R&D NOTE

Solubilities of Carbon Dioxide in Polyethylene

Glycol Ethers
Amr Henni1*, Paitoon Tontiwachwuthikul1 and Amit Chakma2
1. Department of Industrial Systems Engineering, University of Regina, Regina, SK, Canada S4S 0A2
2. Department of Chemical Engineering, University of Waterloo, London, ON, Canada N2L 3G1

New extensive data are reported for the solubility of carbon dioxide in fourteen physical solvents, and compared to two other solvents widely
used in industry (selexol® and sulfolane). The solubility data are expressed by Henry’s law constants and have been measured at 25 °C, 40 °C
and 60 °C, using an Autoclave cell. The study concludes that polyethylene glycol dimethyl ethers, and mixtures of these solvents are the best
solvents for CO2 removal.

Les valeurs de la solubilité du dioxide de carbone dans quatorze solvants physiques sont reportées. Ces valeurs sont comparées avec la solubilté
du dyoxide de carbone dans le sulfolane et le selexol®. Les solubilités sont exprimées par les constantes de la loi d’Henry dans quatorze solvants
et à des temperatures de 25 °C, 40 °C et 60 °C. L’étude conclue que les polyetylène-glycol dimetyleters et leurs mélanges sont les plus perform-
ants pour la décarbonatation du gaz.

Keywords: gas solubility, Henry’s law constant, physical solvent, gas sweetening

K
nowledge of the solubility of carbon dioxide in polar
solvent is important both industrially and for the develop-
ment of theories of solution. Recently, several processes
have been developed for the removal of acid gases from natural
gas. The removal of carbon dioxide from gas streams received
increased attention with the implementation of the Kyoto
Protocol in many countries. Contrary to chemical solvents,
physical solvents are not limited in their absorption capacity by
the stoichiometry of a reaction. This capacity is proportional to
the partial pressure of the acid gas in the stream, which means
lower amounts of circulating solvent. Much lower energy
consumption is required for regeneration compared to chemical
solvents. Physical solvents are also able to absorb mercaptans,
sulfur compounds and other impurities. Although the success of
a solvent based process depends essentially on the identification
of a suitable solvent, there are at present no established quantita-
tive methods to help in choosing the appropriate solvent. Usually
solvents are found by intuition or qualitative screening
procedures, followed by time-consuming laboratory tests (Porter
et al., 1991). There is a great need for methods for preliminary
identification and screening of potential solvents (Macchietto et
al., 1990). Comprehensive screening studies are scarce as they
are both expensive and time consuming. Zawacki et al. (1981)
screened more than 100 physical solvents, and concluded that
n-formyl morpholine (NFM) and tetraethylene glycol dimethyl
ether (TTEGDME) were the most promising in terms of acid gas
removal and hydrocarbon rejection from a typical coal gasifica-
tion stream. In 1997, Krupp Uhde GmbH became the commercial
licensee for the NFM solvent process. TTEGDME is one of a
number of other dimethyl glycol ethers that make selexol, a
popular physical solvent. The selexol process was introduced
over 30 years ago. As of 2002, Universal Oil Products (UOP)
reported the existence of fifty-five selexol units in commercial
service.
In a preliminary literature study, Henni and Mather (1999)
concluded that ethylene glycol ethers are the solvents with the
highest potential for gas sweetening. A solubility program was
initiated to compare the data obtained for fourteen ethylene
glycol ethers available commercially in a pure form to those
industrially successful, such as selexol (a mixture of PEGDME),
NFM, and sulfolane.
Methyl and dimetyl ethers of polyethylene glycols, also
known as methoxypolyethylene glycol and polyglymes, have
been used for over 30 years as physical absorbents for acid gas
or mercaptans removal from natural or synthetic gases.
* Author to whom correspondence may be addressed.
E-mail address: amr.henni@uregina.ca

358 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 83, APRIL 2005
Polyethelene glycol ethers are high molecular weight solvents.
Polyethylene glycol ethers are characterized by low vapor
pressure (high boiling point), miscibility with water and, in
some cases (unfortunately), high viscosities. Most have a low
enthalpy of vaporization that leads to lower desorption energy
consumption. In the case of a mixture of solvents, a high
selectivity of physical solvents to the acid gases over the
hydrocarbon is best achieved by control of solvent polyglyme
distribution, water content, and operating conditions. Sciamanna
and Lynn (1988) measured the solubility of CO2, H2S, propane
and n-butane in five glycol ethers (DEGDME, TEGDME,
TTEGDME, DEGMME, TEGMBE) with an automated gas solubil-
ity measurement and reported the results in the form of Henry’s
law constants at infinite dilution at 25 °C. Sweeney et al. (1988)
reported the solubility of CO2 in DEGDME, TEGDME, and
TTEGDME at 25 °C. Some solubility data of CO2 in glycol ethers
from several sources were collected by Fogg (1992) and
published in the IUPAC Solubility Data Series. Several other
researchers (Sweeney et al., 1988; Porter et al., 1991) reported
values at a temperature close to 25 °C. Porter and Eck (1953)
measured the solubility of CO2 in selexol (patent), as reported by
Macchietto et al. (1990). Xu et al. (1990) measured the solubili-
ties of CO2 in selexol at several temperatures.
EXPERIMENTAL SETUP AND PROCEDURE
The experimental apparatus consists of an Autoclave® glass
reactor cell (Erie, PA, USA). The cell is connected to a water bath
(Cole Parmer, model H-08502-12) maintained at ± 0.04 °C by a
temperature controller (Cole Parmer, model H-01158-65, Anjou,
Québec, Canada). The temperature in the cell was measured by
an Omega thermocouple. The fluid pressure in the cell was
measured with a calibrated digital transducer (PX 800-010GV
and an indicator DP 40 from Omega) with an estimated accuracy
± 0.1% of the scale range (10 psi). The liquid sample line led
from the bottom of the cell to a needle valve.
Prior to the introduction of the fluid, the apparatus was
brought to the desired temperature and purged with nitrogen to
remove traces of oxygen (when necessary the cell was first
heated under deep vacuum to remove any water present). The
solvent was fed by vacuum to the equilibrium cell. The vapour
pressure of the solvent was measured at equilibrium, and then
carbon dioxide was added. In general, the pressure was
maintained at 2-3 psig to allow for the removal of the liquid
sample. To ensure that equilibrium was reached, the mixer was
started and kept in operation for four to eight hours. A liquid
sample of 1 µL was injected in a 5939 series gas chromatograph
(Hewlett-Packard). A 3 m long, 6.35 mm O. D. column packed
with Chromosorb 104 packed column was used. The oven
temperature was programmed to go from 120 °C to 250 °C or
280 °C, depending on the solvent, after the appearance of the
gas peak. The liquid phase was analysed by withdrawing a
sample of approximately 2 g of solution. At least one sample was
mixed with at least 10 grams of 50 wt % aqueous DEA. Care was
taken to ensure that the amount of DEA present was enough to
absorb all the CO2 present in the glass sampler. Depending on
the gas and the amount absorbed, in general, 10 µL of pure
carbon dioxide were injected in the column. Care must be taken
to avoid taking a sample when the mixer is in operation.
Vigorous mixing creates micro size gas bubbles. Solubility
values measured while the mixer was in operation, and the
“micro” gas bubbles present, led to solubility values 20-30 %
higher than when the liquid was allowed to settle for few
seconds after the agitator was turned off. The liquid sample was
VOLUME 83, APRIL 2005
taken from the bottom of the cell. At least three equilibrium
measurements were done and each sample was analysed three
times. The Henry’s law constants reported are the average of the
three equilibrium data points. For most of the systems, the
repeatability of the liquid mole fraction was generally within ±
2 %. The equipment was calibrated by measuring the solubilities
of CO2 in water at 25 °C, 40 °C and 60 °C and in TEGMME at
40 °C and 70 °C. The obtained Henry’s Law values were
compared with the correlation proposed by Carroll et al. (1991),
and experimental data by Henni and Mather (1995). The
measured Henry’s Law constants were less than 2 % (average
absolute error) of the published values.
MATERIALS
Ethylene glycol monomethyl ether (EGMME) was > 99 % pure,
diethylene glycol monomethyl ether (DEGMME) was > 98 %
pure, triethylene glycol monomethyl ether (TEGMME) was > 97
% pure, ethylene glycol dimethyl ether (EGDME) was > 99 %
pure, diethylene glycol dimethyl ether (DEGDME) was > 99 %
pure, triethylene glycol dimethyl ether (TEGDME) was > 98 %
pure, tetraetylene glycol dimethyl ether (TTEGDME) was > 99
% pure, diethylene glycol monoethyl ether (DEGMEE) was 99 %
pure, diethylene glycol diethyl ether (DEGDEE) was > 99 %
pure, ethylene glycol monobutyl ether (EGMBE) was > 98 %
pure, diethylene glycol monobutyl ether (DEGMBE) was 99 %
pure, triethylene glycol monobutyl ether (TEGMBE) was > 70
% pure, polyethylene glycol dimethyl ether 250 (PEGDME 250 )
was > 97 % pure, n-formyl morpholine (NFM) was > 98 %
pure, and sulfolane (TMS) was > 98 % pure. All solvents were
purchased from Fluka except DEGDEE and DEGMEE, which
were purchased from Sigma-Aldrich (Oakville, ON). TTEGDME
and DEGDEE were purchased from Lancaster (Pelham, NH). The
glycol ether solvents are hygroscopic and must be dried before
use. The solvent samples were degassed under vacuum while
being stirred and heated in a fractionator (Buchi, Switzerland).
This procedure reduced the water content in general to less than
about 0.1 wt % as measured by the GC. The degassing was
completed when gas bubbles stopped evolving from the solvent
or when the solvent itself appeared to be boiling. The solvents
were kept under vacuum on molecular sieves.
Figure 1. Solubility of CO2 in Physical solvents.
 EGMBE;  DEGDEE;  NFM;  DEGMBE;  DEGDME;  Sulfolane;
 DEGMEE;  EGDME; • TEGDME;  DEGMME;  TEGMME;
TEGMBE;  EGMME;  Selexol;  PEG250;  TTEGDME.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 359
 Table 1. Henry’s law constant of CO2 in glycol ethers and other promising solvents

Solvents (Acronym, Average boiling points, °C) H (MPa)

25 °C 40°C 60°C
Ethylene glycol monomethyl ether (EGMME, 123) 10.3 10.8 13.9
Diethylene glycol monomethyl ether (DEGMME, 192) 6.4 8.4 10.1
Triethylene glycol monomethyl ether (TEGMME, 122) 6.8 7.7 8.2
Ethylene glycol dimethyl ether (EGDME, 83) 5.5 5.9 7.1
Diethylene glycol dimethyl ether (DEGDME, 162) 4.8 8.2 11.9
Triethylene glycol dimethyl ether (TEGDME, 216) 4.4 6.0 8.9
Tetraethylene glycol dimethyl ether (TTEGDME, 275) 3.0 4.3 6.5
Diethylene glycol monoethyl ether (DEGMEE, 202) 7.7 9.2 10.7
Diethylene glycol diethyl ether (DEGDEE, 185) 4.3 5.4 7.2
Ethylene glycol monobutyl ether (EGMBE, 170) 12.1 13.5 15.7
Diethylene glycol monobutyl ether (DEGMBE, 226) 9.8 11.2 12.8
Triethylene glycol monobutyl ether (TEGMBE, 307) 5.3 6.8 8.2
Polyethelene glycol dimethyl ether (PEGDME250, 250) 3.2 4.3 6.6
N-formyl morpholine (NFM, 240) 9.5 10.8 13.3
Sulfolanea (285) 8.7 11.1 15.8
Selexolb,c 3.6 4.7 6.5
a Jou et al. (1990)
b Xu et al. (1990)
c Schmidt (1997) vapor pressure of 0.00011 kPa at 25 °C

RESULTS AND DISCUSSIONS the best solvents. The solubility increased from EGMME to
The definition of the Henry’s law constant used in this work TEGMME, from DEGMEE to DEGDEE, and from EGMBE to
was TEGMBE. All the solvents are ranked in terms of their increasing
capacity for CO2 absorption in the the legend of figure 1.
P1
H1 = (1)
x1
CONCLUDING REMARKS
Screening studies are expensive and require a long duration of
Henry’s law constant relates the equilibrium mole fraction of
time. This study represents the most comprehensive report on
substance in the liquid phase (x1) to its partial pressure (P1) in
the solubility of CO2 in glycol ethers. Its importance consists in
the gas phase. The solubilities of carbon dioxide in fourteen
the fact that it compares the whole family of commercially
polar solvents were measured at temperatures of 25 °C, 40 °C
available glycol ethers using the same experimental procedure
and 60 °C. The results are presented in Table 1 and plotted in
and calculation technique. The solubility measurements were
Figure 1. The best five solvents in terms of absorption of carbon
done using the same procedure and equipment at low pressures,
dioxide and high boiling points, diethylene, triethylene, tetraeth-
and thus allow a direct comparison based on the same conditions.
ylene glycol of dimethyl ethers, triethelylene glycol monobutyl
The study confirms why some of these solvents are so popular
ether and a commercial mixture of polyethylene glycol of
in gas sweetening. This study presents for the first time a direct
dimethyl ethers (PEGDME 250), were selected and compared to
comparison between the most widely used solvents in the gas
n-formyl morpholine (NFM), a solvent recently promoted as
industry. The results clearly conclude that polyethylene glycols
very promising (Palla and Lee, 1997), sulfolane and selexol, two
dimethyl ethers (DEGDME, TEGDME, TTEGDME) are the best
solvents widely used in the industry.
solvents for CO2 removal. Mixtures of these solvents (PEGDME
The Henry law constants for NFM obtained in this study were
250 and selexol) make also excellent solvents. Widely used in
on average 16 % higher than the values published by Jou et al.
industry, sulfolane and NFM absorb less CO2 than polyethylene
(1989). Jou measured the solubility of CO2 in NFM at high
glycol dimethyl ethers.
pressures. He used the Peng Robinson equation of state to
calculate the fugacities of CO2, and the Krichevsky-Illinskaya
equation to extract Henry’s Law constants. Values of Henry’s ACKNOWLEDGMENTS
Law constants at 25 °C were on average 18 % higher than those
The financial support of the Canada Centre for Mineral and
measured by Sciamanna et al. (1988) for DEGDME, TEGDME,
Energy Technology (CANMET), the International Test Center (U.
TTEGDME and TTEGMBE. Sciamanna used an automated
of Regina), the Natural Sciences and Engineering Research
procedure to make the solubility measurements. The solubilities
Council of Canada (Strategic and Discovery grants), Arctic
of CO2 in PEGDME 250 were identical to those in selexol, and
Container Inc., Saskatchewan Power Corporation, SaskEnergy,
nearly the same as those of TTEGDME for all temperatures. The
Prairie Coal Ltd., Wascana Energy Inc., and Fluor Daniel Inc. is
solubility of CO2 in all the solvents decreased with the increase
gratefully acknowledged.
in temperature. In terms of mole of CO2 per mole of solvent, the
solubility increased with the molecular weight of the solvent
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360 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 83, APRIL 2005
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Manuscript received February 20, 2004; revised manuscript received

August 16, 2004; accepted for publication December 3, 2004.

VOLUME 83, APRIL 2005 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 361