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G P A TP-8 82 3824699 O O L L L L 2 ô27 I

Technical Publication
TP-8

The Solubility of Carbon Dioxide in


Propylene Carbonate at Elevated Pressures
& Higher Than Ambient Temperatures

Philip David Mantor


Osmar Abib, Jr.
Kyoo Y. Song
and
Riki Kobayashi
Rice University
Houston, Texas
July, 1982

Gas
Pro c e s s o r s
Association 1812 First Place Tulsa, Okla. 74103 Phone: 918/582-5112

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GPA TP-8 82 3824699 O O L L L L 3 763 W

FOREWORD

The experimental investigation summarized in the ensuing report was


not sponsored nor financed by GPA, hence, the information is issued as a
Technical Publication (TP-8) rather than our conventional Research Report.
Physical solvents are commonly used in the gas processing industry for
bulk removal of carbon dioxide from natural gas streams to render them salable.
Several of the solvents are associated with proprietary processes, investigation
of which GPA has historically avoided. The data reported herein represent a
portion of unpublished work contained in an M.S. thesis of P. D. Mantor at Rice
University.
GPA wishes to thank Mr. Mantor, Dr. Kobayashi, Rice University, Brown
and Root Inc., and Dow Chemical who provided student support and technical
help for permission to publish this information.
GPA TP-8 82 3 8 2 4 b 9 9 0011114 bTT

TABLE OF CONTENTS

Page
Foreword i
Author's Introduction 1
Experimental Results 1
Experimental Detail ir
Apparatus 4
Reagents 7
Procedure 7
Acknowledgement 9
Glossary 10
Literature Cited 11

LIST OF TABLES

Table I. Experimental and Predicted Solubility of


Carbon Dioxide in Propylene Carbonate 2

Table II. Henry's Law Constants and Partial Molar


Volumes of Carbon Dioxide in Propylene
Carbonate . .. .. . .. .. . 3

LIST OF FIGURES

Figure 1. Isothermal Solubility of Carbon Dioxide in


Propylene Carbonate versus Pressure 5
Figure 2. A Schematic Diagram of the Experimental
Apparatus .. .. . .. . . . 6

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G P A TP-8 82 3824699 O O L L L L 5 536

AUTHOR'S INTRODUCTION

The solubility of carbon dioxide in propylene carbonate at


elevated pressures and higher than ambient temperatures may assume
increasing significance for the processing of carbon dioxide-rich
gases issuing from natural reservoirs and/or carbon dioxide enhanced
oil processing streams.

Despite the fact that propylene carbonate has been used as


solvent for its selective absorption of carbon dioxide from natural
gases, the solubility data for carbon dioxide in propylene carbonate
are highly restricted with respect to pressure (Rivas & Prausnitz,
19791, with respect to accuracy (Kaplan et al., 1971), and/or with
respect to the number of isotherms studied (Isaacs et al., 1977).

Data on the solubility of carbon dioxide in propylene carbonate


are accordingly presented for several isotherms to cover reasonable
processing pressures and temperatures.

EXPERIMENTAL RESULTS

Four isotherms describing the solubility of carbon dioxide in


propylene carbonate were measured at 26.7OC, 37.80C1 71.loC, and 104.4OC
for pressures as high as 68 atmospheres. At 8OoF, the upper experi-
mental pressure was limited to the vicinity of the vapor pressure of
carbon dioxide (Table I). The data were "thermodynamically correlated"
employing the Krichevsky-Kasarnovsky solubility equation to give an
average deviation from the experimental of 1.03 percent (Table I). The
analysis provided both Henry's Law Constants and partial molar volumes
of the dissolved carbon dioxide (Table II). The experimental results

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G P A TP-8 82 3 8 2 4 6 9 9 O O L L L L b 472 =

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G P A TP-8 8 2 U 3824677 O O L L L L 7 309

Table II. Henry's Law Constants and P a r t i a l Molar Volumes of Carbon


Dioxide i n Propylene Carbonate.

T Henry ' s Law Constant P a r t i a l Molar


(OC/OF) atm. Volume (cc/g-mol)

25 / 77 81.13/ 82.80' -
26.7 / 80 81.7 .
-0 06786

37.8 / 100 101.7 -0,04762

40 / 104 . .
103 5/116 5a/112 7b .
50 / 122 120 .8/123 .'1

70 / 158 166 .Ob -


71.1 / 160 159.4 -0.01000

75 / 167 169.8
100 / 212 222.3/220.6C/265a/257.3b

104.4/ 220 227.8 O. 02273

a. Reference (2)
b. Reference (4)
c. Reference (1)

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G P A TP-ô ô 2 I3824677 O O L l L L ô 245

are presented graphically in Figure 1, showing carbon dioxide solu-


bility as high as 0.588mol fraction at the highest pressure and lowest
temperature of this experimental study.

EXPERIMENTAL DETAILS

Apparatus & Procedure

Figure 2 shows the schematic diagram of the experimental apparatus,


which consisted of a rocking equilibrium cell, a pressure maintenance
arrangement, and an analytical train.

The equilibrium apparatus consisted of a high pressure windowed


cell (rated to hold pressures up to 650 atm. pressure) surrounded
by a constant temperature air bath capable of holding the temperature
to within O.OSOC of the selected temperature. The gas charging line
was connected to the top of the cell and the liquid sampling line
connected to the center of the cell.

The constant temperature was maintained in the bath by electrical


heating coils installed in the air stream. The temperature of the cell
was measured by a calibrated copper-constant thermocouple connected to
a Leeds & Northrup precision portable potentiometer. The cell pressure
was measured by a calibrated 2000 psi Heise gauge whose calibration
showed an accuracy of 0.1% of full scale reading.

A gas cylinder, a gas reservoir, and a mercury displacement pump


were used to add or subtract gas to or from the system and to maintain
the equilibrium pressure during sampling.

The analytical train consisted of a gas/liquid burette which also


seryed as a flash chamber. A manometer was used to measure the sample
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GPA TP-8 82 3 8 2 4 6 9 9 O O L L L L S 181
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GPA TP-8 8 2 I3 8 2 4 6 9 9 O O L L 1 2 0 9T3 I

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G P A TP-8 82 3824677 O O L L L 2 L ô3T

pressure. A spherical chamber of predetermined volume was used to


collect the major portion of the flash gas. The tubing connections

were made with India rubber tubing impregnated with paraffin wax.
The known volumes, the burette volume and the volume of the spherical
flask were used to calibrate the volume of the irregular portions of
the analytical train by the gas expansion method.

Reaaents

Carbon dioxide of 99.6 mol % purity was purchased from


Spencer Chemical Company and used without further purification. The

propylene carbonate was obtained from Jefferson. Chemical Company


with a minimum stated purity of 99 weight % .
Procedure

The equilibrium gas sample was bubbled through two gas absorption
chambers which were placed in series containing distilled water. The

amount of propylene carbonate in the gas phase was found to be less


than 0.001 mol fraction at all conditions covered by the measurements.

The liquid sample was taken after flushing the sample tubing with
approximately 5 ml. of the equilibrium liquid phase. The analytical

train was then evacuated and checked for leaks. The sampling valve was
opened just enough to allow the liquid to flash into the burette at
760 m. Hg pressure. The temperature of the reactor jacket surrounding
the gas burette was recorded during and after the sampling period until
the pressure settled to a steady value.

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G P A TP-8 82 3824699 O O L L L 2 2 7 7 b =

Remarks

Carbon dioxide exhibits a high solubility in propylene carbonate,


showing a composition of 58.8 mol % COs in the liquid phase at 26.7OC
and 54.8 atm. As the temperature increased to 104.4OC, the solu-
bility decreased to 0.18 mol % at a comparable pressure.

The experimental data were studied using the Krichevsky-Kasarnovsky


solubility equation (1935), given as follows:

where fo = fugacity of pure carbon dioxide in the vapor,


V1

x1 = the mol fraction of carbon dioxide in the liquid,

K1 = Henry's law constant for that temperature,

t
-
v = the partial molar volume of dissolved carbon dioxide
in the liquid phase, assumed to be a constant,

P = the system pressure,

P2 = the pure propylene carbonate vapor pressure (usually


negligible) ,

R = gas constant, and

T = the absolute temperature of the system.

The values of log (fo


Vl/Xl
) versus ( P - P2)/2.303 RT, when plotted,
showed essential linearity and gave values of the slope and an intercept
at various temperatures. The intercept at P2 is equal to the Henry's
Law constant at that temperature. The slope (equal to ci> were
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GPA TP-8 82 = 3824b99 0011123 602

negative, probably the result of interstitial solubility and strong


attraction between CO2 and the organic carbonate structure.

Table I presents the agreement between the "thermodynamically


consistent" and experimental solubility data to an average deviation
of 1.03 percent. The agreement with high solubility region of carbon
dioxide in propylene carbonate was unexpected in view of the known
capability of the Krichevsky-Kasarnovsky equation (1935) .
The Henry's Law constants, determined from this work, showed good
agreement with the literature values obtained from lower pressure
solubility data at coincidental temperatures, as shown in Table II.

ACKNOWLEDGEMENT

The a u t h o r s acknowledge t h e s u p p o r t of Brown & Root I n c . f o r t h e i r


f i n a n c i a l s u p p o r t of t h e p r o j e c t and Dow Chemical Company f o r t h e i r s u p p o r t
i n a n a l y z i n g t h e d a t a and f i n a l p r e p a r a t i o n of t h e paper.

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G P A TP-8 8 2 E 3 8 2 4 6 7 9 001l1124 549 I

Glossary

f fugacity, atm
K Henry's law constant, atm
P Pressure, atm
R gas constant
T temperature, absolute
-
V
3
partial molar volume, cm /g-mol
x mole fraction in liquid phase

Scripts

1 component 1, carbon dioxide


2 component 2, propylene carbonate
vl vapor state of component 1

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GPA TP-8 82 3824699 0011125 485 I

LITERATURE CITED

1. Rivas, O. R.; Prausnitz, J. M., A.1.Ch.E. J., 25, 975 (1979).


2. Isaacs, E. E.; Otto, F . D.; Mather, A. E., J. Can. C h m . Eng.,
55, 751 (1977).
3. Krichevsky, I. R.; Kasarnovsky, J. S . , J. Am. Chem. Soc., 57,
2168 (1935).
4. Zubchenko, Yu. P.; Shakhova, S . F.; Wei, T.; Titellman, L. I.;
Kaplan, L. K., Prikladnoi Khimii, 4 4 ( 9 ) , 2044 (1971).

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