1004 J. Chem. Eng.

Data 1997, 42, 1004-1006

Heat Capacity of Aqueous Monoethanolamine, Diethanolamine,

N-Methyldiethanolamine, and N-Methyldiethanolamine-Based
Blends with Carbon Dioxide

Ralph H. Weiland,* John C. Dingman, and D. Benjamin Cronin†

Optimized Gas Treating, Inc., 15638 Whitewater Lane, Houston, Texas 77079

New data are reported on the heat capacity of CO2-loaded, aqueous solutions of monoethanolamine (MEA),
diethanolamine (DEA), N-methyldiethanolamine (MDEA), and aqueous MDEA-based blends with MEA
and DEA.
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Introduction Table 1. Heat Capacity (J g-1 K-1) of CO2-Loaded MDEA

Solutions at 25 °C
The work reported here was motivated by the need to
loading 30 mass % 40 mass % 50 mass % 60 mass %
quantify the effect of acid gas loading on the important
(mol/mol) MDEA MDEA MDEA MDEA
physical properties of gas-sweetening solvents. Focus is
on the effect of CO2 loading on the specific heat of amine- 0.00 3.787 3.585 3.407 3.174
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0.05 3.761 3.531 3.366

treating solutions, in the form of both single amines and
0.10 3.703 3.528 3.342
N-methyldiethanolamine-based blends. It should be pointed 0.13 3.087
out, however, that dissolved H2S, which we have not 0.15 3.684 3.526 3.298
studied here, is likely also to have a no-less-important 0.20 3.684 3.473 3.294
impact. Little or no data exist for the effect of H2S loading 0.25 3.636 3.460 3.208 3.005
on physical properties, and data are certainly needed. 0.30 3.607 3.384 3.163
0.35 3.545 3.365 3.136
0.38 2.976
Experimental Section 0.40 3.496 3.350 3.132
Heat capacity was determined by measuring the tem- 0.45 3.436 3.287 3.120
0.50 3.436 3.240 3.094
perature rise of a known mass of sample in response to a 0.51 2.886
known electrical energy input via an immersed ohmic 0.64 2.849
resistance. Samples were contained in a stoppered and
gently-stirred Dewar flask, and the equipment was cali- Table 2. Heat Capacity (J g-1 K-1) of CO2-Loaded DEA
brated (the cell constant determined) using water and Solutions at 25 °C
various salt solutions as standards. This was not an loading 10 mass % 20 mass % 30 mass % 40 mass %
isothermal experiment. Temperature measurements were (mol/mol) DEA DEA DEA DEA
started below 25 °C and continued to above this temper- 0.00 4.047 3.915 3.778 3.566
ature so that measurements bracketing the desired tem- 0.05 3.878 3.699 3.535
perature were made. The repeatability of the heat capacity 0.10 4.034 3.850 3.663 3.486
measurements was (1%. and test runs on standard 0.15 3.834 3.648 3.465
0.20 3.987 3.798 3.639 3.416
systems with known heat capacities gave results also
0.25 3.792 3.616 3.405
within (1% of the reported values. 0.30 3.965 3.761 3.565 3.372
All the amine solutions on which heat capacity measure- 0.35 3.763 3.547 3.239
ments were made were preloaded with known amounts of 0.40 3.946 3.740 3.527 3.315
CO2. For each amine of a specified concentration, a large 0.45 3.729 3.515 3.295
0.50 3.923 3.711 3.474 3.278
batch of aqueous solution was made up and roughly one-
half of it was saturated with CO2 by sparging CO2 into the Table 3. Heat Capacity (J g-1 K-1) of CO2-Loaded MEA
solution through sintered glass disks. Aliquots from these Solutions at 25 °C
two batches, one unloaded and the other saturated with loading 10 mass % 20 mass % 30 wt 40 mass %
CO2 at atmospheric pressure, were mixed together in (mol/mol) MEA MEA MEA MEA
various proportions to make up a series of solutions all
0.00 4.061 3.911 3.734 3.634
having the same amine to water ratio but each one having 0.05 4.015
a different CO2 loading. For each sample containing a 0.10 3.823 3.656 3.508
single amine, the total amine concentration and the CO2 0.20 3.917 3.766 3.570 3.343
loading were determined titrimetrically using the method 0.30 3.915 3.670 3.457 3.238
of Weiland and Trass (1969). For mixtures of two amines, 0.40 3.891 3.648 3.418 3.163
their individual concentrations could not be determined 0.50 3.857 3.597 3.359 3.109
titrimetrically (an inherently high precision method of
analysis compared, say, to gas chromatography), so we
relied on careful, accurate weighing of the constituents and mass basis; however, the CO2 loading was still determined
their mixing together to make the original solutions on a titrimetrically for each sample on which data were taken.
Several kilograms of each original CO2-free solution was
* Corresponding author. E-mail: rweiland@[Link]. made, and each constituent was weighed with an accuracy
† Present address: Mt. Isa Mines, Ltd., Mt. Isa, Queensland, Australia. of (0.1 g. All heat capacities are reported at 25 °C.
S0021-9568(96)00314-7 CCC: $14.00 © 1997 American Chemical Society
 Journal of Chemical and Engineering Data, Vol. 42, No. 5, 1997 1005

Figure 1. Heat capacity of CO2-loaded MDEA solutions at 25 Figure 3. Heat capacity of CO2-loaded MEA solutions at 25 °C:
°C: O, 30 mass % MDEA; 0, 40 mass % MDEA; 3, 50 mass % O, 10 mass % MEA; 0, 20 mass % MEA; 3, 30 mass % MEA; b,
MDEA; b, 60 mass % MDEA. 40 mass % MEA; x, 20 mass % MEA, Dow Chemical Company
(1982).

Figure 2. Heat capacity of CO2-loaded DEA solutions at 25 °C;

O, 10 mass % DEA; 0, 20 mass % DEA; 3, 30 mass % DEA; b, 40 Figure 4. Heat capacity of CO2-loaded DEA-MDEA blends at
mass % DEA; 4, 20 mass % DEA, Kahrim & Mather (1980); *, 25 °C: O, 5 mass % DEA and 45 mass % MDEA; 0, 10 mass %
35.5 mass % DEA, Kahrim & Mather (1980); x, 50 mass % DEA, DEA and 40 mass % MDEA; 3, 20 mass % DEA and 30 mass %
Kahrim & Mather (1980). MDEA

Results Discussion
The heat capacity data for N-methyldiethanolamine As shown in Figures 1-3, measured heat capacities are
(MDEA), diethanolamine (DEA), and monoethanolamine always a decreasing function of loading, and the higher the
(MEA) as a function of CO2 loading are given in Tables amine concentration the greater the sensitivity to CO2
1-3 and in Figures 1-3. Corresponding data for aqueous content. The lines in Figures 1 and 2 are least-squares
DEA/MDEA and MEA/MDEA blends are shown in Tables linear fits to our data; the lines in Figure 3 are least-
4 and 5 and Figures 4 and 5. squares quadratic fits to our data. As shown in Figure 2,
1006 Journal of Chemical and Engineering Data, Vol. 42, No. 5, 1997

Table 4. Heat Capacity (J g-1 K-1) of CO2-Loaded DEA/MDEA Blends at 25 °C

loading 5 mass % DEA 10 mass % DEA 20 mass % DEA
(mol/mol) 45 mass % MDEA 40 mass % MDEA 30 mass % MDEA
0.00 3.404 3.417 3.410
0.10 3.378 3.355 3.340
0.20 3.312 3.305 3.274
0.30 3.262 3.254 3.242
0.40 3.184 3.164 3.135
0.50 3.136 3.136 3.120

Table 5. Heat Capacity (J g-1 K-1) of CO2-Loaded MEA/MDEA Blends at 25 °C

loading 5 mass % MEA 10 mass % MEA 20 mass % MEA
(mol/mol) 45 Mass% MDEA 40 mass % MDEA 30 mass % MDEA
0.00 3.440 3.384 3.445
0.10 3.374 3.315 3.319
0.20 3.257 3.246 3.234
0.30 3.205 3.161 3.158
0.40 3.112 3.079 3.074
0.50 3.064 3.013 2.992

for 35.5 mass % and 49.7 mass % DEA at 25 °C are shown

also in the same figure. In Figure 3 our data for 20 mass
% MEA are compared with data provided by Dow Chemical
Company, and, to within the scatter in the measurements,
the two data sets appear to be in substantial agreement.
In mixed amines (Figures 4 and 5), the data show that
at a given, constant, total amine concentration there is no
consistent dependence of heat capacity on the relative
proportions of the two amines constituting the blend, at
least to within the inherent scatter in the data. Just as
for single amines, the heat capacity of amine mixtures
decreases approximately linearly with CO2 loading.

Acknowledgment

The amines were supplied by Huntsman Corp., courtesy

of Mr. Tom Kenney.

Literature Cited
Dow Chemical Company, Freeport, TX. Private communication, 1982.
Kahrim, A.; Mather, A. E. Enthalpy of Solution of Carbon Dioxide in
Diethanolamine Solutions. Can. J. Chem. Eng. 1980, 38, 660.
Weiland, R. H.; Trass, O. Titrimetric Determination of Acid Gases in
Alkali Hydroxides and Amines. Anal. Chem. 1969, 41, 1709.

Received for review September 23, 1996. Accepted June 30, 1997.X
The heat capacity measurements presented here were made as part
Figure 5. Heat capacity of CO2-loaded MEA-MDEA blends at
of the GRI/GPA Acid Gas Research Program under GRI Contract
25 °C: O, 5 mass % MEA and 45 mass % MDEA; 0, 10 mass % No. 5091-260-2310, Dr. Jeffrey L. Savidge, Senior Contract
MEA and 40 mass % MDEA; 3, 20 mass % MEA and 30 mass % Manager, GRI, and Mr. Mike Hegarty, GPA Liason.
MDEA.
JE960314V
our data for DEA tend to fall slightly below the data of
Kahrim and Mather (1980) for 20 mass % DEA. Their data X Abstract published in Advance ACS Abstracts, August 1, 1997.