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Investigation of Mass-Transfer Performance for CO2 Absorption into Diethylenetriamine (DETA) in a Randomly Packed Column
Kaiyun Fu, Teerawat Sema, Zhiwu Liang,*,, Helei Liu, Yanqing Na, Huancong Shi,, Raphael Idem,, and Paitoon Tontiwachwuthikul,

Joint International Center for CO2 Capture and Storage (iCCS), Department of Chemical Engineering, Hunan University, Changsha, 410082, Peoples Republic of China International Test Centre for CO2 Capture (ITC), Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan, S4S 0A2, Canada ABSTRACT: The mass-transfer performance of CO2 absorption into aqueous diethylenetriamine (DETA) solutions was investigated in an absorption column randomly packed with Dixon rings at 303303 K and atmospheric pressure, and compared with that of monoethanolamine (MEA), which is widely considered as a benchmark solvent for CO2 absorption. The masstransfer performance was presented in terms of volumetric overall mass-transfer coecient (KGav). In particular, the eects of operating parameters, such as inlet CO2 loading, solvent concentration, liquid ow rate, inert gas ow rate, and liquid temperature, were investigated and compared for both MEA and DETA. Over 40 runs of absorption experiments were carried out in this study. The results showed that KGav of DETA was found to be higher than that of MEA. Also, inlet CO2 loading, solvent concentration, liquid ow rate, and liquid inlet temperature had signicant eect on KGav for both systems. However, the inert gas ow rate had an insignicant eect on KGav. Lastly, predictive correlations for KGav for DETACO2 and MEACO2 systems in randomly Dixon ring packed columns were successfully developed. The predicted results were found to be in relatively good agreement with the experimental results, with average absolute deviations (AADs) of 16% and 14%, respectively.

1. INTRODUCTION The accumulation of carbon dioxide (CO2) in the atmosphere leads to an increase in the Earths surface temperature, which is recently gaining worldwide public attention. Therefore, the removal of CO2 from industrial process gas streams is crucial in order to mitigate global warming and climate change problems. Currently, absorption of CO2 into aqueous alkanolamine is one of the most attractive approaches for CO2 removal. This is considered to be the most technically and economically feasible method. Several alkanolamines have been used to capture CO2. Monoethanolamine (MEA) and diethanolamine (DEA), which are considered as primary and secondary amines, respectively, have been widely used, because of their high reactivity with CO2. However, their shortcomings of low absorption capacity and high energy requirements for solvent regeneration oset the bene t of good kinetics.1 3 On the other hand, methyldiethanolamine (MDEA), which is a tertiary amine, has a higher CO2 absorption capacity and lower energy requirement for solvent regeneration, but much lower reactivity with CO2. 2-Amino-2-methyl-1-propanol (AMP), which is a primary sterically hindered amine, is also reactive with CO2. In addition, MDEA and AMP oer higher degradation resistance advantages over MEA and DEA.4,5 However, precipitation is the main drawback of AMP. Thus, developing an ecient absorbent has been considered to be very signicant in todays world of serious atmospheric pollution and energy scarcity.6,7 An absorbent that has great potential for CO2 capture should have a fast absorption rate, high absorption capacity, low regeneration energy requirement, negligible vapor pressure, high thermal and chemical stability, and low corrosiveness.812
2012 American Chemical Society

Recently, diethylenetriamine (DETA), which has two primary amine groups and one secondary amine group, has been considered as a potentially alternative solvent for capturing CO2, because of its fast reaction kinetics and high absorption capacity.8,1317 In addition, the performance evaluation of any solvent is not only based on solubility and reaction kinetics, but also on the mass-transfer performance, because it is a critical parameter for designing the absorption column. The higher the mass-transfer coecient, the shorter the absorption column. Therefore, for an eective solvent, a high mass-transfer coecient is expected. This is because the shorter the absorption column, the lower the capital cost for building the column. In addition, with the shorter absorption column, the operating cost for capturing CO2 can be reduced, because the energy requirement for pumping can be decreased. Thus, the cost of capturing CO2 can be reduced. In the process of post-combustion CO2 capture in packed column systems, in addition to the eective solvent, the higheciency column internals also play a crucial role. In this study, a Dixon-ring random packing (provided by China Haohua, Tianjin, Univtech Co., Ltd., China) was used; a photograph of Dixon rings is shown in Figure 1. A Dixon ring oers higher surface area and void fraction than conventional random packings, such as Rasching ring and Berl saddle.18,19 The high surface area reects high gasliquid phase contact area and the high void fraction helps to reduce operational cost.
Received: Revised: Accepted: Published:
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March 29, 2012 August 16, 2012 August 20, 2012 August 20, 2012
dx.doi.org/10.1021/ie300830h | Ind. Eng. Chem. Res. 2012, 51, 1205812064

Industrial & Engineering Chemistry Research

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and found to be 2.219 108, which is very close to zero and can be negligible. Therefore, several mass-transfer studies20,21,23 assumed that the yA * value was zero and could be neglected from the calculation scheme. Also, the same assumption was applied in the present study. The concentration gradient (d Y A,G /d Z ) can be obtained by measuring the CO 2 concentration along the column and subsequently plotting as the CO2 concentration prole. In such a way, the value of KGav can be calculated at any interesting YA. In this work, the comparison criteria for KGav values were obtained at a CO2 molar ratio of YA = 0.12.

Figure 1. Photograph of Dixon rings.

In this work, the mass-transfer performance characteristics of DETACO2 and MEACO2 systems, in terms of the volumetric overall mass-transfer coecient (KGav), were investigated and compared. By means of determination of KGav, it is simple and eective to describe the mass-transfer behavior of any solvent in a packed column. Aroonwilas and Tontiwachwuthikul20 and Maneeintr et al.21 successfully adopted this method to study the mass-transfer performance for CO2 absorption into AMP, using Sulzer EX structured packing, and into 4-diethylamino-2-butanol (DEAB), with Sulzer DX structured packing.

2. DETERMINATION OF KGaV IN A PACKED COLUMN There are three popularly accepted theories for explaining mass-transfer phenomenon: lm theory, penetration theory, and surface-renewal theory. Each one has its advantages and limitations. Because of the stability of two-phase ow under low-turbulence conditions, which forms a steady gas/liquid interface, the lm theory is applicable to describe the masstransfer process. Based on the lm theory, under steady-state conditions, combining the mass ux equation and material balance equation, KGav can be dened as follows (more detail can be seen in the literature).2023
d Y G A,G K Gv = P(y y*) d Z A,G A

(1)

where G is the inert gas ow rate and P is the operating pressure (which is atmospheric pressure in the present work). The concentration of A (which is CO2) in the gas phase can be measured along the height of the packed column using an infrared CO2 gas analyzer (Model 302WP, Nova Analytical Systems, Inc., Hamilton, Ontario, Canada). The measured CO2 concentration, in terms of mole fraction of A in the gas phase (yA,G), were converted to molar ratio of A in the gas phase (YA,G); then, it is plotted against the height of the column (Z) to obtain the solute molar ratio concentration gradient (dYA,G/ dZ). yA * is the equilibrium concentration, in terms of the mole fraction of A at the interface, which can be calculated using the Henrys law relationship24 via N2O analogy, as mentioned by Hartono et al.16 For an instantaneous chemical reaction, y* A is very close to zero and usually neglected.25 In the work of Naami et al.,25 the yA * value in DEAB solvent was investigated
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3. EXPERIMENTAL SECTION 3.1. Chemicals. Reagent-grade MEA and DETA with purities of 99% were purchased from Tianjin Kermel Chemical Reagent Co., Ltd., China. These amine solutions were prepared to the desired concentration with deionized water. Commercial-grade CO2 cylinder (with a purity of 99%) was supplied by Changsha Jingxiang Gas Co., Ltd., China. 3.2. Experimental Apparatus and Procedure. The absorption experiments were conducted in a randomly packed column that was made of acrylic plastic and enwrapped by thermal insulation material. A Dixon ring (made of 304 stainless steel) was lled into the column. In order to minimize the unfavorable eect of wall ow, a liquid redistributor was placed in the middle of packed bed. Besides the packed column, auxiliary equipment including an air compressor, a CO2 cylinder, a gas mass ow meter with 1% accuracy (Model CS200, Beijing Sevenstar Electronics Co., Ltd., China), a constant liquid-ow pump with 0.3% accuracy (Model BT1300, Shanghai Qi Te Analytical Instruments Co., Ltd., China), a thermostatic water bath with 1 K accuracy (Model HHS-11-4, Shanghai Lei Yun Test Equipment Manufacturing Co., Ltd., China), a gas mixer, and a storage tank were required. The experimental setup for the absorption column is similar to our previous work.21 Prior to the experiment, all the variables were prepared to the desired value. Since the density of liquid phase varies with both the solvent concentration and CO2 loading in solution, the liquid ow rate was calibrated by measuring a known volume of liquid phase, which was driven by constant liquid-ow pump over time in a graduated cylinder. CO2 from cylinder and air from air compressor were owed through mass ow meters at desired rates, then mixed to a desired CO2 concentration before being introduced into the bottom of the column. The liquid solvent was fed from the top of the column. Both the gas and liquid phases were preheated and controlled by the temperature-controlled bath. The gas phase was sampled along the column. Liquid-phase samples were taken at the inlet and outlet of the column. To conrm the validity of each experimental run, a mass balance calculation (the amount of CO2 removed from gas phase versus that of CO2 absorbed into the liquid phase) was conducted. The mass balance error, which is an error in the experiment, obtained in this study was found to be <5% (the calculation procedure can be found in our previous work25). The parameters of the column and the operational variables are presented in Table 1. In the present work, the inlet CO2 concentration was investigated over the range of 14.8%15.8%, which covers the range of CO2 concentration relevant to the post-combustion process of the ue gas from coal-red power generation plant. Also, the CO2 loading range of DETA used in the present work (which is 0.0510.819 mol CO2/mol amine) was found to be
dx.doi.org/10.1021/ie300830h | Ind. Eng. Chem. Res. 2012, 51, 1205812064

Industrial & Engineering Chemistry Research Table 1. Column Parameters and Operational Variables
conditions diameter of the column height of packing gas-phase CO2 concentration inert gas load liquid ow rate solvent concentration CO2 loading feed temperature pressure MEACO2 system 24 mm 1.40 m 14.8%15.3% 24.9839.45 kmol/(m3 h) 3.989.29 m3/(m2 h) 2.05.0 kmol/m3 0.0080.23 mol CO2/mol amine 303323 K (1 K) 103 kPa DETACO2 system 24 mm 1.40 m 15.1%15.8% 28.7846.62 kmol/(m3 h) 2.657.56 m3/(m2 h) 1.04.0 kmol/m3 0.0520.819 mol CO2/mol amine 303323 K (1 K) 103 kPa

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with that of Maneeintr et al.21 It is very necessary to make all the comparisons fairly. The operational conditions (including inlet CO2 loading, MEA concentration, liquid and inert gas ow rates, gas-phase CO2 concentration) between both cases should be virtually the same, so that the dierent KGav values from experiments can be attributed to the type and size of packing. As illustrated by the results shown in Figure 2, the results between two studies followed a similar trend, indicating that

in the range of lean CO2 loading stream, according to the work of Hartono et al.,15 who studies the equilibrium solubility of CO2 in aqueous DETA solutions. In addition, the maximum liquid ow rate of DETA was kept lower than that of MEA, because DETA has faster reaction kinetics and higher absorption capacity than MEA,8,15 which means the CO2 can be consumed faster in the case of DETA than that of MEA. In order to compare the KGav at the same CO2 concentration (YA = 0.12), the liquid ow rate of DETA solutions must be controlled to be lower than that of MEA. If the liquid ow rate that has been used is too high, bubbles might be created. The bubbles directly aect the active contact area between CO2 and absorbent, resulting in a drastic decrease in the mass-transfer performance. 3.3. Sample Analysis. The amine concentrations of solutions were veried by titration with a known volume of 1.0 N HCl, with Methyl Orange as an indicator. The CO2 loading in liquid sample was determined by the standard method given by the Association of Ocial Analytical Chemists (AOAC).26 The gas-phase samples were determined by an infrared CO2 gas analyzer (Model 302K, Nova Analytical Systems, Inc., Hamilton, Ontario, Canada). This analyzer can measure CO2 concentrations up to 20%.

Figure 2. Comparison between CO2 absorption performance in columns packed with Dixon rings and DX structured packing.

4. RESULTS AND DISCUSSION 4.1. Verifying the Packed Column Performance. In order to evaluate the performance of the Dixon ring, the prophase work of the full study is to compare the KGav values for the MEACO2 system by using Dixon rings and DX structured packing. Table 2 shows the packed column characteristics and operational conditions of this work, together
Table 2. Column Characteristics and Operational Conditions

KGav values increase as the solution concentration increases. Normally, one would expect that a higher specic surface area oers superior mass-transfer performance, but this is not always the case. As can be seen from the results, the performance of the Dixon ring was inferior to DX structured packing. The lower KGav values observed in the Dixon rings can be explained as being partially due to the nature of random packing that it is subject to the generation of bridging and cavitation phenomena in a packed bed when installed in a column randomly. When these phenomena are presented, they will deteriorate the ow distributions for contacting phases. This can give rise to unfavorable situations: (i) gases will ee away from the cavities, because of the low ow resistance, and (ii) liquid channeling and wall ow would increase. Therefore, the nonuniform distribution leads to a decrease in the eective interfacial area, which is unfavorable to mass-transfer behavior. Despite the superior performance of DX structure packing in the MEA CO 2 system, it should be noted that the manufacturing cost of structure packing is usually higher than that of random packing. Furthermore, within current industry, there still exist a large number of towers with random packing.

value description diameter of the column packing type surface area void fraction absorption system gas-phase CO2 concentration inert gas ow liquid ow rate solvent concentration CO2 loading Maneeintr et al.21 28 mm DX structured packing 900 m2/m3 0.775 MEACO2 13.9%14.9% 30.5331.19 kmol/(m2 h) 8.088.67 kmol/(m2 h) 1.03.0 kmol/m3 0.0110.204 mol CO2/mol amine
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this work 24 mm 3 3 Dixon ring 2400 m2/m3 0.93 MEACO2 14.0%14.8% 30.6131.10 kmol/(m2 h) 8.238.64 kmol/(m2 h) 1.03.0 kmol/m3 0.0320.197 mol CO2/mol amine
dx.doi.org/10.1021/ie300830h | Ind. Eng. Chem. Res. 2012, 51, 1205812064

Industrial & Engineering Chemistry Research Therefore, it is meaningful to investigate the absorption of CO2 into aqueous DETA in a column randomly packed with Dixon rings. 4.2. Eect of Lean CO2 Loading on KGav. CO2 loading is vital in a gas separation process; it refers to the sum of CO2 dissolved in solution by chemical and physical absorption. The CO2 loading reects the amount of active free amine molecules that have been consumed and that of active free amine molecules left in the solution. Under the same operating conditions of liquid ow rate, amine concentration, and temperature, DETA can absorb more CO2 than MEA, because DETA has higher absorption capacity and faster reaction kinetics than MEA.8,14,15 To ensure that the molar ratio of CO2 at the outlet gas (YA) is close to 0.12, the CO2 loading of DETA and MEA should be in the ranges of 0.0520.819 mol CO2/ mol amine and 0.0080.232 mol CO2/mol amine, respectively. These ranges of CO2 loading for DETA and MEA can be obtained from the absorption experiment, where the CO2 loading range was varied until the value of YA was 0.12. As shown from Figure 3, the mass-transfer performance of DETA is superior to that of MEA. The downtrend curves

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Figure 4. Eect of solution concentration on KGav (liquid ow rate = 3.98 m3/(m2 h); inert gas ow rate = 39.45 kmol/(m2 h); inlet CO2 loading = 0.1790.218 mol CO2/mol amine; T = 303 K).

fast absorption of CO2 into amine solution. However, the increase in solution concentration would lead to an increase in solution viscosity. The high viscosity militates against the diusion of CO2 from the gas/liquid interface to the bulk liquid phase. Aside from the eects on mass transfer, solution concentration also has great inuence on equipment corrosion. Thus, multiple factors should be taken into account to optimize solution concentration. 4.4. Eect of Liquid Flow Rate on KGav. Liquid ow rate has a close bearing on mass-transfer performance. The eect of changing liquid ow rate on KGav is presented in Figure 5. It

Figure 3. Eect of CO2 loading on KGav (liquid ow rate = 3.98 m3/ (m2 h); inert gas ow rate = 39.45 kmol/(m2 h); solvent concentration = 2.0 kmol/m3; T = 303 K).

indicate that KGav decreases as the CO2 loading increases for both systems. The KGav of DETA was reduced by 60% when the lean CO2 loading was reduced from 0.052 mol CO2/mol amine to 0.819 mol CO2/mol amine. It can be interpreted that the higher the CO2 loading, the fewer free active DETA molecules left in the solution, reecting the smaller driving force for mass transfer. However, in the entire absorption desorption process, in order to reach lower lean CO2 loadings, more energy must be consumed to release CO2. Therefore, blindly pursuing low CO2 loadings is not advisible. 4.3. Eect of Solution Concentration on KGav. Solution concentration is an important variable worthy of deep discussion, since it aects the amount of absorbent used and the CO2 removal eciency. The absorption experiments were done over concentration ranges of 1.04.0 mol/L for DETA and 2.05.0 mol/L for MEA in order to investigate the eect of solution concentrations on mass-transfer performance. It can be seen from Figure 4 that DETA performs better than MEA under similar conditions, KGav values of both systems increase as the solution concentration increases. It is mainly because the increase in solution concentration would bring a larger amount of free active amine molecules per unit volume, to improve the enhancement factor, which is conducive to the
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Figure 5. Eect of liquid ow rate on KGav (inert gas ow rate = 39.45 kmol/(m2 h); solvent concentration = 2.0 kmol/m3; inlet CO2 loading = 0.1790.215 mol CO2/mol amine; T = 303 K).

can be seen that the KGav values increase as the liquid ow rate increases for both solvents under certain conditions. This is because increasing the liquid ow rate may yield three universally accepted results: (i) provide more free active amine molecules that make the absorption capacity of CO2 larger; (ii) enlarge the eective interfacial area, because more liquid phase spreads on the packing surface, causing more liquid to be exposed to the gas phase; and (iii) the turbulent extent turns to be more intense, which will lead to a remarkable decrease of the thickness of liquid lm, resulting in an increase in the liquid-side mass-transfer coecient. In addition, Figure 5 also reveals that an upward curve of DETA is steeper than that of MEA. It can be inferred from this observation that the liquid ow rate aects the KGav value of
dx.doi.org/10.1021/ie300830h | Ind. Eng. Chem. Res. 2012, 51, 1205812064

Industrial & Engineering Chemistry Research DETA more than that of MEA. By introducing the same amount of free active amine into the column, the mass-transfer performance of DETA should be higher than that of MEA. This is because DETA not only has faster reaction kinetics, but it also has a higher absorption capacity than MEA.8,14,15 4.5. Eect of Gas Flow Rate on KGav. According to twolm theory, gas-phase mass-transfer coecient (kg) and liquidphase mass-transfer coecient (kL) are two important parameters for KGav. The CO2 absorption process with amine solution is considered to be a liquid lm control process, which means kL is the major determinant of mass-transfer performance. Therefore, Figure 6 shows that the inert gas ow rate has

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Figure 7. Eect of liquid temperature on KGav (liquid ow rate = 3.98 m3/(m2 h); inert gas ow rate = 39.45 kmol/(m2 h); solvent concentration = 2.0 kmol/m3; inlet CO2 loading = 0.1890.206 mol CO2/mol amine).

Figure 6. Eect of inert gas ow rate on KGav (liquid ow rate = 3.98 m3/(m2 h); solvent concentration = 2.0 kmol/m3; inlet CO2 loading = 0.1790.213 mol CO2/mol amine; T = 303 K).

no signicant eect on the KGav value for both the DETA CO2 and MEACO2 systems. This observation corresponds well with the works of Aroonwilas and Tontiwachwuthikul20 and deMontigny et al.,27 who studied the mass-transfer performance of CO2 absorption into aqueous solutions of AMP and concentrated MEA in a structured packed column. 4.6. Eect of Liquid Temperature on KGav. Liquid temperature is also an important parameter impacting the absorption performance. It was found that the KGav values of both DETA and MEA increased as the liquid feed temperature increased over the temperature range of 303323 K, as presented in Figure 7. Such behaviors are attributable to the increasing second-order reaction rate constant (k2) and the decreasing liquid viscosity (), which are benecial to increasing the absorption eciency. However, as the liquid feed temperature increased beyond a certain value, the reverse CO2 absorption reaction dominated the entire reaction process, because the amineCO2 reaction is exothermic, thus; the absorption eciency was found to be deteriorated. Another reason was that the increased temperature resulted in a lower equilibrium CO2 solubility. Therefore, liquid feed temperatures that are too high would discourage CO2 absorption into aqueous DETA and MEA solution.

The calculation approach of KGav used in the present work has been widely accepted to be adequate and applicable in the eld of CO2 absorption.2023,25,27 In order to design a gas absorber with chemical absorption, the mass-transfer performance, in terms of KGav, must be considered, since the height of the column is controlled by KGav.28 However, KGav varies with the operating conditions (e.g., liquid ow rate, liquid-phase CO2 loading, and partial pressure of CO2), types of packing, and amines. Therefore, the eective predictive correlation for KGav is extremely vital. 5.1. Validations of Conventional Mass-Transfer Correlation for MEA. Many researchers have presented shortcut correlations to estimate the mass-transfer performance for dierent packings and systems. Kohl and Riesenfeld1 proposed a correlation for predicting the KGav of MEA system in random packing as
L 0.67 K Gv = F [1 + 5.7(eq )C exp(0.0067T 3.4PCO2)
(2)

5. MASS-TRANSFER CORRELATION It was mentioned by Kohl and Rieseneld,1 Liang et al.,28 and Astarita et al.29 that the mass-transfer performance in the packed column, in terms of mass-transfer coecient (KGav), is considered to be a very important parameter for engineering design of the size of the absorption column, as well as for eectively operating and simulating the absorption column.
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where F is the packing factor, L is the liquid ow rate (lb/(ft2 h)), the liquid viscosity (cps), eq the CO2 loading of solution in equilibrium with PCO2 (mol/mol), the CO2 loading of solution (mol CO2/mol amine), C the amine concentration of the solution (kmol/m3), T the temperature (F), and PCO2 the partial pressure of CO2 over solution (atm) [units are quoted directly from Kohl and Riesenfeld1]. It should be pointed out that this correlation (eq 2) was proposed to predict the KGav value of CO2 absorption into aqueous MEA solution with absorbers packed with early commonly used random packings, such as ceramic saddles, steel rings, glass rings, and polyethylene tellerettes. Equation 2 might not be applicable with other amine systems.20 Also, it was conrmed by deMontigny et al.27 that this correlation is only applicable for random packing, but is not applicable for structured packing. To check against applicability of the predictive correlation (eq 2) in the Dixon rings, the plot of KGaV/(L/)0.67 vs (eq )C exp(0.0067T 3.4PCO2) was investigated, as shown in Figure 8. It can be seen that a linear relationship between KGaV/(L/)0.67 and (eq )C exp(0.0067T 3.4PCO2) was
dx.doi.org/10.1021/ie300830h | Ind. Eng. Chem. Res. 2012, 51, 1205812064

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Figure 8. Relationship between KGaV/(L/)0.67 and (eq )C exp(0.0067T 3.4PCO2) for the MEACO2 system.

Figure 9. Relationship between KGav/(L0.67G0.08) and (eq )C/ PCO2 and for the DETACO2 system.

observed, which reaches observations similar to the work of Kohl and Riesenfeld.1 The coecients in the predictive correlation can be obtained from the slope and x-intercept of the plot in Figure 8. Therefore, the predictive correlation for KGav for CO2 absorption into aqueous solutions of MEA in a randomly Dixon ring packed column can be expressed as
L 0.67 K Gv = [0.00805(eq )C L exp(0.0067T 3.4PCO2) 0.000221]
(3)

to expedite the application of the new mass-transfer correlation for the DETACO2 system.

The dierence in coecients between eqs 2 and 3 can be observed because of the dierent types and sizes of packing. The results show that predicted KGav values are in relatively good agreement with the experimental values, with an average absolute deviation (AAD) of 14% (which is generally acceptable in this eld). 5.2. Mass-Transfer Correlation for DETA. Based on the correlation development procedure used in our previous work,20,21 KGav is found to be a function of the operating conditions:
K Gv LbGc (eq )C PCO2
(4)

6. CONCLUSIONS In the present work, comparative mass-transfer experiments of the absorption of CO2 into aqueous MEA and DETA solutions were investigated in a laboratory-scale absorption column packed with random Dixon ring packing. The absorption performance was evaluated in terms of volumetric overall masstransfer coecient (KGav). The results show that the masstransfer performance of DETA is better than that of MEA. In addition, it was found that liquid-phase CO2 loading, amine concentration, liquid ow rate, and liquid inlet temperature eect KGav in that KGav increases as the liquid ow rate, amine concentration, and liquid inlet temperature increase, and KGav decreases as the liquid-phase CO2 loading increases over ranges of operating conditions, as shown in Tables 1 and 2. However, the inert gas ow rate has no signicant eect on KGav. The predictive correlations for KGav for CO2 absorption into aqueous solutions of MEA and DETA in a randomly Dixon ring packed column were successfully developed with an average absolute deviation (AAD) of 14% and 16%, respectively.

AUTHOR INFORMATION

Corresponding Author

By trial and error, the optimum values of the constants b and c were found to be b = 0.67 and c = 0.08. The plot of KGav/ (L0.67G0.08) and (eq )C/PCO2 and was found to be a straight line, as presented in Figure 9. Based on linear regression analysis, the predictive correlation for KGav for CO2 absorption into aqueous solutions of DETA in a randomly Dixon ring packed column can be expressed as
(eq )C K Gv = L0.67G 0.080.752 + 0.142 PCO2

*Tel.: +86-13618481627. Fax: +86-731-88573033. E-mail address: zwliang@hnu.edu.cn.

Notes

The authors declare no competing nancial interest.

(5)

It was found that the predicted KGav results were relatively in good agreement with the experimental results with an AAD of 16% (which is generally acceptable in this eld). However, it is not known whether this new correlation developed for the DETACO2 system is applicable for other absorption columns, especially to those with structured packing. Therefore, further experimental testing is necessary
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ACKNOWLEDGMENTS The nancial support from National Natural Science Foundation of China (NSFC No. 21276068), Ministry of Hunan Provincial Science and Technology (No. 2010SK2001), Chinas State Project 985 in Hunan UniversityNovel Technology Research & Development for CO2 Capture, National Students Innovation Training (SIT) is gratefully acknowledged. In addition, we would also like to acknowledge the research supports over the past many years to the Industrial Research ConsortiumFuture Cap Phase II of International Test Centre for CO2 Capture (ITC) at the University of Regina. We would also like to acknowledge the research supports from the followings organizations: Natural Sciences
dx.doi.org/10.1021/ie300830h | Ind. Eng. Chem. Res. 2012, 51, 1205812064

Industrial & Engineering Chemistry Research and Engineering Research Council of Canada (NSERC), Canada Foundation for Innovation (CFI), Saskatchewan Ministry of Energy & Resources, Western Economic Diversication, Saskatchewan Power Corporation, Alberta Energy Research Institute (AERI) and Research Institute of Innovative and Technology for the Earth (RITE).

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NOMENCLATURE

(1) Kohl, A. L.; Rieseneld, F. C. Gas Purication, 4th Edition; Gulf Publishing: Houston, TX, 1985. (2) Dawodu, O. F.; Meisen, A. Degradation of Alkanolamine Blends by Carbon Dioxide. Can. J. Chem. Eng. 1996, 74, 960. (3) Sema, T.; Naami, A.; Fu, K.; Edali, M.; Liu, H.; Shi, H.; Liang, Z.; Idem, R.; Tontiwachwuthikul, P. Comprehensive Mass Transfer and Reaction Kinetics Studies of CO2 Absorption into Aqueous Solutions of Blended MDEAMEA. Chem. Eng. J. 2012, in press (DOI: 10.1016/j.cej.2012.08.016). (4) Barth, D.; Tondre, C.; Delpuech, J. J. Kinetics and Mechanisms of the Reactions of Carbon Dioxide with Alkanolamines: A Discussion Concerning the Cases of MDEA and DEA. Chem. Eng. Sci. 1984, 39, 1753. (5) Chakraborty, A. K.; Astrita, G. CO2 Absorption in Aqueous Solutions of Hindered Amines. Chem. Eng. Sci. 1986, 41, 997. (6) Sema, T.; Naami, A.; Liang, Z.; Idem, R.; Tontiwachwuthikul, P.; Shi, H.; Wattanaphan, P.; Henni, A. Analysis of Reaction Kinetics of CO2 Absorption into A Novel 4-Diethylamino-2-Butanol Solvent. Chem. Eng. Sci. 2012, 81, 251. (7) Shi, H.; Sema, T.; Naami, A.; Liang, Z.; Idem, R.; Tontiwachwuthikul, P. 13C NMR Apectroscopy of A Novel Amine Species in the DEAB-CO2-H2O System: VLE Model. Ind. Eng. Chem. Res. 2012, 8608. (8) Hartono, A.; da Sliva, E. F.; Svendsen, H. F. Kinetics of Carbon Dioxide Absorption in Aqueous Solution of Diethylenetriamine (DETA). Chem. Eng. Sci. 2009, 64, 3205. (9) Sema, T.; Naami, A.; Idem, R.; Tontiwachwuthikul, P. Correlations for Equilibrium Solubility of Carbon Dioxide into Aqueous Solutions of 4-Diethylamino-2-Butanol. Ind. Eng. Chem. Res. 2011, 50, 14008.
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av = specic area of contactor (m2/m3) = solution CO2 loading (mol CO2/mol amine) eq = CO2 loading of solution in equilibrium with PCO2 (mol CO2/mol amine) CA,I = concentration of solute at the interface (kg mol/m3) CA,L = concentration of solute in the bulk liquid (kg mol/m3) F = packing correction factor G = inert gas ow rate (kg mol/(m2 h)) KGav = gas-phase volumetric overall mass-transfer coecient (kg mol/(m2 s kPa)) k2 = second order forward rate coecient for reaction i (m3/ (kmol s)) k L = physical liquid-phase mass-transfer coecient (m/s) kL = chemical liquid-phase mass-transfer coecient (m/s) P = total system pressure (kPa) T = temperature (K) = liquid viscosity (cps) y* A = mole fraction of solute A in equilibrium with CA,L(mol/ mol) yA,G = mole fraction of solute A in the bulk gas phase (mol/ mol) yA,I = mole fraction of solute A at the interface (mol/mol) YA = mole ratio (mol/mol) Z = height of packed column (m)

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dx.doi.org/10.1021/ie300830h | Ind. Eng. Chem. Res. 2012, 51, 1205812064