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Manual of Petroleum Measurement Standards Chapter 11—Physical Properties Data

Section 2, Part 5—A Simplified Vapor Pressure Correlation for Commercial NGLs

ASTM Technical Publication [Stock No. PETROLTBL-TP15] GPA Technical Publication TP-15

SEPTEMBER 2007

REAFFIRMED, AUGUST 2012

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Manual of Petroleum Measurement Standards Chapter 11—Physical Properties Data

Section 2, Part 5—A Simplified Vapor Pressure Correlation for Commercial NGLs

ASTM Technical Publication [Stock No. PETROLTBL-TP15] GPA Technical Publication TP-15

Measurement Coordination

SEPTEMBER 2007

REAFFIRMED, AUGUST 2012

Prepared for

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Foreword

The purpose of this procedure is to provide a simplified means of estimating equilibrium vapor pressures of various natural gas liquids (NGLs) from a knowledge of the fluid’s relative density (60°F/60°F) and process temperature. The intended application of this procedure is to provide the values of P e (equilibrium vapor pressure) required to determine the pressure effect contributions to volume correction factors as specified in the American Petroleum Institute Manual of Petroleum Measurement Standards (MPMS) Chapter 11.1-2004 [1] (which superseded Chapter 11.2.1-1984 [2] ) and Chapter 11.2.2 [3] . It is realized that other equations of state are currently in use for specific custody transfer applications and that such methods will continue to be used as acceptable for both buyer and seller.

This procedure is applicable to four major classifications of petroleum fluid mixtures:

commercial propanes, commercial butanes, natural gasolines, and light end fluids.The latter consists of EP mixes and high ethane content fluids. It covers the relative density range of 0.350 to 0.675 over a temperature range of –50°F through 140°F. This procedure is an extension of GPA Technical Publication TP-15 (1988) [9] /API MPMS Addendum to Chapter 11.2.2-1994 [4] to include light end fluids in the relative density range of 0.350 to 0.490.

Variations from the computed vapor pressures to the actual values are to be expected because of the infinite number of possible compositions that can result in the same relative density product. Representative and extreme compositions were selected to develop the correlations, but it is realized that additional streams with compositions from among the infinite potential may well behave differently. This potential for variation is especially true at relative densities in the neighborhood of 0.500. For example, at a relative density of 0.505 the fluid could be propane or Y-grade mix, each having significantly different compositions and vapor pressure behaviors.

As is always the case in correlations published for custody transfer and settlement purposes, additional accuracy may be obtained by developing a modified correlation for certain specific applications if agreed to by all contracting parties. An equation to improve the accuracy of the generalized correlation at 100°F is also included.

It is important to note that the application of the correlations presented in this document to conditions or fluids not specified, will result in untested and unknown results which could contain significant errors.

Nothing contained in any API publication is to be construed as granting any right, by implication or otherwise, for the manufacture, sale, or use of any method, apparatus, or product covered by letters patent. Neither should anything contained in the publication be construed as insuring anyone against liability for infringement of letters patent.

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procedures

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developmental

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designated as an API standard. Questions concerning the interpretation of the content of this publication or comments and questions concerning the procedures under which this publication was developed should be directed in writing to the Director of Standards, American Petroleum Institute, 1220 L Street, N.W., Washington, D.C. 20005. Requests for permission to reproduce or translate all or any part of the material published herein should also be addressed to the director.

Generally, API standards are reviewed and revised, reaffirmed, or withdrawn at least every five years. A one-time extension of up to two years may be added to this review cycle. Status of the publication can be ascertained from the API Standards Department, telephone (202) 682-8000. A catalog of API publications and materials is published annually and updated quarterly by API, 1220 L Street, N.W., Washington, D.C. 20005.

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API Special Notes

API publications necessarily address problems of a general nature. With respect to particular circumstances, local, state, and federal laws and regulations should be reviewed.

Neither API nor any of API's employees, subcontractors, consultants, committees, or other assignees make any warranty or representation, either express or implied, with respect to the accuracy, completeness, or usefulness of the information contained herein, or assume any liability or responsibility for any use, or the results of such use, of any information or process disclosed in this publication. Neither API nor any of API's employees, subcontractors, consultants, or other assignees represent that use of this publication would not infringe upon privately owned rights.

API publications may be used by anyone desiring to do so. This publication is an updated version of MPMS Addendum to Chapter 11.2.2. Previous editions of this publication were numbered MPMS Addendum to Chapter 11.2.2. Users of this standard should take efforts to ensure they are using the most current version of this publication. Every effort has been made by the Institute to assure the accuracy and reliability of the data contained in them; however, the Institute makes no representation, warranty, or guarantee in connection with this publication and hereby expressly disclaims any liability or responsibility for loss or damage resulting from its use or for the violation of any authorities having jurisdiction with which this publication may conflict.

API publications are published to facilitate the broad availability of proven, sound engineering and operating practices. These publications are not intended to obviate the need for applying sound engineering judgment regarding when and where these publications should be utilized. The formulation and publication of API publications is not intended in any way to inhibit anyone from using any other practices.

Any manufacturer marking equipment or materials in conformance with the marking requirements of an API standard is solely responsible for complying with all the applicable requirements of that standard. API does not represent, warrant, or guarantee that such products do in fact conform to the applicable API standard.

All rights reserved. No part of this work may be reproduced, stored in a retrieval system, or transmitted by any means, electronic, mechanical, photocopying, recording, or otherwise, without prior written permission from the publisher.

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ASTM Note

This publication does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this publication to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

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GPA Disclaimer

Neither the GPA nor any person acting on behalf of the GPA makes any warranty, guarantee, or representation, express or implied, with respect to the accuracy, completeness, or usefulness of the information contained in this report. The GPA hereby expressly disclaims any liability or responsibility for loss or damage resulting from the use of any apparatus, method, or process disclosed in this report; and for the infringement of any patent or the violation of any federal, state, or municipal law or regulation arising from the use of, any information, apparatus, method, or process disclosed in this report.

All rights reserved. No part of this work may be reproduced, stored in a retrieval system, or transmitted by any means, electronic, mechanical, photocopying, recording, or otherwise, without prior written permission from the publisher.

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Table of Contents

Foreword

ii

API Special Notes

iii

ASTM Note

v

GPA Disclaimer

vi

Table of Contents

vii

List of Tables

viii

List of Figures

viii

0 Implementation Guidelines

1

1 Background

1

2 Vapor Pressure Correlation for Commercial NGLs

2

3 Correlation Development

3

 

3.1 Propanes

7

3.1.1 Product Specifications

7

3.1.2 Data Collection

8

3.1.3 Data Regression

8

3.1.4 Error Analysis

8

3.2

Butanes

11

3.2.1 Product Specifications

11

3.2.2 Data Collection

11

3.2.3 Data Regression

12

3.2.4 Error Analysis

12

3.3 Natural Gasolines

15

3.3.1 Product Specifications

15

3.3.2 Data Collection

15

3.3.3 Data Regression

17

3.3.4 Error Analysis

17

3.4 Light Ends

19

3.4.1 Product Specifications

19

3.4.2 Data Collection and Validation

20

3.4.3 Data Regression

22

3.4.4 Error Analysis

25

4 Ad Hoc Improvement of the Correlation For Specific Situations

25

5 List of References

26

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List of Tables

Table 1: Parameters for Vapor Pressure Correlation (Use in Equation 2)

3

Table 2: GPA Liquefied Petroleum Gas Specifications: GPA Standard 2140-88 [7]

7

Table 3:

Correlation Parameters for Propanes and Butanes

9

Table 4: SRK Interaction Parameters for Propanes and Butanes

9

Table 5:

Compositions and Relative Densities of Propane Samples

9

Table 6:

Comparison of Vapor Pressure Correlations for Commercial Propanes

10

Table 7: Compositions and Relative Densities of Butane Samples Data Regression

12

Table 8:

Comparison of Vapor Pressure Correlations for Commercial Butanes

13

Table 9: GPA Standard 3132-84, “Natural Gasoline Specifications and Test Methods”

15

Table 10: Grades of Natural Gasoline as specified by the GPA

15

Table 11: Correlation Constants for Natural Gasolines

16

Table 12:

SRK Interaction Parameters for Natural Gasolines

16

Table 13:

Compositions and Relative Densities of Natural Gasolines

17

Table 14: Comparison of Vapor Pressure Correlations for Natural Gasolines

18

Table 15: Compositions of Components Used to Generate Data for Light Ends Correlation

21

Table 16: Representative Comparison of Vapor Pressures Obtained from HYSYS with those from NGLCALC 22 Table 17: Representative Comparison Between HYSYS SRK Vapor Pressures and Vapor Pressures from

23

the Correlation for Light End Fluids

List of Figures

Figure 1: Vapor Pressures from Correlations………………………………………………………………5

Figure 2: “A” Parameter (Equation 2 & Table 1)…… ……………………………………………………6

Figure 3: “B” Parameter (Equation 2 & Table 1) …………………………………………………….…

6

Figure 4: Maximum Temperature vs Relative Density……………………………………………… ….21

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A Simplified Vapor Pressure Correlation for Commercial NGLs

0 Implementation Guidelines

This Revised Standard/Technical Publication is effective upon the date of publication and supersedes all previous revisions of the Standard/Technical Publication and API MPMS 11.2.2A/GPA TP-15. However, due to the nature of the changes in this Revised Standard/Technical Publication and the fact that it is or may be incorporated by reference in various regulations, it is recognized that guidance concerning an implementation period may be needed in order to avoid disruptions within the industry and ensure proper application. As a result, it is recommended that this Revised Standard/Technical Publication be utilized on all new and existing applications no later than TWO YEARS after the publication date. An application, for this purpose, is defined as the point where the calculation is applied.

Once the Revised Standard/Technical Publication is implemented in a particular application, the Previous Standard/Technical Publication will no longer be used in that application.

However, the use of API standards and ASTM and GPA technical publications remains voluntary and the decision on when to utilize a standard/technical publication is an issue that is subject to the negotiations between the parties involved in the transaction.

1 Background

The transfer of ownership of liquids is usually based on the volume of liquid at agreed upon standard conditions, usually 60°F for the U.S. customary system of units and the greater of one atmosphere pressure or the equilibrium vapor pressure of the liquid. Actual measurement of the liquid volumes and the their associated densities occurs at flowing or process conditions. Thus these measurements must be converted to equivalent values at the standard conditions. Once the liquid densities are converted, the conversion of the volumes becomes a trivial exercise. Densities are normally converted from measured conditions to standard conditions by equations of the form:

γ 60 = F t × F p × γ

Where:

Equation 1

γ 60

Relative Density at 60°F and the greater of one atmosphere pressure or the equilibrium vapor pressure of the liquid

γ

Relative Density at measured conditions

F t

Correction factor for temperature effects

F p

Correction factor for pressure effects

Two methods used for calculation of the

Institute: MPMS Chapter 11.2.1-1984 [2] (now superseded by Chapter 11.1-2004 [1] ) and MPMS Chapter 11.2.2-1986 [3] . These methods require a knowledge of the equilibrium bubble point pressure (vapor pressure) at the measured conditions. However, the vapor pressure of the process liquid is generally not measured. The vapor pressure can also be calculated from compositional information, but the composition is not always measured for natural gas liquids, NGLs.

F p

term were standardized by the American Petroleum

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2

A SIMPLIFIED VAPOR PRESSURE CORRELATION FOR COMMERCIAL NGLS

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Therefore, a correlation for the vapor pressure of NGLs based upon normally measured properties is required.

A simple vapor pressure correlation which requires only the vapor pressure at 100°F was developed by Hillburn (1968) [13] . This was developed primarily for use with commercial propanes, but it has been applied to other NGLs. The correlation seems to work fairly well for propane mixtures, but does not work at all well for natural gasolines. Another limitation is that it requires the 100°F vapor pressure value which is sometimes measured to meet transportation regulation requirements, but not always measured in other industrial situations. In addition, the correlation can predict negative absolute vapor pressures. The problems and limitations of the Hillburn correlation and the desire for a less empirical correlation form prompted a project to develop an alternative correlation based only on the relative density, a value that is always measured. That project resulted in the publication of GPA Technical Publication TP-15 (1988) [10] /API MPMS Addendum to Chapter 11.2.2-1994 [4] .

GPA TP-15 (1988)/API MPMS Addendum to Chapter 11.2.2-1994 covered the density range ranging from that of commercial HD-5 propane through 12-14 psia natural gasoline (0.490 to 0.676) over a temperature range of –50°F to 140°F. In May 2000, the API authorized a project to extend the range of GPA TP-15 (1988)/API MPMS Addendum to Chapter 11.2.2-1994 from the lower relative density value of 0.490 to a new low of 0.350. The entire correlation, 1988 and present, is presented in Section 2.0 of this report. The discussion of the 1988 development for each of the three generic products (propanes, butanes, and natural gasolines) is presented in Section 3.0, subsections 3.1 through 3.3. The discussion of the extension is presented in Section 3.0, subsection 3.4, of this document. An equation to improve the accuracy of the generalized correlation at 100°F is also included as Section 4.0 of this document.

2 Vapor Pressure Correlation for Commercial NGLs

Equation 2 is of the same Antoine form as in GPA TP-15 (1988)/API MPMS Addendum to Chapter 11.2.2-1994 except it contains quadratic terms in relative density. The quadratic terms were added to best fit the low density range with as few discrete breaks as possible. Zero values for the quadratic parameters in the relative density range of 0.490 through 0.676, as shown in Table 1, allow Equation 2 to collapse to the identical equation reported in GPA TP-15 (1988)/ API MPMS Addendum to Chapter 11.2.2-1994.

(

ln P

)

=

A

+

B

(

t

+

C

)

A = A 0 + (A 1 × γ 60 ) + (A 2 × γ 60 2 )

B = B 0 + (B 1 × γ 60 ) + (B 2 × γ 60 2 )

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Equation 2

A SIMPLIFIED VAPOR PRESSURE CORRELATION FOR COMMERCIAL NGLS

3

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Where:

P

Vapor pressure at t (psia)

t

Temperature (°F)

γ 60

Relative density (60°F/60°F)

C

A universal constant for all ranges. C = 443.0 (°F)

A 0 , A 1 , A 2 B 0 , B 1 , B 2

Parameters for Equation 2. Values vary with correlation range and are given in Table 1.

Table 1: Parameters for Vapor Pressure Correlation (Use in Equation 2)

 

Range

 

A

0

A

1

A

2

B

0

B

1

B

2

0.350

γ 60 < 0.450

17.5297

–24.604

24.373

–6567.6

19322.0

–24693.3

0.450

γ 60 < 0.490

7.9907

7.562

0.0

1895.5

–10596.9

0.0

0.490

γ 60 < 0.510

–6.4747

37.083

0.0

12038.0

–31296.5

0.0

0.510

γ 60 < 0.560

11.5454

1.749

0.0

1378.8

–10396.1

0.0

0.560

γ 60 < 0.585

6.4827

10.790

0.0

3721.5

–14579.5

0.0

0.585

γ 60 < 0.625

6.5412

10.690

0.0

6514.5

–19353.9

0.0

0.625

γ 60

0.676

20.8537

–12.210

0.0

–6765.6

1894.3

0.0

Notes

1. Range Limits: –50°F t 140°F for 0.425 γ 60 0.676 –50°F t [(695.51 × γ 60 ) – 155.51]°F for 0.350 γ 60 0.425

See Section 3.4.2.2 for a discussion of temperature/relative density limits.

2. The first and second density range are results of the present extension.

The remaining ranges are from GPA TP-15 (1988)/API MPMS Addendum to Chapter 11.2.2-

1994.

3 Correlation Development

Since the vapor pressure curve for a mixture has a shape very similar to a pure component vapor pressure curve at low to moderate pressures, the correlation in GPA TP-15 (1988)/API MPMS Addendum to Chapter 11.2.2-1994 was developed around the simplest pure component vapor pressure model that could reproduce experimental vapor pressure data reasonably well. After the

review of several candidate models, the Antoine vapor pressure model (Reid, et al. 1977 [16] ) was chosen. The same general model was applied to the present extension, however quadratic terms in relative density were added to best fit the low density range with as few discrete breaks as possible. The parameters for the 0.490 to 0.676 relative density range are identical to those published in GPA TP-15 (1988)/API MPMS Addendum to Chapter 11.2.2-1994. In both the original and present work, the overall approach to the model development involved:

1)

regressing vapor pressure data (pressure, temperature points) at each relative density to

2)

obtain parameters specific to that relative density, then cross-correlating these parameters with relative density to obtain the general model presented

in Equation 2, Section 2.0. Table 1 lists the parameters obtained for the correlation in each of its applicable ranges. Figure 1 shows vapor pressures predicted by the new correlation at several key temperatures over the

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A SIMPLIFIED VAPOR PRESSURE CORRELATION FOR COMMERCIAL NGLS

relative density range of the model. Figures 2 and 3 present the “A” and “B” parameters and shows the discrete breaks over the entire relative density range.

For the development of GPA TP-15 (1988)/API MPMS Addendum to Chapter 11.2.2-1994, it was agreed that the vapor pressure data would be generated from the Soave-Redlich-Kwong (SRK) equation of state (Soave, 1972 [17] ), and that densities would be generated from the COSTALD correlation (Hankinson, et al., 1979 [11] and Thomson, et al., 1982 [18] ) using parameters from the Phillips Thermophysical Data System (Embry, 1985) [7] . It was necessary to modify the values of the acentric factors used with the SRK in order to match the 100°F vapor pressures to the desired accuracy. The values of the pure component parameters used are listed in Table 3. Volume percent compositions were converted to molar compositions using the γ 60 values. The binary interaction parameters used for the SRK are shown in Table 4.

The present work was performed on commercial software, HYSYS.Process 2.1 [14] , with the special parameters loaded as customized input.

The COSTALD correlation has been shown by Thomson, et al. (1982) [19] , to give accurate NGL densities, of the order of ± 0.2%. A specially modified version of the correlation has been developed for LNGs (Hankinson, et al., 1982 [12] ), but was not applicable to this work.

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A SIMPLIFIED VAPOR PRESSURE CORRELATION FOR COMMERCIAL NGLS

5

--`,,```,,,,````-`-`,,`,,`,`,,`---

Figure 1. Vapor Pressures from Correlations

1000.0000 100.0000 10.0000 1.0000 0.1000 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 Pressure,
1000.0000
100.0000
10.0000
1.0000
0.1000
0.3
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
Pressure, psia

Relative Density (60 °F /60 °F)

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-50F 0F 60F 100F 140F
-50F
0F
60F
100F
140F

6

A SIMPLIFIED VAPOR PRESSURE CORRELATION FOR COMMERCIAL NGLS

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Figure 2. "A" Parameter (Equation 2 & Table 1)

13.5 13 12.5 12 11.5 11 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 "A"
13.5
13
12.5
12
11.5
11
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
"A" Parameter

Relative Density (60 °F /60 °F)

Figure 3. "B" Parameter (Equation 2 & Table 1)

-6000 -5500 -5000 -4500 -4000 -3500 -3000 -2500 -2000 0.35 0.4 0.45 0.5 0.55 0.6
-6000
-5500
-5000
-4500
-4000
-3500
-3000
-2500
-2000
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
"B" Parameter

Relative Density (60 °F /60 °F)

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A SIMPLIFIED VAPOR PRESSURE CORRELATION FOR COMMERCIAL NGLS

7

Table 2: GPA Liquefied Petroleum Gas Specifications: GPA Standard 2140-88 [8]

 

Commercial

Commercial

Commercial

   

Product Characteristics

Propane

Butane

B-P Mixtures

Propane HD-5

Test Methods

     

Predominantly

Not less than 90 liquid volume percent propane; not more than 5 liquid volume percent propylene

 

mixtures of

Composition

Predominantly

propane and/or

propylene

Predominantly

butanes and/or

butylenes

butanes and/or

butylenes with

propane and/or

ASTM

D2163-82

propylene

Vapor Pressure at 100°F, psig, maximum

       

ASTM

208

70

208

208

D1267-84

Temperature at 95% evaporation, °F, maximum

       

ASTM

–37

36

36

–37

D1837-86

Butane or heavier, liquid volume %, maximum

       

ASTM

2.5

2.5

D2163-82

Pentane or heavier, liquid volume % maximum

       

ASTM

2.0

2.0

D2163-82

Residue on evaporation of 100 mL, maximum

       

ASTM

0.05 mL

0.05 mL

D2158-85

         

ASTM

Oil stain observation

Pass (1)

Pass (1)

D2158-85

Corrosion, copper strip, maximum

       

ASTM

No.1

No. 1

No. 1

No.1

D1838-84

         

ASTM

Total sulfur, ppmw

185

140

140

123

D2784-80

         

GPA Propane

Dryness Test

Moisture content

Pass

Pass

(Cobalt

Bromide) or

     

ASTM

D2713-86

Free water content

none

none

Note: An acceptable product shall not yield a persistent oil ring when 0.3 mL of solvent residue mixture is added to a filter paper in 0.1 increments and examined in daylight after 2 minutes as described in ASTM D2158.

3.1 Propanes

3.1.1 Product Specifications

Product specifications from GPA Standard 2140-88 [8] , “Liquefied Petroleum Product Gas Specifications and Test Methods”, given in Table 2, were used for correlation development.

Although the presence of olefins is allowed by the specifications, it was assumed that no olefins were present since they generally have a much higher market value and would be preferentially recovered. During the course of the correlation development, it became apparent that a propane

mix having a relative density of 0.490 or 0.495 could not meet these specifications. This fact was

later proven by experimental measurements (Parrish, 1987 [15] ). Since several member companies

wanted the correlation to apply to propane mixes having relative densities of 0.490 and 0.495, it

was agreed that for these cases, the 100°F vapor pressure specification would be relaxed in order to obtain the desired relative density range.

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A SIMPLIFIED VAPOR PRESSURE CORRELATION FOR COMMERCIAL NGLS

--`,,```,,,,````-`-`

3.1.2 Data Collection

The compositions of several propane samples which met the product specifications at relative densities of 0.490, 0.495, 0.500, 0.505, and 0.510 were calculated through the process of trial and error. It was found there was enough leeway in the specifications that it was possible to generate more than one composition that would meet them at each relative density. Compositions that were representative of each relative density range were selected.

Vapor pressure data was generated from the SRK for each relative density case over the entire temperature range of –50°F to 140°F in 10° increments. This step provided twenty vapor pressure points for each case, for a total of 160 points.

3.1.3 Data Regression

For the purposes of data regression, a single set of vapor pressure data was selected at each relative density. Only the “representative” vapor pressure data were used in the data regression. These compositions are given in Table 5.

Regression of the generated vapor pressure data was performed in three steps:

1)

Regression of each relative density sample individually to Equation 2.

2)

Regression of A and B as linear functions of relative density.

3)

Regression of all samples simultaneously to the correlation equation (Equation 2).

Step 1 regression of the samples individually yielded fits of the data having a maximum error of 1.0% and an average absolute error of 0.3% over the entire temperature range. A residual plot did not show any significant systematic variations so the correlation form was accepted without any further investigation.

At this point, several different values of C were tried to see if the maximum and average errors could be reduced. There was no significant reduction of error, so the value of C was “frozen” at the reported value of 443°F for all further regression analyses.

Plots of the A and B values determined by the individual regressions as functions of relative density showed an almost linear dependence. Residual plots from the linear regressions of the A and B values showed some systematic variation, but addition of higher order relative density terms neither improved the fit nor removed the systematic deviations. Therefore, the linear dependence was chosen.

This analysis yielded the correlation form given in Equation 2 when all quadratic terms were set to zero. This form was then used to regress all of the propane data.

3.1.4 Error Analysis

For the data included in the regression analysis, the maximum error was 3.9% and the average absolute error was 0.8%. When checked against all of the data rather than just the “representative” data, the correlation had a maximum error of 7.8%, an average absolute error of 1.8% and a bias of –0.2%.

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A SIMPLIFIED VAPOR PRESSURE CORRELATION FOR COMMERCIAL NGLS

9

Comparison of the new correlation to the Hillburn correlation for the propanes shows that the new correlation is superior. Table 6 gives a summary comparison of the new correlation and the old, Hillburn, correlation at selected points for each of the samples. At most temperatures the new correlation is superior.

Table 3: Correlation Parameters for Propanes and Butanes

 

Critical Temperature T c (°F)

Critical Pressure P c (psia)

 

Standard

Costald

 

Acentric

SRK

Parameter

Density (lb/ft 3 )

Component

factors

Acentric

 

V*

factors

(cm

3 /mol)

 

Ethane

90.09

707.80

0.0983

0.0983

 

145.80

22.23

Propane

206.01

616.30

0.1667

0.1532

 

200.10

31.66

n-Butane

305.65

550.70

0.2008

0.2008

 

254.40

36.45

i-Butane

274.98

529.10

0.1867

0.1825

 

256.80

35.12

n-Pentane

385.70

488.60

0.2522

0.2522

 

311.30

39.35

Table 4: SRK Interaction Parameters for Propanes and Butanes

   

Component j

Component i

Ethane

Propane

n-Butane

i-Butane

n-Pentane

Ethane

0.0

0.002

0.005

0.0

0.007

Propane

0.002

0.0

0.0

0.0

0.003

n-Butane

0.005

0.0

0.0

0.0

0.0

i-Butane

0.0

0.0

0.0

0.0

0.0

n-Pentane

0.007

0.003

0.0

0.0

0.0

Table 5: Compositions and Relative Densities of Propane Samples

   

(60°F/60°F)

 

Volume Percent of Component

 

Case Name

Relative

Density

Ethane

Propane

n-Butane

i-Butane

n-Pentane

0.490

Hi V.P.

0.49000

20.00

77.50

2.45

0.00

0.05

0.490

Lo V.P.

0.49000

17.70

82.30

0.00

0.00

0.00

0.495

Hi V.P.

0.49500

15.20

82.30

2.45

0.00

0.05

0.495

Lo V.P.

0.49500

12.73

87.27

0.00

0.00

0.00

0.500

HD-5

0.50036

7.35

92.65

0.00

0.00

0.00

0.505

Hi V.P.

0.50500

4.81

92.69

2.45

0.00

0.05

0.505

Lo V.P.

0.50500

2.36

97.64

0.00

0.00

0.00

0.510

HD-5

0.50950

0.00

97.50

2.45

0.00

0.05

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Not for Resale

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A SIMPLIFIED VAPOR PRESSURE CORRELATION FOR COMMERCIAL NGLS

--`,,```,,,,````-`-`,,`,,`,`,,`---

Table 6: Comparison of Vapor Pressure Correlations for Commercial Propanes – Continued on next page

 

Relative Density

     

Pressure (psia)

GPA TP-15 (1988)/API MPMS Addendum to Chapter 11.2.2-1994

Hillburn Correlation

Case Name

(60°F/60°F)

Temperature

 

SRK Vapor

Vapor

Pressure

Percent

Vapor

Pressure

Percent

(°F)

(psia)

Error

(psia)

Error

     

–50

26.87

27.27

–1.51

11.64

56.66

 

0

68.92

70.30

–2.00

64.30

6.70

“Representative”

0.4900

 

60

168.58

170.83

–1.34

160.00

5.09

0.490

   

100

275.84

276.87

–0.37

275.84

0.00

 

140

423.16

419.97

0.75

437.18

–3.31

     

–50

26.05

27.27

–4.70

11.42

56.17

 

0

67.27

70.30

–4.51

63.37

5.80

0.490

Hi V.P.

0.4900

 

60

165.63

170.83

–3.14

157.78

4.74

   

100

272.08

276.87

–1.76

272.08

0.00

 

140

418.97

419.97

–0.24

431.25

–2.93

     

–50

27.74

27.27

1.67

11.88

57.18

 

0

70.66

70.30

0.50

65.26

7.64

0.490

Lo V.P.

0.4900

 

60

171.63

170.83

0.47

162.27

5.45

   

100

279.71

276.87

1.02

279.71

0.00

 

140

427.43

419.97

1.74

443.27

–3.71

     

–50

22.92

22.05

3.81

10.22

55.39

 

0

60.49

59.44

1.73

58.47

3.33

“Representative”

0.4950

 

60

151.94

150.65

0.85

146.15

3.81

0.495

   

100

252.29

249.83

0.97

252.29

0.00

 

140

392.21

386.52

1.45

400.11

–2.01

     

–50

22.05

22.05

0.03

9.98

54.75

 

0

58.72

59.44

–1.22

57.46

2.15

0.495

Hi V.P.

0.4950

 

60

148.78

150.65

–1.26

143.75

3.38

   

100

248.21

249.83

–0.65

248.21

0.00

 

140

387.57

386.52

0.27

393.69

–1.58

     

–50

23.86

22.05

7.60

10.48

56.08

 

0

62.36

59.44

4.67

59.52

4.55

0.495

Lo V.P.

0.4950

 

60

155.24

150.65

2.96

148.63

4.26

   

100

256.51

249.83

2.60

256.51

0.00

 

140

396.97

386.52

2.63

406.75

–2.46

     

–50

17.73

17.58

0.83

8.44

52.37

 

0

49.52

49.72

–0.40

51.16

–3.30

0.500

HD-5

0.5003

 

60

130.76

131.80

–0.79

128.78

1.52

   

100

222.75

223.96

–0.54

222.75

0.00

 

140

354.10

353.86

0.07

353.61

0.14

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A SIMPLIFIED VAPOR PRESSURE CORRELATION FOR COMMERCIAL NGLS

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--`,,```,,,,````-`-`,,`,,`,`,,`---

Table 6: (Concluded) Comparison of Vapor Pressure Correlations for Commercial Propanes

 

Relative Density

     

GPA TP-15 (1988)/API MPMS Addendum to Chapter 11.2.2-1994

Hillburn Correlation

Case Name

(60°F/60°F)

Temperature

 

SRK Vapor

Pressure

 

Vapor

Pressure

Percent

Error

Vapor

Pressure

Percent

Error

(°F)

(psia)

(psia)

(psia)

     

–50

 

14.54

14.41

0.95

7.28

49.97

 

0

 

42.72

42.49

0.53

46.36

–8.53

“Representative”

0.5050

 

60

117.25

117.17

0.06

117.39

–0.12

0.505

   

100

203.38

203.42

–0.02

203.38

0.00

 

140

327.99

327.41

0.18

323.13

1.48

     

–50

 

15.47

14.41

6.91

7.52

51.42

 

0

 

44.54

42.49

4.59

47.36

–6.33

0.505

Hi V.P.

0.5050

 

60

120.41

117.17

2.69

119.75

0.54

   

100

207.40

203.42

1.92

207.40

0.00

 

140

332.54

327.41

1.54

329.46

0.93

     

–50

 

13.72

14.41

–5.02

7.04

48.66

 

0

 

41.04

42.49

–3.54

45.41

–10.63

0.505

Lo V.P

0.5050

 

60

114.25

117.17

–2.56

115.12

–0.76

   

100

199.51

203.42

–1.96

199.51

0.00

 

140

323.56

327.41

–1.19

317.05

2.01

     

–50

 

11.59

11.89

–2.59

6.18

46.73

 

0

 

36.36

36.54

–0.50

41.85

–15.10

0.510

HD-5

0.5095

 

60

104.54

104.64

–0.09

106.67

–2.04

   

100

185.14

185.45

–0.17

185.14

0.00

 

140

303.35

303.84

–0.16

294.43

2.94

Average Percent Error

   

0.12

 

3.90

Average Absolute Percent Error

   

1.76

 

7.13

Maximum Percent Error

   

7.60

 

57.18

3.2

Butanes

3.2.1

Product Specifications

Specifications given by the Gas Processors Association for butanes are shown in Table 2. For the purposes of correlation development, two classes of commercial butane were used. All correlation development was based around the following butanes products:

A normal butane product having at least 96.5 volume percent n-butane and containing no more than 3.5 volume percent i-butane

An i-butane product having at least 95.5 volume percent i-butane and containing no more than 4.5 volume percent normal butane or 2.5 volume percent propane

3.2.2 Data Collection

The same general data collection techniques used for the propanes were used for the butanes. The SRK parameters used in the data point generation are shown in Table 3 and Table 4.

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A SIMPLIFIED VAPOR PRESSURE CORRELATION FOR COMMERCIAL NGLS

--`,,```,,,,````-`-`,,`,,`,`,,`---

A different approach for generating the compositions was used for the butanes products than was used for the propanes. Five different compositions were used for each product:

1)

A low vapor pressure case containing the maximum allowable pentanes.

2)

A low vapor pressure case containing the minimum amount of the primary component and no

3)

lights. A pure component case.

4)

A high vapor pressure case containing the minimum amount of the primary component and

5)

no heavies. A typical commercial product composition supplied by one of the member companies.

These compositions are given in Table 7. Vapor pressure data for each case was generated at 10° temperature increments over the range of –50°F to 140°F.

Table 7: Compositions and Relative Densities of Butane Samples Data Regression

   

(60°F/60°F)

 

Volume Percent of Component

 

Case Name

Relative

Density

Ethane

Propane

n-Butane

i-Butane

n-Pentane

i-C4 Lo V.P. -1

0.5643

0.00

0.00

0.00

98.00

2.00

i-C4 Lo V.P. -2

0.5639

0.00

0.00

4.50

95.50

0.00

i-C4 Pure

0.5628

0.00

0.00

0.00

100.00

0.00

i-C4 Hi V.P.

0.5616

0.00

2.50

0.00

97.50

0.00

i-C4 Koch

0.5624

0.00

1.70

1.50

96.80

0.00

n-C4 Lo V.P. -1

0.5854

0.00

0.00

98.00

0.00

2.00

n-C4 Lo V.P. -2

0.5852

0.00

0.00

98.50

0.00

1.50

n-C4 Pure

0.5844

0.00

0.00

100.00

0.00

0.00

n_C4 Hi V.P.

0.5837

0.00

0.00

96.50

3.50

0.00

n-C4 Koch

0.5843

0.00

0.00

97.50

2.00

0.50

3.2.3 Data Regression

The butane data were fit using the same procedure used for the propanes except that no “representative” data were generated.

3.2.4 Error Analysis

The average absolute error for each case fit individually was 2.7%. The fit of all data to the final butanes correlation resulted in an average absolute error of 1.1% and a maximum error of 4.5%.

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A SIMPLIFIED VAPOR PRESSURE CORRELATION FOR COMMERCIAL NGLS

13

--`,,```,,,,````-

Comparison of the new correlation to the Hillburn correlation for the butanes shows that the new correlation is superior. Table 8 gives a summary comparison of the new correlation and the Hillburn correlation at selected points for each of the samples. At most temperatures the new correlation is superior.

Table 8: Comparison of Vapor Pressure Correlations for Commercial Butanes – Continued on next page

 

Relative Density

   

SRK Vapor Pressure (psia)

GPA TP-15 (1988)/ API MPMS Addendum to Chapter 11.2.2-1994

Hillburn Correlation

Case Name

(60°F/60°F)

Temperature

 

Vapor

Pressure

Percent

Error

Vapor

Pressure

Percent

Error

(°F)

(psia)

(psia)

     

–50

3.26

3.25

0.40

–0.42

112.98

 

0

12.01

11.71

2.50

14.74

–22.74

i-C 4 Hi V.P.

0.5616

 

60

39.77

38.98

1.99

42.30

–6.36

 

100

75.66

74.97

0.91

75.66

0.00

 

140

131.43

131.82

–0.30

122.12

7.08

     

–50

3.16

3.18

–0.61

–0.50

115.89

 

0

11.71

11.50

1.76

14.42

–23.12

i-C 4 Koch

0.5624

 

60

38.99