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J. Chem.

Thermodynamics 42 (2010) 802–807

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J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Equilibrium solubility of carbon dioxide in the amine solvent system
of (triethanolamine + piperazine + water)
Pei-Yuan Chung a, Allan N. Soriano a,b, Rhoda B. Leron a, Meng-Hui Li a,*
a
b

R&D Center for Membrane Technology and Department of Chemical Engineering, Chung Yuan Christian University, Chung Li 32023, Taiwan, ROC
School of Chemical Engineering and Chemistry, Mapúa Institute of Technology, Manila 1002, Philippines

a r t i c l e

i n f o

Article history:
Received 31 December 2009
Received in revised form 3 February 2010
Accepted 4 February 2010
Available online 10 February 2010
Keywords:
Carbon dioxide
Solubility
Blended amines
Triethanolamine
Piperazine

a b s t r a c t
In this study, a new set of data for the equilibrium solubility of carbon dioxide in the amine solvent system that consists of triethanolamine (TEA), piperazine (PZ), and water is presented. Equilibrium solubility
values were obtained at T = (313.2, 333.2, and 353.2) K and pressures up to 153 kPa using the vapourrecirculation equilibrium cell. The TEA concentrations in the considered ternary (solvent) mixture were
(2 and 3) kmol  m3 and those of PZ’s were (0.5, 1.0, and 1.5) kmol  m3. The solubility data (CO2 loading
in the amine solution) obtained were correlated as a function of CO2 partial pressure, system temperature, and amine composition via the modified Kent–Eisenberg model. Results showed that the model
applied is generally satisfactory in representing the CO2 absorption into mixed aqueous solutions of
TEA and PZ.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction
Carbon dioxide has long been identified as one of the major contributors to global warming. Thus, its removal and recovery from
industrial process streams and emissions have become vital and
the search for efficient and economical absorbents has gained significant interests [1–3].
In industrial gas treating processes, aqueous alkanolamine solutions have been widely used to remove acid gases such as CO2 and
H2S, triethanolamine (TEA), a tertiary amine, being one of the first
amines used for such application. Although it was superseded by
methyldiethanolamine (MDEA) and monoethanolamine (MEA)
[4], its application in the removal of acid gas is still recommended.
This has been proven throughout the decades as research interests
on TEA continuously increased resulting in the availability of
numerous experimental solubility data (H2S and CO2 in aqueous
ethanolamine solutions) in a wide range of temperatures, pressures, solvent compositions, and acid gas loadings [4–8]. The use,
however, of such solutions is subject to limitations in loading
capacity and absorption rate. Thus, the search for an effective promoter, such as piperazine (PZ), has gained recent interests in research [9].
Studies have been conducted on the effect of piperazine (PZ)
on the rate of absorption of CO2 when blended in aqueous

* Corresponding author. Tel.: +886 3 265 4109; fax: +886 3 265 4199.
E-mail address: mhli@cycu.edu.tw (M.-H. Li).
0021-9614/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2010.02.005

alkanolamines solutions. It has been found out that PZ has higher
reaction rate with CO2 than monoethanolamine (MEA), 2-amino2-methyl-1-propanol (AMP), and dimethylethanolamine (DMEA)
and has been reported to be superior than MEA, AMP, and DMEA
for CO2 absorption [9]. The small addition of PZ in aqueous AMP
solutions can also promote the reaction rates with CO2 [1,9] and
has significant effect on the enhancement of the CO2 absorption
rate [2]. The mixture of MEA and PZ also exhibited efficient CO2
removal with the CO2 removal efficiency increasing at higher
amounts of PZ [9]. In general, PZ-alkanolamine blends yield
improvements in absorption, such as higher loading capacity, faster rate of reaction, and lower solvent regeneration energy
requirements [3,10]. Although a number of studies have already
investigated the effect of PZ, when blended with known alkanolamines, on the absorption of CO2, no data is yet available on CO2
solubility in aqueous mixtures of TEA and PZ. Thus, it is the main
aim of this work to present new set of solubility data for CO2 in
aqueous solvent system containing blended amine solutions of
TEA and PZ. The solubilities of CO2 in the TEA–PZ [(2 and
3) kmol  m3 and (0.5, 1.0, and 1.5) kmol  m3, respectively] solvent systems were measured using a vapour-recirculation equilibrium cell at temperatures (313.2, 333.2, and 353.2) K and CO2
partial pressures of up to 153 kPa. Validation of the applied
experimental methods was done by measuring the CO2 solubility
in aqueous MDEA solution (2.0 kmol  m3) at 313.2 K and CO2
partial pressures of up to 90 kPa. The obtained equilibrium solubility data (CO2 loading in the total amine solution) in the aqueous blended amine systems were correlated as a function of CO2

and (PZ and MDEA). Chem.887 6.28 0.15%. thus. Results and discussion Prior to the measurement of CO2 solubility in the concerned solvent systems. Only the most pertinent details are discussed in the following paragraph. i.38 11.0580 0.2 . The excess NaOH was titrated with HCl solution using phenolphthalein as indicator.5-dm3 stainless steel sample cylinder was connected to the equilibrium cell to increase the volume of the vapour phase.60 3. The overall average absolute deviation (AAD). (model EX-810B) whose stability was within 0. Thermodynamics 42 (2010) 802–807 partial pressure. with an accuracy of ±0. temperature is ±0. adapted with a thermocouple (Pt).224 0. of the measured values (this work) from the corresponding data predicted by equation (1) was 9. model 3002.1 AAD % = 9.0 kmol  m3) MDEA solution at T = 313. A Mettler–Toledo (model AL204) digital balance with accuracy ±1  104 g was used in the preparation of the aqueous alkanolamine solutions. nitrogen was injected into and mixed with CO2 stream and the partial pressure of CO2 was determined via on-line gas chromatography.8 0. At equilibrium. which was compared with the readings from a CROPICO digital thermometer.1.0680 0.95 92. having an accuracy of ±0.7 AAD % = 2. a liquid sample was withdrawn from the equilibrium cell and placed directly into a vessel containing an excess of 1. When both the system pressure and the gas concentration did not change for 2 h. The solution was shaken well to permit all (physically and chemically) absorbed CO2 to precipitate the carbonate as BaCO3.177 0. with a precision of ±0.99) was purchased from SHOWA.2 101 0.441 0. The equilibrium pressure during the process was indicated by an Ashcroft test gauge with the scale reading range of 414 kPa and has an accuracy of ±0. Two cylinders were mounted vertically in a thermostat-installed air bath.866 1.48 13. All the experimental results for all the systems studied are the average of such replicate experiments. TEA– PZ–H2O.2 K from this work together with the available data from the literature [15–17].0960 0. model PTX-1400. The solubility of CO2 (also denoted here as CO2 loading capacity.240 0. A 1. Table 1 contains the results of our solubility measurements for aqueous (2. The liquid water used to prepare the solutions was a Type I reagentgrade water (resistivity = 18. The thermometer and pressure gauge used were periodically calibrated by the National Measurement Laboratory (ROC). Jou et al. An excess amount of BaCl2 solution was then added to the solution. the methods used in the measurements could be expected to give results with acceptable accuracy P ¼ 0:6632  24:31a þ 355:4a2  1322a3 þ 2215a4  1093a5 : ð1Þ TABLE 1 Solubility of CO2 in aqueous (2. 3.2%.. [15] MacGregor and Mather [16] Austgen and Rochelle [17] This work P CO2 =kPa aa P CO2 =kPa a P CO2 =kPa a P CO2 =kPa a 0. Measurement of CO2 solubility The solubility apparatus (vapour-recirculation equilibrium cell) and methods of analyses employed in this work are similar as those used in our previous works [11–14].17 4.7 a a is the CO2 loading in mol of CO2 per mol of amine.442 0. Considering all possible sources of uncertainty the average uncertainty for the following experimental results are estimated as follows: concentration in aqueous solutions is ±0. model 1502A.999 was obtained from Liehwa Industrial Gases. respectively. Experimental section 2. The standard deviation was obtained from the carried out replicate measurement runs (three to five times).2. and CO2 loading (mol of CO2 per mol of total amine) is estimated to be around 2% to 3% (standard deviation).90 0.2 K.686 0. Chung et al.0 M NaOH solution that would convert free dissolved CO2 into non-volatile ionic species.e. equilibrium was assumed to have been reached.. This was done to ensure that the applied procedures and method for the solubility measurements would yield valid and acceptable results.3 MX  cm and total organic carbon content (TOC) <15  109) and produced via Barnstead Thermodyne (model Easy Pure 1052) water purification system.).0 kmol  m3) MDEA solution at T = 313.44 89. From the amount of HCl added.803 AAD %b = 21. the solubility of CO2 in terms of the moles of CO2 per mole of amine was then calculated. Usually it would take (6 to 8) h for the system to attain equilibrium. The aqueous (2.99.842 0.267 0.184 2. Such consistency was quantified by the smoothed curve in figure 1. the solution was titrated with HCl with methyl orange as indicator. The temperature of the system was controlled by a basic immersion circulator obtained from NESLAB Instruments Inc.419 0. The 1-M (kmol  m3) standard solutions of NaOH(aq) and HCl(aq) were supplied by Fluka and the BaCl2 (mass fraction purity >0.113 0.01 K. Then. 2.1 kPa (readings above 100 kPa).005 K. 2. the solubility results obtained from this work appear to be consistent with the available data from the literature [15–17]. which was regressed from the combined data from this work and the available literature values [15–17] and is represented as in equation (1).0440 0. b Calculated using equation (1).01 kPa (readings below 100 kPa) and ±0. were acquired from TEDIA and ACROS Organics Co.9 0. The graphical comparison among the different measurements for this system is shown in figure 1. and amine composition using a modified Kent–Eisenberg model. Chemicals The alkanolamine samples. The thermometer used to register the temperature in the system was a Hart Scientific (Fluke) digital thermometer.02 kmol  m3.522 0.0-dm3 stainless steel vapour-recirculation equilibrium cell was used in the measurement of the equilibrium solubility of CO2 in the investigated aqueous blended amine system. system temperature. which were all reagent grade with a minimum mass fraction purity 0. Another 0. AAD % = 4. / J. Reagent grade carbon dioxide with a minimum mass fraction purity 0. Ltd.2 K and CO2 partial pressure of up to 90 kPa were measured. a) in amine solutions was determined by the standard acid–base titration method. (KUN Technology.2 K condition were chosen for the validation since there were a number of consistent data available in open literature for such condition.124 0.-Y.26 18.006 K. a standard centre for calibration. TEA. partial pressure is ±5 kPa (readings below 100 kPa) and ±10 kPa (readings above 100 kPa).362 0. Co.15 48.0 kmol  m3) MDEA solution at T = 313. the CO2 solubility in aqueous (2..803 P.74sss0 0. The pressure indicator was calibrated by a digital pressure gauge from GE Druck. To ensure low partial pressures of CO2.697 0.0 kmol  m3) MDEA solution at T = 313.1 °C of the set-point temperature.67 46. As presented in table 1 and also seen in figure 1.

14 137.633 117. Chem.519 0.2 K a a P CO2 =kPa a (2. and amine solvent systems’ compositions were obtained by measurement.699 3.9 0. MacGregor and Mather [16]. the solubility data at the considered CO2 partial pressures. P is the CO2 partial pressure in kPa and a the CO2 loading capacity in (mol CO2  mol amine1).00 0. calculated using equation (1).545 0.134 0.486 0. temperatures.356 0. and a is the CO2 loading capacity of the solvent system (mol CO2  mol amine1).128 0.651 80. which was also a modification of the original Kent–Eisenberg model [18] was applied to represent the CO2 solubility in the aqueous blended amine system of (TEA + PZ + H2O).399 2.544 32.49 87. [15]. respectively.359 0.24 0.108 0. T = 313. ð12Þ K 4 =ðkmol  m3 Þ2 ¼ exp½39:5554  9:879  104 =ðT=KÞ þ 0:568827  108 =ðT=KÞ2  0:146451  1011 =ðT=KÞ3 þ 0:136145  1013 =ðT=KÞ4 . (2) at constant CO2 partial pressure and solvent composition.97 0.785 0. and line.1 0. as a function of molar concentrations of the species (the one in bracket) present in their specific reactions 0:332647  1011 =ðT=KÞ3  0:282393  1013 =ðT=KÞ4 .73 23.22 0.5 kmol  m3) PZ 1.12 91.691 120.98 36. were modified forms (for units consistency) adapted from Kent and Eisenberg [18].04 87.17 9. Tables 2 and 3 show the results obtained.01 3. / J. K5 HCO3 $ Hþ þ CO2 3 : ð2aÞ ð3aÞ ð4aÞ ð11Þ 3 where mTEA and mPZ are the molar concentrations (kmol  m ) of TEA and PZ.421 18.97 11.09 0.05 20.474 0.0 kmol  m3) TEA + PZ solutions. ½R3 N½Hþ  . h.460 18.861 T = 353. K3 H2 O þ CO2 $ Hþ HCO3 . a correlation to describe the behaviour of the data obtained from the experimental measurements is essentially required. Plot of pressure against the solubility of CO2 in aqueous MDEA (2. The chemical reactions that describe the equilibrium of the quarternary system (CO2 + TEA + PZ + H2O) with TEA denoted as R3N.534 0.191 TEA + (0.275 16. After validating the methodology.77 0. s.00 21.433 103. K3 to K5.493 0. For the purpose of comparison and application.161 0.346 19.446 0.22 2. Chung et al.77 0.68 98. ð13Þ .169 0.5 kmol  m3) PZ 1. For acid gas solubility in various aqueous alkanolamine systems.31 4.01 98.342 0. Thermodynamics 42 (2010) 802–807 TABLE 2 Solubility of CO2 in aqueous (2.553 1.62 6. ð7Þ where P CO2 is the CO2 partial pressure in kPa and HCO2 is the Henry’s law constant.19 0.14 0.446 0.13 0. In this work. K2 ¼ ½PZHþ   þ ½H HCO3  . From these tables and figures.345 0.402 0.4 0.490 1.374 7.682 TEA + (1.470 30.384 0.740 0.91 6.533 45.587 54.15 0.08 87.56 9.18 0.205 0. K1 R3 NHþ $ Hþ þ R3 N.9 0.178 0.75 0.305 0.91 0.114 32. HCO2 .598 0. the CO2 loading (solubility) increases with increasing CO2 partial pressure.60 0.701 0. the CO2 loading decreases with increasing temperature.59 35.44 0. This work. and (3) at constant temperature and TEA concentration in the ternary mixture.283 0.53 0.58 0.47 47.73 0.2 K P CO2 =kPa FIGURE 1.56 14. ½R3 NHþ  þ ½PZ½H  . the increase in PZ concentration significantly increases the CO2 loading capacity of the aqueous blended amine system.2 K a TEA + (1. These relations are given as follows: K 3 =ðkmol  m3 Þ ¼ exp½241:818 þ 29:8253  104 =ðT=KÞ  1:48528  108 =ðT=KÞ2 þ ð5aÞ Equations (2) to (6) show the expressions for the apparent equilibrium constants.0 kmol  m3) solution at T = 313. smoothed values.257 90.37 30.203 0. are given as equations (1a) to (5a) a T = 333.37 7.94 0.19–22].99 2.389 6.26 55. the model developed by Li and Shen [12].15 22.0 kmol  m3) PZ 2. ð1aÞ ð9Þ ðmTEA þ mPZ Þa ¼ ½CO2  þ ½HCO3  þ ½CO2 3 .28 0. Austgen and Rochelle [17].603 0.17 0.485 5.51 7.67 0.27 92. The mass balance equations for the reacting species are as follows: mTEA ¼ ½R3 NHþ  þ ½R3 N.1 0.340 153.30 0.245 0.804 P.44 46.569 67.265 0.296 0.98 0.567 0. þ K2 þ PZH $ H þ PZ.42 8.827 1.207 53.56 43. K1 ¼ K5 ¼ ð2Þ ð3Þ ð4Þ ð5Þ ½Hþ ½CO2 3  : ½HCO3  ð6Þ Henry’s law relating the CO2 partial pressure to the concentration of the physically dissolved CO2 in the solvent is given as PCO2 ¼ HCO2 ½CO2 .43 8. Figures 2 to 4 also show that the applied model.077 8.87 103. satisfactorily predicts the obtained solubility data. In equation (1). K4 H2 O $ Hþ þ OH .80 0. Figures 2 to 4 show a representative trend of the general behaviour of the observed results. it had been deduce that (1) at constant temperature and solvent (TEA–PZ–H2O) composition. mentioned in equations (4) to (6) and the Henry’s law constant for CO2.432 0.88 0.635 0.368 37.75 0.243 60. Ki.0 0.91 0.00 3.44 15.335 0.2 K: j.45 43.215 6.085 0.83 52.645 0. ð10Þ ½R3 NHþ  þ ½PZHþ  þ ½Hþ  ¼ ½OH  þ ½HCO3  þ 2½CO2 3 . K3 ¼ ½CO2   þ K 4 ¼ ½H ½OH . The apparent equilibrium constants.83 12.538 P CO2 =kPa 1.0 kmol  m3) TEA 2.342 0.405 43. Jou et al.066 0.84 16. ð8Þ mPZ ¼ ½PZHþ  þ ½PZ. described in the succeeding paragraphs.746 a is the CO2 loading in mol of CO2 per mol of amine.433 0.28 25. the modified form of the original Kent–Eisenberg model [18] seems to be the simplest and yet has a theoretical basis that could be used [15. 4.398 0.84 18.080 0.-Y.08 41.97 0.416 0.

05 11.0 kmol  m3) TEA.362 1.43 49.55 0.53 0.0 kmol  m3) TEA + (1.14 0. a is the CO2 loading in mol of CO2 per mol of amine.353 2.308 0.40 15.73 29.50 29.77 0.0 kmol  m3) TEA + (0.85 6.0 kmol  m3) TEA + PZ solutions.507 0.034 0.42 14.5 kmol  m3) PZ.26 6.18 0.613 0.16 0.5 kmol  m3) TEA. TEA + (1.239 0.68 8.43 89. the apparent equilibrium constants. (2.338 27.96 0.0 kmol  m3) PZ.2 K.41 0.546 0. 333.18 4.226 0.2 K a P CO2 =kPa a P CO2 =kPa T = 353.81 0.2 K). d.323 0. Chem.77 0.184 0.16 58.40 40.31 84.66 106.074 0. for the main amine reactions.2 K.01 55. 4. Chung et al.5 kmol  m3) PZ. T = 313.1 a 0. N.5 kmol  m3) PZ 1. equations (1a) and (2a). d.175 99.36 22.601 TEA + (1.95 14.91 109.212 0.2 K T = 333.42 0.76 15. and [solid lines.353 0. O.2 K.33 49.279 0. 333.411 68.258 0. Applying the least- .85 61.313 0.308 12.373 3 1. [h.32 31.368 0. d. calculated using the modified Kent–Eisenberg model.265 48.11 0.78 28.200 0.00 0. HCO2 =½kPa  ðkmol  m3 Þ1  ¼ exp½2:97068  0:184393  104 =ðT=KÞþ 0:009217  108 =ðT=KÞ2  0:002078  1011 =ðT=KÞ3 þ 0:0016  1013 =ðT=KÞ4 : 3 4 8 2 K 5 =ðkmol  m Þ ¼ exp½294:74 þ 36:4385  10 =ðT=KÞ  1:84157  10 =ðT=KÞ þ 0:415792  1011 =ðT=KÞ3  0:354291  1013 =ðT=KÞ4 . 3 3 (2. K1 and K2.0 kmol  m ) TEA solutions].107 0.086 0.444 0.128 29.29 0.0 kmol  m3) TEA 2.309 0. and lines. calculated using the modified Kent–Eisenberg model. 353.18 37. dashed lines.316 28. were assumed to be dependent on temperature (T).245 0.0 kmol  m3) TEA solution at the considered temperatures: (j.21 0.196 15.34 0..44 36.2 K: [j.00 80.209 0.064 0. s.250 8.01 0.75 0. FIGURE 4.77 88.24 0.241 1.258 4.342 0.63 3.180 0.34 0.0 kmol  m3) PZ 2.59 6. Plot of pressure against the solubility of CO2 in aqueous (2.362 42.443 0. TEA + (1.329 99.09 36. Plot of pressure against the solubility of CO2 in {aqueous (2. CO2 loading (a). N.2 K.5 kmol  m3) PZ} solution at the considered temperatures: (j.237 0.285 0.137 32. PZ].18 6.17 0.125 0.37 0. ð14Þ ð15Þ In this work.519 TEA + (0.393 63.84 24.17 2.805 P.392 0. 313. 353. this work. and amine compositions (mTEA and mPZ).0 kmol  m ) TEA solutions.434 0.5 kmol  m3) PZ].157 0.68 55.265 1.345 0.182 0.84 95.91 0.31 23.83 82.73 2.34 34.0 0.165 0.472 0.52 64.311 0.05 46. 313.18 0.0 0.150 6.86 31.66 4. TEA + (1.0 kmol  m3 and 3.255 0.642 TEA + (1.055 6.147 2.64 13. (3. calculated using the modified Kent–Eisenberg model.0 0.045 0.39 0.353 45.7 0. .74 0.5 kmol  m ) PZ 1. FIGURE 2.134 0.87 121. (3.315 0.303 69.44 0. Plot of pressure against the solubility of CO2 in {aqueous (2.-Y.425 (3. / J. this work.300 15.329 0. and lines.408 103.562 0.0 kmol  m3) TEA + PZ} solution at T = 353.2 K a P CO2 =kPa a 1.41 0. Thermodynamics 42 (2010) 802–807 TABLE 3 Solubility of CO2 in aqueous (3.22 0.2 K).43 3. TEA + (0.145 54.26 0. N.0 kmol  m3) PZ.249 0.259 0.073 16.386 0.226 30.67 0.269 0.437 101. TEA + (0.462 FIGURE 3.25 14.080 0.

Aside from figures 2 to 4.6 0. [Bmim][BF4]). TEA + (1.0 kmol  m3) TEA + (1. calculated using the modified Kent–Eisenberg model. ð16Þ FIGURE 5. h. . K1 and K2 were determined to give the following expressions as in equations (16) and (17).-Y.2 K. 323. reference [25]. Chung et al.5 kmol  m3) PZ. aqueous (2.2 K). 353. Thermodynamics 42 (2010) 802–807 squares fit to the equilibrium solubility values obtained for CO2 in aqueous blended amine system of (TEA + PZ). Mason and Dodge [5]. .806 P. 313. and lines. interpolated.2 K). reference [26].2 K. (4. j. respectively: K 2 =ðkmol  m3 Þ ¼ expf55:928 þ 10263=ðT=KÞ  2627900=ðT=KÞ2 þ 65:922a 42:321a2  4:5132mTEA =ðkmol  m3 Þþ 6:9725mPZ =ðkmol  m3 Þ  3:8987mTEA mPZ þ 3:6595m2PZ g: 2 K 1 =ðkmol  m3 Þ ¼ expf58:088  45718=ðT=KÞ þ 6820300=ðT=KÞ þ 3:7833a ð17Þ 7:6473a2 þ 0:050349mTEA =ðkmol  m3 Þ 6:4299mPZ =ðkmol  m3 Þ þ 1:0139mTEA mPZ þ 1:939m2PZ g. 313. [Emim][MDEGSO4].5 kmol  m3) PZ. 273. calculated using the modified Kent–Eisenberg model. and (solid lines. [Bmim][triflate]). d. 333. Plot of pressure against the solubility of CO2 to compare solubility for various solvent systems at T = 313. 348. reference [24]. PCO2 / kPa 4000 3000 2000 1000 0 0.2 K.5 kmol  m-3) PZ} solution at different temperatures: (j.2 K. N. (s.9%.0 kmol  m3) TEA solution to compare data: T = (j. extrapolated).2 K).5 kmol  m3) PZ solution.0 kmol  m3) TEA + (1. TEA + (1. /. 353.4 0. which has a total of 163 data points.0 kmol  m3) TEA + PZ} solutions: d. Plot of pressure against the solubility of CO2 in {aqueous (2. h.2 0. d. (O.0 0. The constants satisfactorily represent the experimental solubility results as shown by an acceptable overall AAD of 18.0 kmol  m3) TEA. 333. [Emim][BF4].2 K: j. which contains the plot of the comparison between the predicted and measured partial pressure of CO2 in the considered aqueous blended amine system of (TEA + PZ). such a satisfactory result is also shown in figure 5. this work. FIGURE 7. Plot of pressure against the solubility of CO2 in aqueous (2. reference [23]. this work. / J. s. 4. }. this work.. (16) and (17) were regressed from the experimental solubility results of CO2 in aqueous system of (TEA + PZ) obtained in this work.2 K. (2.8 -1 α / (mol CO2 mol solvent ) FIGURE 6. Plot of the predicted (the predicated values are calculated by the modified Kent–Eisenberg model) partial pressure against the measured partial pressure for CO2 in {aqueous (2. Chem. dashed lines. [Emim][EtSO4]. TEA + (0. s. FIGURE 8. [Emim][triflate]. 298.2 K. [Bmim][PF6]). O. (h.0 kmol  m3) PZ. N. The constants presented in Eqs.2 K.

Chem.N. Lyudkovskaya. Chem. F.-E.M. C. 268 (2008) 121–129. Figure 8 contains the plot of the comparison of the CO2 solubility of the present system against the IL systems considered. B.J. Li. AIChE 32 (1936) 27–48. 39 (2000) 2062–2067. which further validates the applied methodology for this work. J. C. Chang. Can. Soriano. 94 (1990) 53–61. results from our previous works on ILs [23–26] were used at similar temperature condition (T = 313. Thermodynamics 42 (2010) 802–807 The applicability of the determined constants. 298. [9] C.2. Chem. 40 (2009) 387– 393. Ind.D. Dev. the determined constants satisfactorily represent the solubility data of Mason and Dodge [5].-H. Chem..2. [22] D. Hydrocarbon Process. Doma Jr. Thermodyn. [8] F. For the present system. Can.5) kmol  m3. Prog. B. was validated using the available data of Mason and Dodge [5] for CO2 solubility in aqueous (2. As this figure shows. 69 (1991) 1357–1366. W.-H. Phukan.-H. Iliuta. J. Eng. Dodge. Chem. Eng.N. Mather. Chin. 63 (1985) 122–125.E. [17] D. Chen. Otto. Chem. For the representative IL system. Hu. Thermodyn. M. 41 (2009) 525– 529. J. Kent.2 K isotherm. Data 38 (1993) 105–108. 333.-Y. B.-H. Mather.-H.D. B. Eng. [18] R. A. Chem. B. 1. Tung.-C.2 and 373.. [14] M. Eng. J. as shown in figure 6. Yong. Acknowledgement This research was supported by Grants.-C.5 kmol  m3) PZ} solutions at T = 313.T. References [1] D. B. S.-C. Chem. K.K. [5] J.0 kmol  m3) TEA solution at T = (273. Prok. B. Chakravarty.-H. JCT 10-2 . A. Mather. A. Ind. The model was further validated by investigating its capability to predict values for conditions where there are no data available yet. Shen. Lim.T.L. Eng.2. the studied system in this work has the highest CO2 loading per mole of the solvent used. Mather. / J. Chem. [15] F. J.E. Chung et al. Li. As seen in this figure (dashed lines). M. Seo. Chem. Chem.-H.0 kmol  m3) TEA + (1.0. Jou.. The CO2 absorption performance of the considered system was also compared to the performance of another class of solvent called ionic liquids (ILs). Soriano.H.2. J. 39 (2008) 13–21. Otto. Tontiwachwuthikul. Jou. J. J.-P. K. Otto. Tan.-H. A modified Kent–Eisenberg model satisfactory correlated the measured equilibrium loading (solubility)/partial pressure pairs at different temperatures and amine concentration levels. and 353. M. Figure 7 representatively shows such validation.-H.P.-H. Process Des. A. R. Eng. J. [10] T. Res.-Y. Li. A. [3] S.E. J. Shen. 21 (1982) 539–544. F. Leibush. Li. Li. Ind. 4. Hong. Chem. Sun. Chakma. [7] F. 60 (2005) 503–516.T.F. Chiang. the model applied systematically extrapolates the behaviour of the solubility data at conditions beyond the experimental setting at T = (293. and pressures up to 153 kPa have been determined.-F. Meisen. Inst. [19] J. The equilibrium solubility values of CO2 were obtained via measurements in a vapour-recirculation equilibrium cell for TEA and PZ concentrations of (2 and 3) kmol  m3 and (0. A. [11] K.G. Chem. 30 (1991) 543–555. I. [6] M. Eng. was considered for such comparison. B. [26] A. Sci.N. U.-C.. A.D. as shown by an acceptable AAD of 18. Soriano. M.T. Li. 22 (1949) 558–567. As shown in this figure. [21] P. Chem..-Y. Fluid Phase Equilib.P. Zh. MacGregor. Chem. F. G.2 K). F. Here. Chem. Mather. This observation arises from the fact that the CO2 absorption of ILs was merely physical and that of the considered system is chemical in nature.E.-Y. Conclusions A new set of results for the equilibrium solubility of CO2 in the aqueous blended amine system of (TEA + PZ) at T = (313. Data 36 (1991) 130– 133.-L. Purif. thus. in aqueous {(2. Austgen. [4] Y.N. NSC 98-2221-E-033029 and NSC 98-3114-E-007-013.2) K. [2] W. [23] A.2) K.T. J. Chem. J. M. 54 (1976) 214–219. J. Taiwan Inst. of the National Science Council of the Republic of China. 49 (2006) 174–180. Chem. P. Eng. figure 6 also shows that the solubility results obtained are consistent with the reported data of Mason and Dodge [5]. Li. Fradette. Rochelle. 35 (1996) 4804–4809. Mather. Chem. Eng. 323. Khim.A. the applied model (together with the obtained parameters) can also be recommended to be used for a wider range of conditions of temperature and CO2 partial pressures. Doma Jr. Eisenberg. A. Mason. [16] R.E. [13] M. 81 (1985) 32–36. Eng. Commun. K1 and K2.-H. respectively.D.2) K. Chem. Eng.9% for a total of 163 data points. Data 53 (2008) 2550–2555.2. Data 41 (1996) 1181.W. the condition in which the maximum solubility was observed. Eng. Eng. 55 (1976) 87–90. [20] W. with the exception of the 273.C. The model applied was also proven to be applicable over a wider range of conditions as it represented well the available data from the literature and systematically al- 807 lowed extrapolation of the data at conditions beyond the experimental setting. Eng.J. Li.G. F. Sep. Hsieh. J. 40 (2008) 1654– 1660. Eng. Larachi. Iliuta. Technol. Eng. J. Data 40 (1995) 328–331. Res.-B. Data 39 (1994) 448–452. M. Can. Otto. Trans. Lin. Soriano. C.J. Le Tourneux. Lee. Chem.5. i. Eng. Doma Jr. Eng.E. Eng.H.2 K. Chem. and 348. Jou. and 1.-S. Li. Doma Jr. Li.I. [25] A. Res. Data 37 (1992) 96–100. Weiland. M.e. the CO2 absorption performance was based on the CO2 solubility in terms of mol of CO2 per mol of solvent. Ind. M. [12] M. Chang. Li. [24] A. A.