepoints and retrograde gases exhibit dewpoints. Fig. 2 is a portion of Fig. I with the data points indicating that the fluid had either a dewpoint or a bubblepoint at reservoir conditions. The scatter in the data reflects both the compositional differences among the fluids and the differences in surface separation facilities and conditions. Differences in the molecular weight of the heptanes plus are a major contribution to the scatter.

Notice in Fig. 2 that only two fluids indicate dewpoints at initial producing GOR's less than 3,200 scf/STB and that only one fluid indicates a bubblepoint above this value. Thus, a value of 3,200 scf! STB appears to be a fairly distinct transition point between volatile oils and retrograde gases.

Also notice that only two fluids with heptanes-plus compositions less than 12.5 rnol% exhibit bubblepoints and only three with concentrations above this value exhibit dewpoints. Thus, l2.5 mol% heptanes plus appears to be a useful dividing line between volatile oils and retrograde gases. Actually, volatile oils have been observed with heptanes-plus contents as low as 10 mol% and retrograde gases as high as 15 mol%.2 These cases are very rare and typically have unusually high stock-tank oil gravities (i.e., high molecular weights and specific gravities of the heptanes-plus fraction).

The retrograde liquid formed in a retrograde-gas reservoir at pressures below the dewpoint pressure of the gas is virtually immobile.l! Thus, this liquid is lost to production, and the condensate saturation increases as pressure declines. This causes a rapid decrease in effective permeability to gas as total liquid saturation increases. Many operators notice a sharp decrease in gas production rate soon after a retrograde gas reservoir passes through the dewpoint.

Although the flow stream from the retrograde-gas reservoir is virtually all gas, the surface producing GOR will increase after the reservoir pressure declines below the dewpoint (see Fig. 3). This results from the loss of condensate in the reservoir. condensate that would otherwise have ended up in the stock tank. The stock-tank liquid gravity increases as reservoir pressure decreases because the retrograde behavior in the reservoir removes some of the heaviest components from the gas; these components do not get to the stock tank, and the stock tank liquid is lighter (has higher API gravity).

Special laboratory procedures for retrograde gases provide data suitable for predicting future performance of retrograde-gas reservoirs.2 Compositional material-balance calculations, either with K factors or with EOS, also can be used for future perf or-

.....

22.5

September 1994 • JPI'

Stack Oil

Volatile Oil

Retrograde Gas

We! Gas

Dry Gas

81 I' 81 /\ 81 _/ ~8~ ~I No

~ ~ c_ l_ 8L:__

TIME

TIME

TIME

TIME

TIME

TIME

TIME

Fig. 3-Production trends for the five reservoir fluids.17

mance prediction. The results of the laboratory procedures are necessary to derive the K factors or to "tune" the BOS for these calculations.IO,l1 An interesting correlation is available for estimating the composition of the reservoir gas at pressures below the dewpoint. 12

Retrograde Gases and Wet Gases

Retrograde behavior has been observed in laboratory studies of retrograde gases with initial GOR's exceeding 150,000 scf/STB, although the amount of retrograde liquid is very small (less than about I % of the reservoir pore space). It appears that nearly all gases that release condensate at the surface probably release some condensate in the reservoir. That is, there are probably very few true wet gases (liquid at the surface but no liquid in reservoir). However, wet gas theory can be applied to retrograde gases that release small amounts of liquid in the reservoir.

The concept of a wet gas is very useful for engineering purposes.

The gas material-balance equation can be applied to a wet gas by simply (I) combining the surface gas and condensate by calculation to determine the properties of the reservoir gas and (2) adding the gaseous equivalent of the surface condensate to the surface gas production.P Remember, though, if there is a stock-tank gas, its specific gravity (which will be relatively high) must be included with the specific gravity of the separator gas or gases (weighted by gas production rates) to get an estimate of surface gas specific gravity. If the gas production rate and specific gravity of the stock tank vent gas are not known, correlations are available.U

If the concentration ofheptanes plus is less than 4 mol%, the gas can be treated as if it were a wet gas even though some retrograde liquid forms in the reservoir. 14 Fig. 2 shows that an initial producing GOR of 15,000 scf/STB and greater corresponds to heptanes-plus concentrations of less than 4 mol%. Thus, if the initial producing GOR is greater than 15,000 scflSTB, the fluid can be treated, for engineering purposes, as a wet gas (although there surely will be some retrograde liquid formed in the reservoir).

The producing GOR of a true wet gas remains constant throughout the life of the reservoir. Remember, though, that the guidelines for identifying a wet gas for engineering purposes cut fairly deeply into the range of fluids that exhibit some retrograde behavior. Thus, an increase in GOR later in the production period of a wet gas (as defined for engineering purposes) might be expected.

JPT • September 1994

TIME

TIME

TIME

Wet and Dry Gases

True wet and dry gases remain gaseous in the reservoir throughout depletion; i.e., neither has a dewpoint and neither releases condensate in the reservoir. The difference between the two is that wet gases release condensate as pressure and temperature are reduced to separator conditions, while dry gases remain entirely gaseous at the surface. Note that the words "wet" and "dry" as used in this classification system do not refer to the presence or absence of water or water

. vapor. Water is always present in petroleum reservoirs, and all gases normally are saturated with water vapor; however, water is excluded from this discussion.

The "gas material-balance equation" was derived originally for dry gases.l'' But it can be used for wet gases if the equivalent gaseous volume of the condensate is included in the cumulative gas production and the quantity and properties of the condensate are added to the surface gas to determine the properties of the reservoir gas. 13 Further, the equation is valid for a retrograde gas if the reservoir is volumetric and if two-phase gas compressibility factors are used. 14,15

The effects of condensate volume on reservoir gas specific gravity and on cumulative gas production are insignificant when the yield of condensate is 10 bbl!MMscf or less (i.e., when the initial producing GOR is 100,000 scf/STB or more). 16 Even though some condensate is produced to the surface and possibly some retrograde condensate is formed in the reservoir, reservoir fluids with initial producing GOR's this high can be treated as dry gases. The surface gas specific gravity can be used to represent the specific gravity of the reservoir gas, and the surface gas production rates can be equated to reservoir production rates. Fig. 1 shows that gases with less than 0.7 mol% heptanes plus have producing GOR's this high; i.e., if the heptanes-plus concentration is less than this, the fluid can be treated as a dry gas.

Review

Table 1 summarizes the guidelines for determining fluid type from field data.!? If any of these three properties fails to meet the criteria of Table 1, the test fails and a representative sample of the reservoir fluid must be examined in a laboratory to establish fluid type.

Table 2 shows the expected results of laboratory analysis of the tluids.l? Fig. 3 summarizes schematically the trends of producing GOR and stock-tank liquid gravity.!? These fluid types are

749

TABLE 1-5UMMARY OF GUIDELINES FOR DETERMINING FLUID TYPE FROM FIELD DATA17
Black Oil Volatile Oil Retrograde Wet Gas Dry Gas
Gas
Initial producing gas/liquid <1,750 1,750 to 3,200 >3,200 >15,000' 100,000'
ratio, scf/STB
Initial stock-tank liquid gravity, <45 >40 >40 Uplo 70 No liquid
°API
Color of stock-tank liquid Dark Colored Lightly colored Water white No liquid
"For engineering purposes. TABLE 2-EXPECTED RESULTS OF LABORATORY ANALYSIS OF THE FIVE FLUID TYPES17
Black Oil Volatile Oil Retrograde Wet Gas Dry Gas
Gas
Phase change in reservoir Bubblepoint Bubblepoint Dewpoint No phase change No phase change
Heptanes plus, mol% >20% 20 to 12.5 <12.5 <4' <0.7*
Oil FVF at bubblepoint <2.0 >2.0 - - -
"For engineering purposes. defined for engineering purposes. They should not be confused with reservoir fluid descriptions defined by legal agencies that regulate the petroleum industry. Regulatory definitions of oil, crude oil, condensate, gas, natural gas, casing-head gas, etc., are not related to these engineering definitions and, in fact, often contradict them.

References

1. McCain, W.O. Jr.: The Properties of Petroleum Fluids, second edition, PennWell Books, Tulsa (1990) 148-58,409-11.

2. Moses, P.L.: "Engineering Applications of Phase Behavior of Crude Oil and Condensate Systems," JPT(July 1986) 715.

3. McCain, W.O. Ir.: "Reservoir-Fluid Property Correlations-State of the Art," SPERE (May 1991) 266.

4. McCain, W.O. Ir.: "Chemical Composition Determines Behavior of Reservoir Fluids," Pet. Eng. Inti. (Oct. 1993) 18.

5. McCain, W.O. Jr.: "Black Oils and Volatile Oils-What's the Difference?," Pet. Eng, Inti. (Nov. 1993) 24.

6. Jacoby, R.H. and Berry, V.J. Jr.: "A Method for Predicting Depletion Performance of a Reservoir Producing Volatile Crude Oil," Trans" AlME (1957) 210, 27.

7. Schilthuis, R.I.: "Active Oil and Reservoir Energy," Trans., AIME (1936) 118, 33.

8. Cordell, J.e. and Ebert, C.K.: "A Case History-Comparison of Predicted and Actual Performance of a Reservoir Producing Volatile Crude Oil," JPT(Nov. 1965) 1291.

9. Reudelhuber, F.O. and Hinds, R.E: "Compositional Material Balance Method for Prediction of Recovery for Volatile Oil Depletion Drive Reservoirs," Trans., AIME (1957) 210, 19.

10. Coats. K.H. and Smart, G.T.: "Application of a Regression Based EOS PVT Program to Laboratory Data," SPERE (May 1986) 277.

11. McCain, W.D. Jr. and Bridges, B.: "Volatile Oils and Retrograde Gases-What's the Difference"," Pet. Eng. Inti. (Jan. 1994) 35.

12. Niemstschik, G.B., Poetmann, EH., and Thompson, R.S.: "Correlation for Determining Gas Condensate Composition," paper SPE 26183 pres-

750

ented at the 1993 SPE Gas Technology Symposium, Calgary. June 28-30.

13. Gold, O.K., McCain, W.O. Jr., and Jennings, I.W.: "An Improved Method for the Determination of the Reservoir-Gas Specific Gravity for Retrograde Gases," JPT (July 1989) 747, Trans., AIME.287.

14. Rayes, D.G. et al.: "Two-Phase Compressibility Factors for Retrograde Gases," SPEFE (March 1992) 87, Trans .• AlME, 293.

15. Craft, B.C. and Hawkins, M.E: Applied Petroleum Reservoir Engineering, Prentice-Hall, Englewood Cliffs, NJ (1959) 39-44. 82.

16. McCain, W.O. Jr. and Piper, L.D.: "Reservoir Gases Exhibit Subtle Differences," Pet. Eng. Intl., (March 1994) 45.

17. McCain, W.O. Jr.: "Revised Gas-Oil Ratio Criteria-Key Indicator of Reservoir Fluid Type," Pet. Eng. IntI. (April 1994) 57.

William D. McCain Jr. is a senior executive with SA Holditch & Assocs. Inc. In College station, TX, and a part-time visiting professor of petroleum engineering at Texas A&M U. He has written two editions of Properties of Petroleum Fluids. He holds a BS degree from Mississippi State U. and MS and PhD degrees from Georgia Inst. of Technology. McCain teaches the SPE short course "Review for the Principles and Practice Examination' and taught the short course on reservor fluid properties. He Is a member of the Editorial Review Committee and was a member of the 1986-89 Career Guidance, 1972-75 Textbook, and 1967-71 Education and Accreditation (1970 chairperson) commiltees.

September 1994 • JPT


Lecture #10

Chapter 6 - Properties of Dry Gas

Phase diagram of dry gas reservoir

·Reservoir gradually deplete: reduction in reservoir pressure

·Production path from reservoir to separator conditions is outside phase diagram

·No liquid produced at surface

Petroleum reservoir fluids

·Five types of reservoir fluids

-Black oil, volatile oil, retrograde gas, wet gas and dry gas

·Indicated by production information -Initial producing gas-oil ratio

-Stock-tank liquid gravity (OAPI) :

-Stock-tank liquid color

·Confirmed by laboratory test

-Phase change in reservoir

-Heptanes plus

-Oil formation volume factor (FVF) at bobble

point

Features of Dry Gas

·Primarily methane

·Initial gas-oil ratio (GOR): >100,000 scf/STB

Standard conditions

·Standard conditions: to report volume of gas on common ground

-Standard temperature: 60°F

-Standard pressure: 14.65 to 15.025 psia

-Volume at standard condition: standard cubic

feet

-Standard conditions in our textbook: ·Tsc=60oF and Psc=14.65 psia

Properties of dry gas

'Gas formation volume factor 'Coefficient of isothermal compressibility -Ideal gas

-Real gas

'Viscosity of gas

Gas formation volume factor

B = 0.0282 zT ft) bbl

g P sci 5.61Sft3

Unit: ft3/scf or res bbl/scf

11

~~

---

Pressure _______.,.

Gas formation volume factor, 8g, decreases as pressure increases


·Definition: volume of gas at reservoir conditions required to produce one standard cubic foot of gas at the surface

Reservoir conditions

Standard conditions

same mass of gas

B = zT(l4.65) = 0.0282 zT ft3

g (I.O)(S20)p P sci

At standard condition:

Tse= 460 + 60 °F= 520 OR, Pse = 14.65 psia, Zse = 1


B = 0.00502 zT res bbl

g P sci

Z-factor value:

'If experimental z-factor is available, it should be used

·If composition of gas is known,

-Calculate Ppe and Tpe

Ppc = LYjPq T; = LY);'J

-Calculate Ppr and T pr

-z-factor obtained from Fig. 3-7

·If only specific gravity of gas is known, - Find Ppe and Tpe from Fig. 3-11

-Following steps are the same as above

Example 1-8g calculation

A. Calculate Bg of a dry gas with a specific gravity of 0.818 at reservoir T = 220 of and p = 2100 psig.

Solution:

1. Calculate pseudocritical properties yg=0.818

Ppc= 647 psia, Tpc = 406 OR

2. Calculate pseudoreduced properties

T . = (220 + 460)" R = 1.68

P' 4060 R

p = (2100 + 147)psia = 327

P' 647 psia .

3. From Fig. 3-7, we obtain z = 0.855

4. Calculate B9

B = 0.00502 ::T res bbl

g p scf

B, =0,00502 0.855(220+460) = 0,00138res bbl

g (2100+14.7) scf

Coefficient of isothermal

com pressibility

·Definition: fractional change of volume as pressure is changed at constant temperature

cg =-~(:l =-~M (a;; JT =-~(:l

V: volume of gas; V M: molar volume v: specific volume

·Unit of cg: 1/ psi, psi:'

Constant T

'.

Compressibility, cg, decreases as pressure increases

Example 1-8g calculation

B. One well is producing this gas in a 320-acre drainage area which has an average formation thickness of 20 ft, porosity of 15% and water saturation of 30%. What is the original gas in place if the initial p = 2100 psig.

E;'0" .;: (l

)

14~' r: r-

~--i ~\ i~j (:

Coefficient of isothermal

compressibility

-For ideal gas (J

1 8V

cg =-- -

V 8p T

With

pV=nRT

Or

V= nRT p

1

==> cg =p

-For real gas

With

pV=znRT

Or V= znRT p

'i

-;c" ...)v

Coefficient of isothermal compressibility

·For real g;s: in/[ed~:ed) form

C =------

pr Ppr Z appr '

Ip'

Pseudoreduced compressibility

<.

C =-g

Ppe

Coefficient of viscosity of pure gas

Viscosities of pure gases at atmospheric pressure

Coefficient of viscosity of gas

·Dynamic viscosity: a measure of resistance to flow exerted by fluid, with unit

centipoise = g mass/100 sec cm

Pressure

·Viscosity, u,

-J.l1' asp l'

- At low p, J.l l' as T 1"-

- At high p, J.l -4t as T l'

Coefficient of viscosity of gas mixture

·Viscosity of gas mixtures at one atmosphere pressure: -Composition of gas mixture known

~ M1I2

L,!-'g;Y; j

j

-Composition of gas mixtures not available Using Fig, 6-8 to obtain J.lg

Ma

r, =2"9

·Viscosity of gas mixtures at high pressure -Using Figs. 6-9 to 6-12 (covering different specific gravity range)

Correlation: ~i~g1 - Ppr, Tpr

I-'g I-'g=-I-'gl I-'gl

J.lg1: viscosity at 1 atm

;t{ Example 6-11 in Textbook (page 185)

Viscosity of gas mixture at atmospheric pressure

·Composition of gas mixture is not known:

Gas specific gravity

,016
<I>
,!I ,015
~ ,Mot
i
8 ,013
... ,Q12
""
:;, .011
i ,01()
<I>
'tit
~
J .006
.005
,0114
10 20 Molecular Might

Viscosity of gas mixture at high pressure

Check this range

Gas specific gravity from 0..56 to 0.9

Pseudoreduced temperature. Tpr

Example 6-11 in Textbook (page 185)

"/

1,'-'

'.\

(~·( .. I

" f\

\ t)

! (D l\\~\

(5. \ Ie

" . ()


Lecture #11

Chapter 7 - Properties of Wet Gas

Phase behavior of wet gas

-Fluid is always gas in reservoir conditions ·Liquid condenses as gas moves to surface condition

·Surface gas is different from reservoir gas -in composition and properties

Re-Cap of Lecture 10 ·Dry gas reservoir

-Prirnarily methane

-No liquid produced at normal surface condition

-Initia: gas-oil ratio (GOR): >100,000 scffSTB

·Properties of dry gas =Gas formation volume factor

B = 0 00502::T res bbl

K' p sci

-Coefficient of isothermal compressibility

1. -, =-H~;l =- ~I (8~f 1 =-~(:;l

2. I 1 (8::)

-, =-;;--; 3p T

-Viscosity of gas

--At 1 atm

LJ1giYjM~/2

_ J

1. Cornposttion is known:

f.igl- ~ Ml.i2 ~Yj J

f

2. Specific gravITy is known: Fig. 6-8

-- At high pressure

Jig

Jig = -Jig! Figs. 6-9-6-12 Jig!

Recombination of surface fluids

·Properties of reservoir gas: determined by recombination of surface fluids

• Two-stage separation system

-Separator gas, stock-tank gas, stock-tank liquid

Wellhead

(Ib - mo/ega, ),p

!fb-moleq~ +ib - moleci!)""

= Vb - male • as

~ IIIJ-moie..,1

i/b - m~e",. -+- II) - ~~~Ieoi/I&T

Recombination of surface fluids

·Composition known

-Surface compositions known-(Procedure 1)

-Separator composition known-(Procedure 2)

·Composition unknown

-Separator gas and stock-tank vent gas properties known--(Procedure 3)

-Properties of stock-tank gas unknown -(Procedure 4)

Procedure 1-surface composition known

·Steps-cont.

-Convert Rsp and RST to Ib-mole gas/lb-mole stocktank liquid

rt;;"J sef ST gaS)<==l> i = RsrM STU i !!'_moJe ST gas

~ STB i 2138pslV: lb mole 8TO

-Calculate mole fraction for reservoir gas


·Composition of reservoir gas can be obtained

·Steps

-Calculate molecular weight of stock-tank liquid

MSlD = ~xM.

L.. } }

j

-Calculate density of stock-tank liquid

a API = 141.5 - 131.5 Yo

and

PSTO r;=':">

PH'

... __ .-_. __ .... _ .... -r-r-r-r-r-r-rr- .. _._----

Component Composition. ComposJtJon, Composition,

... parator gas, stock'lank gas, stock·lank liquid,

mole fraction mole fraction mole fraction

0.8312 0.3190 0.0018

0.0960 0.1949 0.0.063

0,0455 0,2532 0,0295

0.0060 0.0548 0,0177

0.0087 0,0909 0.0403

0,0028 0,0382 0,0417

0,0022 Q,Q3!J3 0.0435

0,0014 0,0191 0.0999

0.0002 0,0016 0,7193

1.0000

1,0000

1.0000

plus ot tho stock~~ank liquid

0.794 113 !bIlbmo!f)


-Steps

-Calculate molecular weight of stock-

tank liquid

MSTO = 2>jMj = 100.9 Ib/lb mole j

-Calculate density of stock-tank liquid

o API = 141.5 -131.5 Yo

PSTO = 47.11 lb/ft"

Procedure 1--surface composition known

.Table ~ Example 7..:_~ ... _ .

.comp05i1#m, Oompodliorl, C!;mpoej1lol1.

stoeIc..wgu. stack43nkDil rtetlmbiMdIl'P

1JI{)\e~ mttIafroolioo mo~1t'l!I:tiOII

/

For one mole of STO (stock tank oil)

Procedure 1--surface composition known

-Steps-cont.

-Convert Rsp & RST to Ib-mole gasl Ib-mole

stock-tank liquid

(69 551scf SP gas)

• STB

RspM,I"lO I Ib mole SP gas 2138psTO Ib mole STO

=69.69 lb mole SP gas Ib mole STO

(366 scf ST gas) STB

RITM sm lIb mole ST gas i2138PI7V lb mole STO

=0.3667 Ib mole ST gas Ib mole STO

Procedure 1-summary

-Known data:

-Surface compositions: separator gas,

stock-tank gas, stock-tank liquid

-Rsp, RST scf/STB

-YSTO

-Solution: composition of reservoir

gas

-Use: calculate properties, z-factor

Procedure 2-separator composition known

·Known data:

-Compositions: separator gas, separator liquid

-Rsp: scf/STB

-Ratio of volumes of separator liquid to

stock-tank liquid, R, (SP bbI/STB)

'Solution: composition of reservoir gas 'Steps

1. Calculate molecular weight and density of separator liquid

2. Calculate ratio of Rs/Rx, scf/SP bbl

Procedure 3-composition unknown

-Known data: separator gas and stock-tank vent gas property known

- YgSP and YgST' separator gas and stock-tank gas

-Rsp and RST

-Specific gravity of stock-tank liquid, YSTO

-Molecular weight of stock-tank liquid, MsTO, or

5954 42.43ySlO

Msro

a API - 8.8 1.008 - YSTO

(If MSTO is not known)

-Solution: specific gravity of reservoir gas can be obtained

Procedure 2-separator composition known

'Steps

3. Convert Rsp/Rx to Ib-mole gas/lb-mole separator liquid

(I ~~ Iscl~!Pb~~S

RspM,\po lb mole SP gas Ibmole~

4. Calculate composition of reservoir gas


-Steps (two-stage separation)

1. Calculate specific gravity of surface gas

2. Calculate gas-oil ratio of surface gas

3. Calculate specific gravity of reservoir gas

R r. +4600yS1O

YgIl

R + 133,300yS1O / MS10

Exercise

A wet gas reservoir is produced through two stages of separation. The initial daily production is 25,900 Mscf of separator gas with a specific gravity of 0.61, 100 Mscf of stock tank gas with a specific gravity of 1.05, and 242 stock tank barrels of condensate with a 55 °API. Calculate the specific gravity of the reservoir gas.

10

\2.s 1

141,5

~--".~-~- ;

I'M·S 55

6C(£t.! _

~~.~,.--' -

J 15

Three-stage separation system

O.Cali'7


·Steps (three-stage separation)

1. Calculate specific gravity of surface gas

RSPIYgSPl +RSP2Yg~P2 + RSTYgST

Y = '

g RSP1 + RSP2 + RST

2. Calculate gas-oil ratio of surface gas

3. Calculate specific gravity of reservoir gas

R r, + 4600ySTO

Y R = ~~~~~~~~-

g R+133,300YsT01M.;"]v


·Known data: properties of primary separator gas and stock-tank liquid known, but stock-tank gas unknown

·Solution: specific gravity of reservoir gas can be obtained

·Step

-Specific gravity of reservoir gas

RSP1YgSPl + 4600ySTO + AGP

YgR = R V.EQ

SF] +

(a) For two-stage separation:

VEQ = R,'T + 133,300ysTO / MSTO

(From Fig. 7-4)

AGP = RSTY gST

(From Fig. 7-5)

(b) For three-stage separation:

VEQ = RSP2 + RST + 133,300ysTO / MSTO (From Fig. 7-2)

AGP = RSP2YgSP2 + RSrYgST (From Fig. 7-3)


Lecture #12

Chapter 8 - Properties of Black Oil - Definitions

Chapter 9 - Properties of Black Oil - Field Data

Properties of Black Oil ·Specific gravity of oil

·Formation volume factor of oil ·Solution gas-oil ratio

-Total formation volume factor ·Coefficient of isothermal compressibility -ou viscosity

Specific gravity of oil

·Definition: ratio of oil density to water density at same condition (temperature and pressure)

Yo = Po Pw

·API gravity:

o API = 141.5 -131.5 Yo

Re-Cap of Lecture 11 ·Recombination of surface fluids: properties of reservoir gas

-Procedure 1: compositions of reservoir gas ·Separator and stock tank compositions known -Procedure 2: compositions of reservoir gas ·Separator compositions known

-Procedure 3: specific gravity of reservoir gas • Y9sP , Y9ST ' Rsp , RST ' YSTC ' MSTO known -Procedure 4: specific gravity of reservoir gas • Y9sP' Rsp, YSTC' MSTOknown

ena GOR (set I 8TB) ~OR (scfiSTB) Wellhead L--=~e[kJ

Stock tank

Formation volume factor of oil

-Oil shrinks when it moves from reservoir to surface

Gas out of oil solution

~

Reservoir P &T

Reservoir P below Pb

Surface P &T

Formation volume factor of oil

·Definition: volume of reservoir oil required to produce one barrel of oil in stock tank.

B = volume of oil + dissolved gas at resen'oir condition

U volume of oil entering stock - tan k at stan dard condition

·Unit: res bbllSTB

So

Reservoir T = constant

I

iPb

,

Reservoir Pressure

Total formation volume factor

Free gas volume and oil volume at pless than Pb for one barrel of stock tank oil

<

P' .1\

Solution gas-oil ratio ·Definition: quantity of gas dissolved in oil at reservoir conditions

R = volume of dissolved gas at stan dard condition

S volume of oil entering stock - tan k at stan dard condition

·Unit: scf gas/STB oil


._--_ ..........•• ,"""_ ... - ..... , ..... -----

Reservoir pressure


·Also called two-phase formation volume factor

·Unit

- Bt: res bbll STB

- Bo: res bbll STB

- Bg: res bbll sef

- Rsb, Rs: sef/STB

iIi ci III

So

i

;

I/Pb


St

Reservoir pressure

-j

V tI r~ S

~

VI.I'St_,A IG~':

j"J 5.1 "! i -I {.60 1.

Exercise 1

A reservoir oil sample of 63.316 cc was placed in a PVT cell at 220 of and the bubble point pressure of 2635 psia. When pressure in the cell was reduced to 2465 psia, 3.606 cc of gas was generated and oil volume became 62.016 cc. Then the generated gas was removed from the cell and measured at standard conditions (60 of and 14.65 psia) as 0.02235 set, When pressure in the cell was finally reduced to 14.65 psia, the total volume of removed gas from the cell was 0.21256 scf (measured at standard conditions). The volume of the residual oil left in the cell was also measured, which is 39.572 cc. Calculate the total formation volume factor at 2465 psia.

5( 1. ::,(~ "; -' ()_,(JG_§3_(8, ~=

·r

Exercise 2

There is a reservoir with the initial pressure of 3515 psia and temperature of 195 of. The oil in the reservoir has its bubble point pressure of 3045 psia. The oil formation volume factor at the bubble point pressure is 1.558 res bbI/STB.

(a) Determine the value of the coefficient of isothermal compressibility between the bubble point and the initial reservoir pressure, given that the oil formation volume factor is 1.546 res bbVSTB at the pressure of 3515 psia.

(b) If the reservoir oil density at the bubble point pressure is 51 A Ib/ft3, what is the oil density at the pressure of 3515 psia?

Coefficient of isothermal compressibility of oil

-Definition: fractional change in volume of a oil as p is changed at constant T (P>Pb)'

-Unit: co-1/psi

-P> Pb

Or v2 = VI exp[co(PI - P2)]

Or

Coefficient of viscosity of oil

-Viscosity (!-Lo) is a measure of resistance to flow exerted by a fluid

-Unit: centipoise = 9 mass/100 sec cm

-Use: calculation of fluid flow in reservoir,

well bore and pipeline

-Variation of !-Lo

- T increases, 110 decreases

-P decreases, flo increases, for P<Pb

P increases, 110 increases, for P>Pb -Molecular size and complexity increase, 110 increases

Properties of Black Oil from Field Data

·Initial reservoir pressure -Higher than p,

-No free gas in reservoir

-Lower than Pb

·Gas cap (above oil zone): Pb at interface between gas cap and oil zone

·Gas production trends

-At pressure> Pb.

·Only dissolved gas

·Constant producing gas-oil ratio

-At pressure < Pb'

·Dissolved gas and free gas ·Increase in producing gas-oil ratio

Production history data of black oil reservoir

Ctlmufatlve oil production, MMSTa

Black oil reservoir

·Pressure trends -At pressure> Pb.

·Reservoir pressure decreases rapidly during production

-At pressure < Pb.

·Reservoir pressure decreases relatively slowly during production

Slope change on pressure plot can be used to identify Pb

Adjustment of surface gas data

Ignoring the vented gas. estimated solution GOR can be low by 10 -20 %

XiST Stock tank

Two-stage separation system

Adjustment of surface gas data

·Gas volume from separator are recorded

·Gas from stock tank is often vented

-ignore this vented gas

-estimate of Rsb can be low by 10% -

20%

·Solution

-Add stock tank gas-oil ratio obtained from correlation (fig. 9-3) to separator gas-oil ratio from field data

Example

7000

1000

r········_· == I
f'&
-. ~s~ .
"
"
~ "I
-.
. i -.~-
~"
" . "
.. . -.,-- 1000

900

6000

5000

800

700

3000

600

500

400

500000 1000000 1500000 200000O 2500000

Cumulative production, MSTB

\

r»

Estimation of stock tank gas-oil ratio

Exercise 3

The Kelly-Snyder Canyon Reef Reservoir produces a 40 oAPI stock tank oil and a 0.75 specific gravity separator gas. The early-time field pressure and production history are shown in the following figure. The field separator conditions are 100 psig and 120 of.

(a) Estimate the bubble-point pressure for this reservoir.

(b) If the gas from the stock tank is vented and its volume is not measured, the producing gas-oil ratio only includes gas from the separator. In this situation, make your adjustment for the solution gas-oil ratio at the bubble point

I

•

I

p,ooI·"

JR,. _

Cumulatlw Pfoouctioll/MStb)

Pressure and production history

l\\ )

1100" Ii 1


Lecture #13 Chapter 10 - Properties of Black Oils - Reservoir Fluid Studies

Reservoir Fluid Studies

·Objective

-Provide values of physical properties required in material balance calculation

·Method

-PVT properties determined by laboratory procedures

·Five laboratory procedures -Flash vaporization

-Differential vaporization

-Separator test

-Oil viscosity measurement

-Composition measurement

Sampling before reservoir pressure drops below Pb

Re-Cap of Lecture 12 ·Properties of black oil

-Specific gravity of oil

Yo = p" "API = 141.5 -131.5

o; Yo

-Formation volume factor of oil

volume of oil at reservoir

B () volume of oil at stan dard condition

-Solution gas-oil ratio

R_ volume of dissolved gas at standard condition

, volume of oil at stan dard condition

-Total formation volume factor B, = B" + Bg (R" - Rs l

-Coefficient of isothermal compressibility (p>Pbl

I (iJV) 1 (WH) 1 (iJV)

c" =-v- Dp 7' =-V,ll D;J T =-~ 8P T

·From field data

-Reservoir pressure trend: Pb

-Producing gas-oil ratio: Rsb

Reservoir Fluid Studies

-Fluid properties determined

-Black oil

oPb -a,

-a,

-s,

oCo

o ~o

-Gas oZ-factor oBg

o ~g

-Compositions of oil and gas

-Separator gas

-Stock tank gas

-Stock tank oil

(

Flash vaporization test (CCE)

Pressure is reduced by increasing volume. Equilibrium is reached

Differential vaporization test

Atmospheric

pren·T",

Atmospheric pressure, 60°F

Pressure is reduced by increasing volume. Equilibrium is reached

d '-yO ;) G )(,

r lQ

/.

Flash vaporization test (CCE)

-Data measured

-Pressure and total volume

-Properties determined

-Pb' from plot of pressure against total volume

-co in single liquid phase


9., C vtjVJ'}

.... _

1P~ ~:flt


·Data measured

-Gas volume (at cell conditions and standard condition) and specific gravity

-Remaining oil volume and residue oil volume (at standard condition)

·Properties determined

-BoDb at p, and BoD at pressure below p,

-z-tactor

-Bg

-RsDb at Pb and RsD pressure below Pb

-BtD

All these properties can be determined at different pressures and the reservoir temperature

Separator tests

·Properties determined -Formation volume factor of oil

B _ volume of liquid expelled from cell nSb - volume of liquid in stock - tan k

-Solution gas-oil ratio

At bubble point

Separator tests

·Data measured

-Volume of liquid expelled from cell

-Volume of liquid in stock tank

-Volume of separator gas and stock tank gas

-Specific gravities of separator gas and stock

tank gas

f'tt"''It
1:5 m r.ost rU!40
41 41 40.S \A$i },001 lolJS
m
617 £74 V?ft].; 1.001: 'C.7S6
91 ..2l S. :~.<174 1,001 L36S
"'~'r
'" &0:11 f'A'1 l.lH 0.131:
m rse 4U,. 1.4$J LOOi 1.329-
*
41& s .. t;,HIJ
i45 ~ 40,1 '.<195 1.00;
'" f" I !

@//:: r{\r{HJ. \

t

,

~ ,

.:»>: pt": n1 If'L "

17

VYl_C1 ~ I

iff s~()C t To~ k'

Selection of optimum separator conditions

150

200

250

300

Seperator pressure, psia

Reservoir fluid properties from laboratory

'At pressure above Pb -Combining flash vaporization and separator test

s, =(~) BoSh

b F

'At pressure below Pb

-Combining deferential vaporization and separator test

69.0

Separator tests

TABLE 10-3

Nomencla! .. !"",,~d In ana~l. of reservoir fluid studies _

Sci> "" relative olll!Olume by differential vaporization, page 5, column 3, Table 10-1

!J<>J;t; relative oil volume ar bubble point by differential vaporization, page 5, colcmn 3, Table 10-1

B<>$it formation volume factor at 5eparator pressure), page 1, column

separafCf test (at selected

(V~AJb)F "'" retanve total volume (Oil and gas) by flash veportaenon, page 4, column 2, Tobie 10-1

relative total volume (oil and gas) by differential vaporization, page 5, column 4, 10-1

gas remaining In solution by ditfarenlial vaporization, page 5, column 2-, Table

gas In solution er bubble point (and above) by djfferential vapmlzalion, page 5, 2, T.bi<JIO-l

and stocK-tank gas from separator teet (at selected conenn 4, TAhiA 10_1

iYl4)(

'!'i\, n t),"

Y)\."{",

Exercise

1. Given the test data and analysis of reservoir fluid study in the table below, answer the following questions:

Differential Vaporization at 176°F Flash Vaporization
at 176 of
relative gas incremental
oil solution deviation oil gas relative
pressure volume GOR factor density gravity pressure volume
p BoD RsD Z Po t« P V/Vb
(psig) (bbl/bbl) (set /bbl) (glee) (psig)
3,000 0.9831
2,500 0.9874
2,000 0.9919
1,600 0.9958
1,400 0.9979
1,208 1.256 355 0.7428 1,208 1
1,050 1,154 1.0182
900 1,102 1.0386
750 1.216 261 0.929 0.7553 0.723 1,031 1.0692
600 1.202 229 0.94 0.7597 0.75 955 1.1101
450 1.187 196 0.95 0.7644 0.787 862 1.1716
300 1.17 162 0.963 0.7697 0.844 767 1.2533
150 1.149 120 0.981 0.7761 1.006 662 1.3765
85 1.133 95 0.988 0.7806 1.229 552 1.5614
0 1.053 0 0.8034 1.795 460 1.7978
Separator Tests
Stock
pressure tank FVF
p T Rssb gravity Bosb
(psig) (OF) (scf/sra) CAPl) (res bbl/srs)
Separator 25 71 279
Stock tank 0 71 19 37.8 1.208

Separator 50 71 252
Stock tank 0 71 40 38 1.203

Separator 100 71 223
Stock tank 0 71 72 37.9 1.205 (a) Determine values of oil formation volume factor for use in reservoir engineering calculations at the following pressures. Assume the separator operates at 50 psig and 71°F.

pressure (psig)

2000 1208 450

oil formation volume factor (rb/stb)

\.l OJ '3

(b) Determine values of solution gas-oil ratio for use in reservoir engineering calculations at the following pressures. Assume the separator operates at 50 psig and 71°F.

pressure

~ 2000

1208

solution gas-oil ratio (scf/stb)

450 146 '~:.i' _jf'l_o'\tk& -z. 'ct0.i -CS5:>19 \.I'\5"P[, "so) B "

e ;.i~~

(c) Determine values of total formation volume factor for use in reservoir engineering calculations at the following pressures. Assume the separator operates at 50 psig and 71°F.

~/t\

total formation (7 ~--"'I B-i:_ i: ::-7 IS" IY; 3

volume facto; I

(rb/stb) ))''':/ P '" P,b,

I, ~ ~7B ~

, l ~

L ? 0:: ______./ ~/ P LPb

~) ~-~/ t:;»:;\~ D ..

\ ~ 8.t., 'S' \i

(d) Determine a value of coefficient of isothermal compressibility of oil for use in rese;.~;rt engineering calculations at the pressure between 2000 psig and 1600 psig.

2000

8~~' 0,

pressure

~

1208

450

(e) Determine the value of oil density for use in reservoir engineering calculations at the pressure of 2000 psig.

Exercise

2. During the differential vaporization test, 1.87 ems of gas and 88.2 ems of oil were measured in the cell at 900 psig and 176 of. The gas was expelled from the cell at the constant pressure and its volume at standard conditions (14.65 psia and 60°F) was 101.8 ems. Calculate the z-factor.

~(

\

Wu)

/

illv-

I


Lecture #14 Chapter 11 - Properties of Black Oils - Correlations

Solution gas-oil ratio

Bubble-point pressure

-Correlation: Pb

-Rs: early production data

- Yg: separator gas

-Yo-API

-T

-Accuracy

-Within 15%

Density of liquid

-ldeal liquid solution

-No special attraction force

-No change in internal energy\

-No change in character of liquid

-Dilution of one liquid by the other

-Liquid mixture of hydrocarbons can

be treated as ideal liquid solution -Components with similar characteristics

1

Density of liquid at surface conditions

·Procedure (Ideal solution principle) -Calculate mass and volume of components

-Add mass and volume to get total mass and volume of mixture

-Divide mass by volume of mixture to obtain density

Density of reservoir liquid

·Procedure

-Calculate liquid density at standard conditions

* ·C1 and C2 are not liquid: apparent liquid density (Fig. 11-2)

·A liquid mixture partially vaporizes at standard conditions: pseudo-liquid with the same composition as reservoir liquid

-Adjustpseudoliquid density to reservoir conditions

·Coefficient of compressibility ·Coefficient of expansion

f; 0 ~jP'''-'

~--+-7

Use ideal solution principles to calculate the density at 14.7 psia and 60 of of a

hydrocarbon liquid with the following

composition" {"i -

rJ' P -.l;- /

)g Mi 29:M.l yj ill Xi'Mi/pi
Ib mole Ib/lb mole !Q Ib/cu It cu It
n-G5 0.225 72.15 16.23 0.6311 39.40 0.4120
n-G6 0.425 86.177 36.63 0.6638 41.44 0.8838
G7+ 0.350 219 76.65 0.8525 53.22 1.4402
1.000 129.51 2.7360
Properties of heptanes plus
Specific gravity 0.8525
Molecular weight 2191b/lb mole f

Pressure adjustment (Fig. 11-3)

,.

P - f

I I) "

Temperature adjustment (Fig.11-4)

o

30 40 so 60

Density at 60" F and pressure p, lb per cu ft

1

P(PR,TR) = P(PR' T,J - ;:"'p(TR)

6[> 0R):: YVlfilv, .---iP. (Pii. T~( (Jo( 'r""

. c.,

Density of reservoir liquid

·Solution gas-oil ratio, gas specific gravity and stock-tank oil gravity known

Methods

·Composition of saturated liquid known

-Iterative method

-Correlation method

·Solution gas-oil ratio, gas composition and stock-tank oil gravity known

·Solution gas-oil ratio, gas specific gravity and stock-tank oil gravity known

Pa: from Fig. 11-8

Ppo: density at standard condition

Exercise 2

Determine the density of a reservoir liquid at its bubble point of 3385 psia and 205°F. The solution gas-oil ratio at the bubble point is 1000 scf/STB, and the specific gravity of gas and stock-tank oil are 0.756 and 40.3 °API, respectively.

6'.)"(6 -: 141

c.

Density correction for H2S

H It

Wclgtu: P(lfctmt tryd"Ogef\ lWlfltW

Formation volume factor of oil at saturation pressure

'Using

s, = PSTO +O.OI357RsYg

PoR

U . I t· F· 11 ~9\'-~

• sing corre a ion, Ig. -

!j 00' ro{l,

Density of reservoir liquid at pressure above Pb

'Calculate density at Pb

'Then, calculate density at pressure above Pb based on

Formation volume factor of oil at pressure above Pb

'Calculate formation volume factor at p, and reservoir temperature

'Then, adjust this formation volume factor at pressure above p, based on

4

11_13 /~( I if

))0\;.'" {,IS e. t' .~/ ;iAOb: (1:::; (I' qc.

·At pressure above Pb

-Using correlation in Fig. 11-11 ·At pressure below Pb

-Using correlation in Fig. 11-12


Coefficient of isothermal compressibility of oil

·Equations

B( = Bo + Bg(Rsb -Rs) zT res bbl s, = 0.00502

p scf

-o- correlation in Fig. 11-10

~

I,

~l R:o\-c:

)/1

Oil viscosity

·At pressure below p,

-Using correlation in Fig. 11-13 for viscosity at one atmospheric pressure and reservoir temperature

-Then using correlation 11-14 for adjustment of viscosity to saturation pressure

·At pressure above p, -First obtain viscosity at Pb from Fig. 11-14

-Then obtain viscosity at pressure above Pb from Fig. 11-15

I:.

5


Lecture #15

Chapter 12 - Gas-Liquid Equilibria

Ideal behavior

·Ideal gas

-Molecular interactions are zero

-Molecules have no volume

·Idealliquid solution

-There is no chemical interactions due to mixing

-Molecular forces are the same regardless of molecular species

-Volumes are additive

Solving ...

·Calculation of behavior of hydrocarbon mixtures in two phase region

-Dew point

-Bubble point

-Quantities and compositions of

gas and liquid in two phase region

·Prediction of reservoir fluid behavior and optimization of processing conditions at surface

Ideal behavior models in gasliquid equilibrium

·Raoult's equation

Pj: partial pressure

Xi mole fraction in liquid P'.j: vapor pressure

·Dalton's equation

Pi =YiPl~ J

Pi partial pressure

Yi mole fraction in gas Pvi system pressure

1

Ideal behavior models in gasliquid equilibrium

·Resulting equation

YJ = P'f Xl P

·For a two-component mixture

nil x]=--

~

n,

nil +ng] z]=-n, +ng

Dew point pressure in ideal gasliquid system

·System at Pd and a given T

P=Pd

YiP = XiPvj ~ ZiPd=XiP',i

·Dew point pressure evaluation

Here

·Example 12-3

Bubble point pressure in ideal gas-liquid system

·System at Pb and a given T

P=Pb ,. >

·Bubble point pressure evaluation

Here

Z. = n/i +ngi

J n/ +ng

·Example 12-2

Composition and quantity of equilibrium gas and liquid in ideal system

·System of equations -Equilibrium equation

-Material balance equation

r __ n/_ )1-

n/ +ng

2


·System of equations LXj = L z,

i 11+fg(;-IJ

by replacing

Or

by replacing

Limitations of model in ideal gas-liquid system

·Ideal gas (Dalton's equation) ·Ideal liquid (Raoult's equation) ·Conditions with temperature below the critical temperatures of any component in mixture


• Trial-and-error method ·See Example 12-1

3


Lecture #16

Chapter 12 - Gas-Liquid Equilibria

Re-Cap of Lecture 15 Ideal gas-liquid system -Systern of equations

Or

Re-Cap of Lecture 15

Ideal gas-liquid system -Equilibriurn equation

-Bubble point pressure

r, = L ZiPVj J

-Dew point pressure 1

Pd==~~L...zi I e; j

Real solution system

K- factor (equilibrium ratio)

Yj = P'i :Xj P

k = Yj •• !.&:.

.I :Xj P

L ,

kj is function p, T and composition and can be obtained from appendix A

1

Composition and quantity of equilibrium gas and liquid in real system

~e/1\\

f\

Bubble point in real solution system

.,,= 1, at P=Pb z.

2:>J= L J =1

j jl+.0Uj-1J

·Example 12-6 (see spreadsheet) for

Composition and quantity of equilibrium gas and liquid in real system

·Example 12-4 (see spreadsheet)

Dew point in real solution system

·fg= 1, at P=Pd LXj=L1+/(k_lrl

} J g }

".[> LZj / k, = 1

J

2

Gas-liquid equilibrium conditions

·Mixture: liquid

2>jkj <1 X -::~.

j ~'

·Mixture: gas

·Mixture: gas and liquid two phases

2>jk; > 1 and

3


Lecture #17

Chapter 13 - Surface Separation

Re-Cap of Lecture 16 Real gas-liquid system -Bubble point

-Dew point L:>jlkj=1

I

Re-Cap of Lecture 16

Real gas-liquid system -Equilibriurn ratio

k=YI

} XI

-Systern of equations 2:xl = 2: 1+ /(k -If 1

J ) g )

Or

"y=" z, =1

L.,J L., (1 J

j j 1+J;lkj-1

Surface separation system

Two-stage separation

Separator feed

Three-stage separation

1

Separator calculation for black oil

-For a two-stage separator system: one separator and one stock tank

Separator calculation (two-stage) -Exercise (see spreadsheet)

Separator calculation (two-stage)

-Formation Volume Factor

B - MoRPSTO

ob - M STO PoR fu fL2

Separator calculation for volatile oil and retrograde gas

-At least three-stage separation system: two separators and one stock tank

2

Separator calculation (three-stage)

·Total Gas-Oil Ratio

·Formation Volume Factor

B MoRPSTO

ob MSTOPoRfUfL2fLJ

3

r

1/,.1 <;; 6,~o~,

(' 1('~1 :

{

,,$.c~·-'

'S'"1(


Lecture #18

Chapter 14 - Equilibrium-Ratio Correlations

Behavior of K-factor -K-tactors plotted against pressure on log-log scale

10

100 1000 10000

Pressure, psia

Equilibrium ratios for a crude oil-natural gas mixture

Pressure, psia

Equilibrium ratio - K-factor

-Kfactor is influenced by

-Pressure

-Temperature

-Types and quantities of

components in mixture

-Converqence pressure

-K-factor is a function of

pressure, temperature and convergence pressure

Behavior of K-factor

-At low pressure: ideal-solution behavior

-Slope is approximately -1

-K-value is unity at pressure

close to Pvj at T of interest

-At high pressure: non idealsolution behavior

-Curves tend to converge toward K-value of 1

Convergence pressure

·Definition: pressure at which kfactors appear to converge to unity

-For black oil: 10,000 psia

-For volatile oil: 5000-10,000 psia

-For retrograde gas: 5,000 psia

-For wet gas: 5,000 psia

Estimation of convergence pressure

·Convergence pressure is estimated iteratively

·Procedure is lengthy and tedious

·Interpolation may be needed between charts

Convergence pressure

·At true critical T of mixture, convergence pressure is the critical p

·Convergence pressure has little effect on k-factors at low pressure

-k-factor correlation with convergence pressure of 5000 psia can be used in separator calculations

·k-factors is sensitive to convergence pressure at pressure close to convergence pressure

EXAMPLE 14-1

! SOlution!

Step 1: convert mole fraction of liquid composition into weight fraction

EXAMPLE 14-1

! SOlution!

Step 3: calculate weighted-average critical pressure and temperature for hypothetical heavier component (C2+)

Composition Critical Critical

exCluding Cit temperature, pressure.,

weight fraction "ll psla

~~~ !'L !-'L.. w,T.. _ __!?g_ wiP.,

54950 9,9 m6,S 12,7

665,64 9,4 616_0 K7

734,()4

16,7 436,9

EXAMPLE 14-1:

! SOlution!

Step 2: separate liquid components to form a pseudo-binary (two-component) mixture:

1, Lightest component: C1

2_ Hypothetical heavier component: C2+ (Note: weight fraction of C2+ needs to be adjusted)

EXAMPLE 14-1 ! SOlution!

Step 4: plot two critical points on Fig_ 14-3 (convergence pressure locus, binary critical locus)

1_ C1: Pc=666A psia, Tc=-116,67 of 2, C2+: Pc=274 psia, Tc=837 of

EXAMPLE 14-1

~

~terpolate convergence pressure locus using adjacent critical locus as guide

EXAMPLE 14-1

~

~d convergence pressure at 160 of: 10,000 psia

Step 7: redo gas-liquid equilibrium calculation based on k-factor at convergence pressure of 10,000 psia

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Petroleum Property /Phase Behavior

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Petroleum Property /Phase Behavior

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PNGE 332 - Spring 2010