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25-1

Nomenclature

Ki = equilibrium ratio, yi/xi P* =

L = ratio of moles of liquid to moles of total R =

mixture

N = mole fraction in the total mixture or system T =

ω = acentric factor V =

Subscripts i =

KEY

= Example calculation from the book

= Application worksheet for user to fill out

= Numbers that must be filled in according to the user's data and specific situation (also includes numbers

vapor pressure, psia

universal gas constant,

(psia · cu ft)/(lbmole · °R)

temperature, °R or °F

pressure

mole fraction of component I in the liquid

phase

mole fraction of component I in the vapor

phase

component

Example 25-1 -- Binary System Calculation

Component 2 Ethane = 40 lb moles

Temperature = -125 °F

Pressure = 50 psia

How many moles are in the vapor phase and how many in the liquid phase?

K1 = 10 Page 25-10

K2 = 0.35 Page 25-10

K1 = y1/x1 = 10

K2 = y2/x2 = 0.35

For a binary system, x1 + x2 = 1 and y1 + y2 = 1, so

(1-y1)/(1-x1) = 0.35 and (1-y2)/(1-x2) = 10

x1 = 0.0674

y1 = 0.674

x2 = 0.9326

y2 = 0.326

To find the amount of vapor in the mixture, let v denote the number of lb moles of vapor.

Summing the moles of Methane in each phase gives:

S lb moles for component 1 + 2 = 100 lb moles

x1 + y1 = 60 lb moles

(y1 * v) + (x1 * [100 - v]) = 60 lb moles

v = 87.9

The mixture consists of:

Vapor = 87.9 lb moles

Liquid = 12.1 lb moles

The sample calculations, equations and spreadsheets presented herein were developed using examples published in the Engine

While every effort has been made to present accurate and reliable technical information and calculation spreadsheets based on

The Calculation Spreadsheets are provided without warranty of any kind including warranties of accuracy or reasonableness of

In no event will the GPA or GPSA and their members be liable for any damages whatsoever (including without limitation, thos

These calculation spreadsheets are provided to provide an “Operational level” of accuracy calculation based on rather broad as

Application 25-1 -- Binary System Calculation

Component 2 Ethane = 40 lb moles

Temperature = -125 °F

Pressure = 50 psia

How many moles are in the vapor phase and how many in the liquid phase?

K1 = 10 Page 25-10

K2 = 0.35 Page 25-10

K1 = y1/x1 = 10

K2 = y2/x2 = 0.35

For a binary system, x1 + x2 = 1 and y1 + y2 = 1, so

(1-y1)/(1-x1) = 0.35 and (1-y2)/(1-x2) = 10

x1 = 0.0674

y1 = 0.674

x2 = 0.9326

y2 = 0.326

To find the amount of vapor in the mixture, let v denote the number of lb moles of vapor.

Summing the moles of Methane in each phase gives:

S lb moles for component 1 + 2 = 100 lb moles

x1 + y1 = 60 lb moles

(y1 * v) + (x1 * [100 - v]) = 60 lb moles

Therefore, v = 87.9

The mixture consists of:

Vapor = 87.9 lb moles

Liquid = 12.1 lb moles

examples published in the Engineering Data Book as published by the Gas Processor Suppliers Association as a service to the gas processin

calculation spreadsheets based on the GPSA Engineering Data Book sample calculations, the use of such information is voluntary and the G

s of accuracy or reasonableness of factual or scientific assumptions, studies or conclusions, or merchantability, fitness for a particular purpo

(including without limitation, those resulting from lost profits, lost data or business interruption) arising from the use, inability to , referenc

lculation based on rather broad assumptions (including but not limited to; temperatures, pressures, compositions, imperial curves, site cond

n as a service to the gas processing industry. All information and calculation formulae has been compiled and edited in cooperation with G

nformation is voluntary and the GPA and GPSA do not guarantee the accuracy, completeness, efficacy or timeliness of such information. R

bility, fitness for a particular purpose or non-infringement of intellectual property.

om the use, inability to , reference to or reliance on the information in thes Publication, whether based on warranty, contract, tort or any oth

sitions, imperial curves, site conditions etc) and do not replace detailed and accurate Design Engineering taking into account actual process

ted in cooperation with Gas Processors Association (GPA).

ss of such information. Reference herein to any specific commercial product, calculation method, process, or service by trade-name, tradem

y, contract, tort or any other legal theory and whether or not advised of the possibility of such damages.

nto account actual process conditions, fluid properties, equipment condition or fowling and actual control set-point dead-band limitations.

vice by trade-name, trademark, and service mark manufacturer or otherwise does not constitute or imply endorsement, recommendation or f

t dead-band limitations.

ent, recommendation or favoring by the GPA and/or GPSA.

Example 25-2 -- Flash Calculation

A typical high pressure separator gas is cooled to liquefy heavier hydrocarbons prior to cooling to a lower temperature where t

components would freeze out as solids.

Temperature = -20 °F

Pressure = 600 psia

What is the ratio of moles of liquid to the moles of the total mixture under these conditions?

Solution Steps

The feed gas composition is given in Column 1. The flash equation, 25-5, is solved for three estimated values of L as shown in

Columns 3, estimated

By plotting 4, and 5. values of L versus calculated Sum(xi), the correct value of L where Sum(xi) = 1.00 is L = 0.03. This sol

entered into Cell I17 and then whose solution is shown in columns 6 and 7. The gas composition is then calculated using yi =

Column 8.

This 'correct' value is used for purposes of illustration. It is not a completely converged solution, for xi = 1.000478 and yi =

0.999985, columns 7 and 8. This error may be too large for some applications.

[Note: The trial values used for L should bracket S(Ni/(L+VKi) [Calculated Total] = 1.00. If not, chose different values. When

have three acceptable values, please enter them in numerical order in Cells D20 - E20 in order to have unidirectional line in th

below. This will assist identifying the value of L where the line crosses S(xi) = 1.00.]

Column

1 2 3 4 5 6

Component Final value of L from plot

Feed Pk = Trial values of L (note: V + L = 1) =

below =

Composition

2000 0.02 0.04 0.06

L+VKi

Ni Ki*** Ni/(L+VKi) Ni/(L+VKi) Ni/(L+VKi)

C1 0.9010 3.7 0.24712 0.25084 0.25466 3.61900

CO2** 0.0106 1.23 0.00864 0.00867 0.00870 1.22472

C2 0.0499 0.41 0.11830 0.11508 0.11203 0.42770

C3 0.0187 0.082 0.18633 0.15751 0.13642 0.10954

iC4 0.0065 0.034 0.12191 0.08948 0.07068 0.06298

nC4 0.0045 0.023 0.10578 0.07249 0.05513 0.05231

iC5 0.0017 0.0085 0.06001 0.03530 0.02500 0.03825

nC5 0.0019 0.0058 0.07398 0.04170 0.02903 0.03563

C6 0.0029 0.0014 0.13569 0.07014 0.04730 0.03136

C7* 0.0023 0.00028 0.11344 0.05712 0.03817 0.03027

TOTALS 1.0000 1.17120 0.89833 0.77713

C7* 0.00042

C8 0.00014

* C7+ = average of nC7 + nC8 properties

** KCO2 = sq.rt (KC1 · KC2)

*** Ki values used above and in Fig. 25-3 are found in the K-Data Charts at the end of Chapter 25. These data are for P k = 30

psia although the charts specifies Pk = 2000 psia. The pressures refer to convergence pressure, P k, of the charts from the Tenth

Edition of this data book. They should not be used for design work or related activities. Again, their retention in this edition i

illustration and approximation purposes only; however, they can be very useful in such a role. The critical locus chart used in

convergence pressure method has also be retained (Fig. 25-8).

1.40000

1.20000

1.00000

Calculated Totals

0.80000

0.60000

0.40000

0.20000

0.00000

0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05 0.055 0.06 0.065

Trial Values of L

NOTE: The table above reverses columns 4 and 5 compared to Fig. 25-3 in the 13th Edition Data Book. This was done to eas

plotting and interpolation between the two trial values of L.

The sample calculations, equations and spreadsheets presented herein were developed using examples published in the Engine

While every effort has been made to present accurate and reliable technical information and calculation spreadsheets based on

The Calculation Spreadsheets are provided without warranty of any kind including warranties of accuracy or reasonableness of

In no event will the GPA or GPSA and their members be liable for any damages whatsoever (including without limitation, thos

These calculation spreadsheets are provided to provide an “Operational level” of accuracy calculation based on rather broad as

Application 25-2 -- Flash Calculation

Temperature = -125

Pressure = 600

What is the ratio of moles of liquid to the moles of the total mixture under these cond

Solution Steps

e estimated values of L as shown in The feed gas composition is given in Column 1. The flash equation, 25-5, is solved fo

um(xi) = 1.00 is L = 0.03. This solution is Columns 3, estimated

By plotting 4, and 5. values of L versus calculated Sum(xi), the correct value of L w

sition is then calculated using yi = Kixi in entered into Cell I17 and then whose solution is shown in columns 6 and 7. The gas c

Column 8.

ution, for xi = 1.000478 and yi = This 'correct' value is used for purposes of illustration. It is not a completely converg

0.999985, columns 7 and 8. This error may be too large for some applications.

f not, chose different values. When you [Note: The trial values used for L should bracket S(Ni/(L+VKi) [Calculated Total] = 1

der to have unidirectional line in the plot have three acceptable values, please enter them in numerical order in Cells D20 - E20

below. This will assist identifying the value of L where the line crosses S(xi) = 1.00.]

Column

7 8 1 2 3

Final value of L from plot Component

0.030 Feed Pk = Trial values of L (note: V + L = 1) =

below =

Composition

Liquid Vapor 3000 0.02

xi = Ni/

(L+VKi) yi Ni Ki Ni/(L+VKi)

0.24896 0.92117 C1 0.9010 3.7 0.24712

0.00866 0.01066 CO2** 0.0106 1.23 0.00864

0.11667 0.04783 C2 0.0499 0.41 0.11830

0.17071 0.01400 C3 0.0187 0.082 0.18633

0.10321 0.00351 iC4 0.0065 0.034 0.12191

0.08603 0.00198 nC4 0.0045 0.023 0.10578

0.04445 0.00038 iC5 0.0017 0.0085 0.06001

0.05333 0.00031 nC5 0.0019 0.0058 0.07398

0.09248 0.00013 C6 0.0029 0.0014 0.13569

0.07598 0.00002 C7* 0.0023 0.00028 0.11344

1.00048 0.99999 TOTALS 1.0000 1.17120

C7* 0.00042

C8 0.00014

* C7+ = average of nC7 + nC8 properties

** KCO2 = sq.rt (KC1 · KC2)

ure, P k, of the charts from the Tenth

ain, their retention in this edition is for

e. The critical locus chart used in the

1.40000

1.20000

1.00000

Calculated Totals

0.80000

0.60000

0.40000

0.20000

0.00000

0.045 0.05 0.055 0.06 0.065

0.015 0.02 0.025 0.03 0.035

Trial Valu

examples published in the Engineering Data Book as published by the Gas Processor Suppliers Association as a service to the gas processi

calculation spreadsheets based on the GPSA Engineering Data Book sample calculations, the use of such information is voluntary and the G

es of accuracy or reasonableness of factual or scientific assumptions, studies or conclusions, or merchantability, fitness for a particular purp

(including without limitation, those resulting from lost profits, lost data or business interruption) arising from the use, inability to , referenc

alculation based on rather broad assumptions (including but not limited to; temperatures, pressures, compositions, imperial curves, site con

°F

psia

1. The flash equation, 25-5, is solved for three estimated values of L as shown in

ated Sum(xi), the correct value of L where Sum(xi) = 1.00 is L = 0.03. This solution is

s shown in columns 6 and 7. The gas composition is then calculated using yi = Kixi in

e too large for some applications.

et S(Ni/(L+VKi) [Calculated Total] = 1.00. If not, chose different values. When you

in numerical order in Cells D20 - E20 in order to have unidirectional line in the plot

L where the line crosses S(xi) = 1.00.]

Column

4 5 6 7 8

Final value of L from plot

Trial values of L (note: V + L = 1) = 0.030

below =

0.04 0.06 Liquid Vapor

L+VKi xi = Ni/

Ni/(L+VKi) Ni/(L+VKi) (L+VKi) yi

0.25084 0.25466 3.61900 0.24896 0.92117

0.00867 0.00870 1.22472 0.00866 0.01066

0.11508 0.11203 0.42770 0.11667 0.04783

0.15751 0.13642 0.10954 0.17071 0.01400

0.08948 0.07068 0.06298 0.10321 0.00351

0.07249 0.05513 0.05231 0.08603 0.00198

0.03530 0.02500 0.03825 0.04445 0.00038

0.04170 0.02903 0.03563 0.05333 0.00031

0.07014 0.04730 0.03136 0.09248 0.00013

0.05712 0.03817 0.03027 0.07598 0.00002

0.89833 0.77713 1.00048 0.99999

1.40000

1.20000

1.00000

0.80000

0.60000

0.40000

0.20000

0.00000

0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05 0.055 0.06 0.065

Trial Values of L

ciation as a service to the gas processing industry. All information and calculation formulae has been compiled and edited in cooperation w

such information is voluntary and the GPA and GPSA do not guarantee the accuracy, completeness, efficacy or timeliness of such informati

hantability, fitness for a particular purpose or non-infringement of intellectual property.

ing from the use, inability to , reference to or reliance on the information in thes Publication, whether based on warranty, contract, tort or an

ompositions, imperial curves, site conditions etc) and do not replace detailed and accurate Design Engineering taking into account actual pr

been compiled and edited in cooperation with Gas Processors Association (GPA).

s, efficacy or timeliness of such information. Reference herein to any specific commercial product, calculation method, process, or service

ther based on warranty, contract, tort or any other legal theory and whether or not advised of the possibility of such damages.

Engineering taking into account actual process conditions, fluid properties, equipment condition or fowling and actual control set-point de

method, process, or service by trade-name, trademark, and service mark manufacturer or otherwise does not constitute or imply endorsemen

uch damages.

d actual control set-point dead-band limitations.

itute or imply endorsement, recommendation or favoring by the GPA and/or GPSA.

Example 25-3 -- Dew Point Calculation Application 25-3 -- Dew Point Cal

A gas stream is being cooled in a heat exchanger. The initial conditions are: A gas stream is being cooled in a he

Pressure = 800 psia Pressure

Find the temperature at which the gas starts to condense. (Dew Point) Find the temperature at which the g

The equation for dew point conditions (SNi/Ki = 1.0) is solved for two The equation for dew point conditio

estimated dew point temperatures. By interpolation, the temperature at which estimated dew point temperatures.

Ni/Ki = 1.00 is estimated below. Ni/Ki = 1.00 is estimated below.

[Note: The trial values used for dew point temperature should bracket [Note: The trial values used for dew

S(Ni/Ki) = 1.00. If not, chose different values.] S(Ni/Ki) = 1.00. If not, chose diffe

Column

1 2 3 4 5

Feed Pk = 1000 Pk = 1000

-50 °F -40 °F

Ni Ki Ni/Ki Ki Ni/Ki

CH4 0.854 2.25 0.380 2.3 0.371 CH4

CO2* 0.051 0.787 0.065 0.844 0.060 CO2*

C3H8 0.032 0.092 0.348 0.105 0.305 C3H8

S= 1.000 1.021 0.940 S=

Note that the heaviest component is quite important in dew point calculations. Note that the heaviest component is

For more complex mixtures, the characterization of the heavy fraction as a For more complex mixtures, the cha

pseudocomponent such as hexane or octane will have a significant effect on pseudocomponent such as hexane o

dew point calculations. dew point calculations.

NOTE: Table 25-4 in the 13th edition is reproduced below:

The reason for Ni/Ki differences between this table and the one above is not

known.

Column

1 2 3 4 5

Feed Pk = 1000 Pk = 1000

-50 °F -40 °F

Ni Ki Ni/Ki Ki Ni/Ki

CH4 0.854 2.25 0.313 2.3 0.311

CO2* 0.051 0.787 0.059 0.844 0.056

C2H6 0.063 0.275 0.229 0.31 0.210

C3H8 0.032 0.092 0.457 0.105 0.400

S= 1.000 1.058 0.977

Note that the heaviest component is quite important in dew point calculations.

For more complex mixtures, the characterization of the heavy fraction as a

pseudocomponent such as hexane or octane will have a significant effect on

dew point calculations.

The sample calculations, equations and spreadsheets presented herein were developed using examples published in the Engine

While every effort has been made to present accurate and reliable technical information and calculation spreadsheets based on

The Calculation Spreadsheets are provided without warranty of any kind including warranties of accuracy or reasonableness of

In no event will the GPA or GPSA and their members be liable for any damages whatsoever (including without limitation, thos

These calculation spreadsheets are provided to provide an “Operational level” of accuracy calculation based on rather broad as

on 25-3 -- Dew Point Calculation

= 100 °F

= 800 psia

ion for dew point conditions (SNi/Ki = 1.0) is solved for two

dew point temperatures. By interpolation, the temperature at which

00 is estimated below.

= 1.00. If not, chose different values.]

Column

1 2 3 4 5

Feed Pk = 1000 Pk = 1000

-50 °F -40 °F

Ni Ki Ni/Ki Ki Ni/Ki

0.854 2.25 0.380 2.3 0.371

0.051 0.787 0.065 0.844 0.060

0.032 0.092 0.348 0.105 0.305

1.000 1.021 0.940

complex mixtures, the characterization of the heavy fraction as a

mponent such as hexane or octane will have a significant effect on

calculations.

s published in the Engineering Data Book as published by the Gas Processor Suppliers Association as a service to the gas processing indust

on spreadsheets based on the GPSA Engineering Data Book sample calculations, the use of such information is voluntary and the GPA and

uracy or reasonableness of factual or scientific assumptions, studies or conclusions, or merchantability, fitness for a particular purpose or no

ng without limitation, those resulting from lost profits, lost data or business interruption) arising from the use, inability to , reference to or re

n based on rather broad assumptions (including but not limited to; temperatures, pressures, compositions, imperial curves, site conditions et

to the gas processing industry. All information and calculation formulae has been compiled and edited in cooperation with Gas Processors A

voluntary and the GPA and GPSA do not guarantee the accuracy, completeness, efficacy or timeliness of such information. Reference herei

or a particular purpose or non-infringement of intellectual property.

ability to , reference to or reliance on the information in thes Publication, whether based on warranty, contract, tort or any other legal theory

ial curves, site conditions etc) and do not replace detailed and accurate Design Engineering taking into account actual process conditions, fl

tion with Gas Processors Association (GPA).

rmation. Reference herein to any specific commercial product, calculation method, process, or service by trade-name, trademark, and serv

t or any other legal theory and whether or not advised of the possibility of such damages.

ual process conditions, fluid properties, equipment condition or fowling and actual control set-point dead-band limitations.

ame, trademark, and service mark manufacturer or otherwise does not constitute or imply endorsement, recommendation or favoring by the

ndation or favoring by the GPA and/or GPSA.

These charts show the vapor-liquid equilibrium ratio, Ki, for use in example and approximate

flash calculations. The charts do not give accurate answers, particularly in the case of

nitrogen. They are included only for illustrative purposes and to support example flash

calculations and quick estimation of K-values in other hand calculations. These charts should

not be used in design calculations.

Previous editions of this data book presented extensive sets of K-data based upon the GPA

Convergence Pressure, Pk, method. A component’s K-data is a strong function of temperature

and pressure and a weaker function of composition. The convergence pressure method

recognizes composition effects in predicting K-data. The convergence pressure technique can

be used in hand calculations, and it is still available as computer correlations for K-data

prediction.

Availability of computers, coupled with the more refined Kvalue correlations in modern process

simulators, has made the previous GPA convergence pressure charts outdated. Complete sets of

these charts are available from GPA as a Technical Paper, TP-22.

For example 25-2, Ki values used and in Fig. 25-3 are found in the K-Data Charts at the end of

Chapter 25. These data are for Pk = 3000 psia although the charts specifies Pk = 2000 psia.

The pressures refer to convergence pressure, P k, of the charts from the Tenth Edition of this

data book. They should not be used for design work or related activities. Again, their

retention in this edition is for illustration and approximation purposes only; however, they can

be very useful in such a role. The critical locus chart used in the convergence pressure method

has also be retained (Fig. 25-8).

For example 25-3, note that the heaviest component is quite important in dew point

calculations. For more complex mixtures, the characterization of the heavy fraction as a

pseudocomponent such as hexane or octane will have a significant effect on dew point

calculations.

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