International Journal of Greenhouse Gas Control 12 (2013) 390398

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International Journal of Greenhouse Gas Control

journal homepage: www.elsevier.com/locate/ijggc

1D absorption kinetics modeling of CO2 DEABH2 O system

Teerawat Sema a,b , Abdulaziz Naami b , Zhiwu Liang a,b, , Raphael Idem a,b , Hussameldin Ibrahim b , Paitoon Tontiwachwuthikul a,b,
a b

Joint International Center for CO2 Capture, and Storage (iCCS), College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, PR China International Test Centre for CO2 Capture (ITC), Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan S4S 0A2, Canada

a r t i c l e

i n f o

a b s t r a c t
The experimental kinetics data for carbon dioxide (CO2 ) absorption into aqueous 4-diethylamino2-butanol (DEAB) solutions were measured by laminar jet absorber at atmospheric pressure over a temperature range of 298318 K, a DEAB concentration range of 12 M, and a CO2 loading range of 0.0010.18 mol CO2 /mol amine. These data were interpreted with the aid of 1 dimension comprehensive numerically solved CO2 absorption rate/kinetics model, which takes into account the coupling between chemical equilibrium, mass transfer, and chemical kinetics of all possible chemical reactions between CO2 and aqueous DEAB solutions. The partial differentialnonlinear algebraic equations of the model were solved by the nite element method (FEM) based on COMSOL software. The results show that CO2 absorption reaction with DEAB is faster than that with MDEA, also comparable with those with AMP and DEA, but slower than those with MEA and PZ, respectively. In addition, the reaction kinetics in terms of enhancement factor was found to increase as DEAB concentration increased, and increase as temperature increased, but decrease as CO2 loading increased. 2012 Elsevier Ltd. All rights reserved.

Article history: Received 17 April 2012 Received in revised form 6 August 2012 Accepted 13 November 2012 Keywords: Absorption Carbon dioxide Kinetics Modeling

1. Introduction It has been over three decades since the rst assessment report of the Intergovernmental Panel on Climate Change (IPCC) pointed out that the drastically increasing of greenhouse gases, such as carbon dioxide (CO2 ), methane, and chlorouorocarbons (CFCs), are mainly emitted from human activities. The emissions will enhance the greenhouse effect, resulting in the increasing of earth surface temperature (Houghton et al., 1990; Williams et al., 2012). Recently, global warming and climate change issues are receiving attention globally. One of the urgently policies is to control the greenhouse gas emissions to the atmosphere (Meinshausen et al., 2009; Ibrahim et al., 2012). CO2 is generally accepted as a major greenhouse gas since it responsible for about 57% of the contribution on the global warming potential (Lashof and Ahuja, 1990).

Corresponding author at:Joint International Center for CO2 Capture, and Storage (iCCS), College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, PR China; International Test Centre for CO2 Capture (ITC), Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan S4S 0A2, Canada. Tel.: +86 73188573033. Corresponding author at: Joint International Center for CO2 Capture, and Storage (iCCS), College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, PR China; International Test Centre for CO2 Capture (ITC), Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan S4S 0A2, Canada. Tel.: +86 13618481627. E-mail addresses: zwliang@hnu.edu.cn (Z. Liang), paitoon@uregina.ca (P. Tontiwachwuthikul). 1750-5836/$ see front matter 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.ijggc.2012.11.023

Almost 60% of CO2 emissions are from coal-red power generation plants and other industrial processes, such as reneries and natural gas processing plants. In order to control the CO2 emissions, several technologies have been applied. However, post-combustion amine based CO2 capture technology is recently accepted as one of the most cost effective and environmental friendly manner (Devid and Herzog, 2000; Rao and Rubin, 2002; Liang et al., 2011). A wide variety of amines such as monoethanolamine (MEA), diethanolamine (DEA), methyldiethanolamine (MDEA) have been industrially used for capturing CO2 for a number of years (Kohl and Nielsen, 1997; Sema et al., 2012a). Recently, Tontiwachwuthikul et al. (2008), Maneeintr et al. (2009), Sema et al. (2011) have developed and investigated the performances of a newly developed amino alcohol solvent, 4-diethylamino-2-butanol (DEAB). They found that the absorption capacity of DEAB is competitive with that of piperazine (PZ) and higher than those of 2-amino-2methyl-1-propanol (AMP), MDEA, DEA, and MEA. Moreover, they also found that the regeneration energy of DEAB is lower than those of MDEA, DEA, and MEA, respectively. Regarding to these outstanding performances, DEAB is now being considered as a promising alternative solvent for capturing CO2 . However, a better solvent for capturing CO2 should not only provide high absorption capacity and low regeneration energy, but should also have fast reaction rate (reaction kinetics), low solvent degradation, and low corrosiveness. More importantly, the effective design of the absorber for amine based CO2 treating plant needs an understanding of reaction kinetics data between CO2 and amine (Astarita et al., 1983).

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Nomenclature AMP Ce Cj0 CFCs CO2 d Di DEA DEAB E FDM FEM h HeCO2 k2i
0 kL

Ki L MEA MDEA N Nave PCO2 PZ RA T TEA u x

2-amino-2-methyl-1-propanol equilibrium concentration of gas at interface, mol/L or kmol/m3 bulk concentration for species j, kmol/m3 chlorouorocarbons carbon dioxide jet diameter, m diffusivity of chemical species i, cm2 /s or m2 /s diethanolamine 4-diethylamino-2-butanol enhancement factor nite difference method nite element method jet height, cm or m Henrys constant, kPa m3 /kmol second order forward rate coefcient for reaction i, m3 /kmol s liquid phase mass transfer coefcient for physical absorption of CO2 , m/s chemical equilibrium constant for reaction i liquid ow rate, cm3 /s or m3 /s monoethanolamine methyldiethanolamine local CO2 absorption rate per unit area, kmol/m2 s average CO2 absorption rate per unit area, kmol/m2 s partial pressure of CO2 , kPa piperazine rate of gas absorption, mol/s temperature, K triethanolamine velocity, m/s penetration depth, m

both FDM and FEM provide very accurate predicted CO2 absorption rate. Also, no signicant difference between the results obtained from FDM and FEM were observed. In this study, the experimental kinetics data of CO2 and aqueous DEAB solutions were measured using the laminar jet absorber over ranges of temperatures, DEAB concentrations, CO2 loadings, and contact times. The obtained experimental data were then used to develop the 1D numerically solved comprehensive CO2 absorption rate/kinetics model (using the FEM based on COMSOL software) for the absorption of CO2 in aqueous solutions of DEAB. The chemical equilibrium, the mass transfer, and the chemical kinetics of all possible reactions were also taken into account in this comprehensive model. 2. Materials and methods 2.1. Chemicals DEAB was synthesized according to the procedure described by Tontiwachwuthikul et al. (2008) in our solvent synthesis laboratory in the International Test Centre for CO2 Capture (ITC) at the University of Regina. The purity of synthesized DEAB was determined by GCMS and found to be 95%. Aqueous DEAB solutions of desired concentrations were prepared by adding a known amount of de-ionized water and predetermined amounts of DEAB. CO2 with purities of 99.9% were supplied by Praxair Inc., Canada. 2.2. CO2 absorption rate The CO2 absorption rate was measured using the laminar jet absorber. A detailed description of the laminar jet absorber and its operation can be seen in Al-Ghawas et al. (1989) and Aboudheir et al. (2004). Briey, the amine solution was degassed by spraying it into a vacuum, and then the degassed amine solution was passed through the temperature-controlled water jacket in order to reach the desired temperature. The degassed amine solution was then passed through the jet nozzle in order to continuously generate a smooth-surfaced rod-like jet in the absorption chamber. The soaplm meter (ranging from 0.1 to 10 ml/min with 1% accuracy) was used to measure the rate of absorption (RA ). The two dimensional microscope was used to measure jet height (h) and jet diameter (d). Finally, the discharged liquid was collected and liquid ow rate (L) was measured. According to the penetration theory for physical absorption, RA can be dened as:
RA = 4Ce (DLh) 1/2

Greek letters CO2 loading, mol CO2 /mol amine viscosity, g/cm s contact time, s

Laminar jet absorber is one of the apparatuses that provide very accurate and reliable kinetics data because (i) the interfacial area is known accurately and (ii) the physical absorption rate has been shown to agree with the Higbies penetration theory prediction (Astarita et al., 1983; Aboudheir et al., 2003, 2004). One of the very rst numerical comprehensive CO2 absorption rate/kinetics models for aqueous amine solutions was developed by Hagewiesche et al. (1995). They studied the absorption of CO2 in aqueous solutions of blended MEAMDEA using laminar jet absorber based on the Higbies penetration theory. However, the experiments were performed at only 313 K. Recently, more comprehensive kinetics model for CO2 absorption into loaded aqueous amine solutions of MEA, blended MEAMDEA, and blended MDEAPZ were developed by Idem et al. (2009), Edali et al. (2009, 2010), and Edali (2010). In their studies, the experimental kinetics data were obtained from laminar jet absorber at various temperatures, amine concentrations, CO2 loadings, and contact times. Moreover, the chemical equilibrium, the mass transfer, and the chemical kinetics of all possible reactions were taken into account in their comprehensive models. Two numerical techniques, which are the nite difference method (FDM) based on Barakat-Clark scheme and the nite element method (FEM) based on COMSOL software, were used for solving the CO2 absorption rate/kinetics model. They found that

(1)

Ce can be determined by: Ce =

PCO2 HeCO2

(2)

where Ce is the equilibrium concentration of gas at the interface, D is the diffusivity of gas in the liquid, L is the liquid ow rate, h is jet height, PCO2 is partial pressure of CO2 , and HeCO2 is Henrys

constant. A plot of RA and (Lh) at various ow rates and jet heights should provide a straight line through the origin with a slope of 4Ce D1/2 . The laminar jet absorber was validated with water for the diffusivity of CO2 at 298 K, which was found to be 1.97 105 cm/s (while Al-Ghawas et al. (1989) and Aboudheir et al. (2004) found to be 1.95 105 cm/s and 1.96 105 cm/s, respectively). Also some CO2 diffusivity measurements were repeated for the repeatability. The results show that the deviation percentage of CO2 diffusivity measurement is 0.7%.

1/2

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3. Theory Based on the proposed mechanism for the reaction between CO2 and DEAB, a vaporliquid equilibrium (VLE) model and an absorption rate/kinetics model for predicting the kinetics data were developed. 3.1. Chemical reaction scheme for CO2 DEAB aqueous system The chemical reactions in CO2 DEAB aqueous system are governed by the following equations: RR2 N + H+ RR2 NH+ CO2 + RR2 N + H2 O
K5 K4 ,k24 ,k24 K3

CO2 in the solution or Henrys constant (He; kPa m3 /kmol). The con0 0 centrations of C1 C7 can be obtained by simultaneously solving the mass balance equations, equilibrium constant equations, and Henrys law relationship as shown below:Total DEAB balance:
0 0 [DEAB]0 = C6 + C7

(11)

Total carbon balance:

0 0 0 [DEAB]0 = C1 + C2 + C4

(12)

Charge balance:
0 0 0 0 0 C5 + C7 = C2 + C3 + 2C4

(3) RR2 NH+ + HCO 3 (4) (5) (6) (7) (8)

(13)

Independent equilibrium constants: K4 =

0 0 C2 C7 0 0 C1 C6 0 0 C2 C5 0 C1 0 C2 0 0 C1 C3

H2 O + CO2 H+ + HCO 3 CO2 + OH

K6 ,k26 ,k26

(14)

HCO 3

K7 HCO H+ 3 K8

+ CO2 3

K5 =

(15)

H2 OH+ + OH

K6 =

(16) (17)

RR2 N represents DEAB where R is (CH2 )2 CH(CH3 )OH and R is CH2 CH3 . Ki is the chemical equilibrium constant for reaction i. k2i is the second order forward rate coefcient for reaction i, DEAB is considered as a tertiary amine since it has 3 carbon atoms attached to the nitrogen atom. In this case, DEAB does not react directly with CO2 but it acts as a base which catalyzed the hydration of CO2 (Hagewiesche et al., 1995; Kohl and Nielsen, 1997) as presented in Eq. (4). Reactions (4) and (6) are considered to be reversible with nite reaction rates. Whereas reactions (3), (5), (7), and (8) are considered to be reversible and instantaneous with respect to mass transfer and at equilibrium, since they involve only proton transfer (Hagewiesche et al., 1995). Based on Eqs. (3)(8) it can be seen that not all of the chemical equilibrium constants are independent. Only 4 chemical equilibrium constants (K4 , K5 , K6 , and K8 ) are independent. The remaining two (K3 and K7 ) can be obtained by the combination of independent chemical equilibrium constants as shown in Eqs. (9) and (10). Also, water concentration is considered to be constant due to the presence of excess amount of water in the solution (the water concentration is much higher than DEAB concentration). K3 = K7 = [H+ ][RR2 N] [H+ ][CO2 ] 3 [HCO ] 3 [RR2 NH+ ] = = K4 K5 K4 K3 K8 (9)

0 0 K8 = C3 C5

Henrys law relationship: HeCO2 =

CCO

PCO2
2

(18)

The chemical equilibrium constants K4 , K5 , K6 and K8 can be found in the works of Kent and Eisenberg (1976), Edwards et al. (1978), and Sema et al. (2011). The physical solubility of CO2 into aqueous DEAB solutions or HeCO2 can be estimated by the correlation proposed by Sema et al. (2012b). The 8 coupled nonlinear algebraic equations, i.e. Eqs. (11)(18), were then simultaneously solved for the 8 unknowns, which are 0 0 C1 C7 and equilibrium partial pressure (PCO2 ), by inputting the initial guess for each unknown. In the present study, the FEM based on COMSOL 4.1 software with 0D stationary solver mode was applied. After the software had been operated with the rst set of initial guess, values of the unknowns were obtained. Then these new values are subsequently used as the second set of initial guess for solving of the 8 unknowns. This procedure is repeated until different percentage deviation of the results of each unknown for successive attempts is less than 0.01%. 3.3. CO2 absorption rate/kinetics model A comprehensive CO2 absorption rate/kinetics model was developed in order to interpret the absorption rate data of CO2 in aqueous DEAB solutions, from which the kinetics data were extracted. This model takes into account the coupling between chemical equilibrium, mass transfer, and chemical kinetics of all possible chemical reactions. Also, the model is capable to predict the CO2 absorption rate and enhancement factor from the system physiochemical properties, as well as predicting the kinetics of reaction (which is the second order forward rate coefcient for reaction 4 or k24 or kDEAB ) from the experimental CO2 absorption rate data. The model was derived from a full 3D cylindrical coordinate system, which is the shape of the cylindrical liquid jet generated in the laminar jet absorber as shown in Fig. 1. The gasliquid interface is considered as an outer boundary. Also, the diffusion in radial direction is taken into account. Therefore, the absorption of CO2 into the cylindrical liquid jet, with constant density and diffusivity, is governed by Eq. (19) (Astarita et al., 1983). This equation indicates

(10)

The chemical species in Eqs. (3)(8) have been renamed for convenience in the numerical treatment as follows: C1 = [CO2 ], C5 = [H+ ], C2 = [HCO ], 3 C6 = [RR2 N], C3 = [OH ], C4 = [CO2 ], 3

C7 = [RR2 NH+ ]

Also, the subscripts 17 are represented the chemical species of CO2 , HCO , OH , CO2 , H+ , [RR2 N], and RR2 NH+ , respectively. 3 3 3.2. Vaporliquid equilibrium (VLE) model The bulk concentrations of all chemical species in liquid phase 0 0 at equilibrium (C1 C7 ), which are required for the kinetics study, can be estimated by the VLE model (Shi et al., 2012a). The input parameters for this model are initial concentration of DEAB in the solution ([DEAB]0 ; kmol/m3 ), equilibrium CO2 solubility in aqueous solutions of DEAB or CO2 loading (; mol CO2 /mol DEAB), equilibrium constants of involved reactions (Ki ), and physical solubility of

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Total carbon balance: C2 C4 2 C1 2 C2 2 C4 C1 + + = D1 + D2 + D4 2 2 t t t x x x2 Total DEAB balance: C7 2 C6 2 C7 C6 + = D6 + D7 2 t t x x2 Total charge balance: 2 C2 2 C3 C3 C4 C5 C7 C2 + +2 + D3 = D2 t t t t t x2 x2 + 2D4 2 C4 2 C5 2 C7 D5 D7 2 2 x x x2 (24) (23) (22)

All reactions at equilibrium (only the independent equilibrium constants): including K4 , K5 , and K8 , are given in Eqs. (14), (15) and (17), respectively. where R4 and R6 , which are the reaction rate expressions for reactions (4) and (6), respectively, can be presented as: R4 = kDEAB C1 C6 + R6 = k26 C1 C3 +
Fig. 1. Schematic diagram of the liquid jet in the laminar jet absorber.

kDEAB K4 k26 K6 C2

C2 C7

(25) (26)

that the molecular transport is equal to the sum total of convection term, accumulation term (C/t), and reaction rate (R). If the diffusant is being created, R will be negative. D 2 C = u C + C +R t (19)

where D is diffusivity (m2 /s), C is concentration (m3 /kmol), u is velocity (m/s), and t is time (s). The assumption of constant density and diffusivity is valid in the laminar jet absorber because the change of concentration does not represent a substantial variation in the mole fraction of the diffusant due to the short contact time (Aboudheir et al., 2004). Eq. (19) can be simplied by following assumptions: (a) the penetration theory is applicable for the transport of the gas into liquid, in which the reaction takes place by unsteady state molecular diffusion in the liquid; (b) the penetration depth of the absorbed molecule is much smaller than the jet diameter due to the short contact time (created in the laminar jet absorber) between the absorbed gas and the liquid jet. Therefore, there is no curvature effect. The absorption of gas into liquid is then considered to be an innite depth with at surface; (c) the diffusion in the ow direction is negligible; (d) the liquid jet is quiescent so that no convection movements affect the transport of the absorbed gas. Regarding to these conditions, Eq. (19) can be simplied to the diffusion equation of Eq. (20). This equation governs the variation of time and space of the concentration of all reactants and products in the liquid phase (one equation for each component or material balance). C 2 C +R D 2 = t x (20)

Di is the diffusivity of chemical species i into the solution (m2 /s). The diffusivity of CO2 in aqueous solution of DEAB (D1 ) can be calculated from the predictive correlation developed by Sema et al. (2012b). Hikita et al. (1980) measured the diffusivity of MEA, DEA, and triethanolamine (TEA) in aqueous solution. They reported that the diffusivity affected by the group complexity. Since DEAB is a tertiary amine as same as TEA, it is reasonable to estimate the diffusivity of DEAB from that of TEA (the same assumption has also been made in the case of MDEA) (Hagewiesche et al., 1995). Thus, the diffusivity of DEAB (D6 ; cm2 /s) can be estimated by: D6 = (1.739 109 )
0.569842

(27)

CO2 , H+ , and RR2 NH+ were assumed to be equal to that of DEAB, 3 which is the most abundant species in the solution (Hagewiesche et al., 1995). The forward rate coefcient of Eq. (6) (k26 ; m3 /kmol s) was calculated from the correlation developed by Pinsent et al. (1956) as follow: log(k26 ) = 13.635 2895 T (28)

is solution viscosity (g/cm s), which can be calculated where based on the predictive correlation developed by Maneeintr et al. (2008), and T is temperature in K. Also, the diffusivity of HCO , OH , 3

Thus, there are 7 partial differentialnonlinear algebraic equations (Eqs. (14), (15), (17) and (21)(24)), which can be solved for the concentration of chemical species C1 C7 . Initial conditions: for all chemical species, j = 1, 2, 3, . . ., 7 Cj (x, 0) = Cj0 at t = 0 and 0 x (29)

Thus, the partial differential equations (PDEs) and the nonlinear algebraic equations govern the diffusion-reaction process of Eqs. (3)(8) can be described as follows: CO2 balance: 2 C1 C1 + R4 + R6 = D1 t x2 (21)

Boundary conditions: for all chemical species, j = 1, 2, 3, . . ., 7 Cj (, t) = Cj0 at x = and 0 t (30)

for volatile chemical species, j = 1 Cj (0, t) = Cj = Pj Hej at x = 0 and 0 t (31)

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for non-volatile chemical species, j = 2, 3, 4, . . ., 7 Cj t (0, t) = 0 at x = 0 and 0 t (32)

of species j in liquid phase (kmol/m3 ), which can be obtained by the vaporliquid equilibrium model. For laminar jet absorber, the contact time ( ) is found to be: = d2 h 4L

where C1 is the interfacial concentration of CO2 in the solution (kmol/m3 ), which is dened as the partial pressure of CO2 in the gas (P1 ; kPa) divided by the physical solubility of CO2 in the solution or Henrys constant (He1 ; kPa m3 /kmol). Cj0 is the bulk concentration

(33)

where d is jet diameter (m), h is jet height (m), and L is volumetric liquid ow rate (m3 /s). From Higbies penetration theory, the liquid phase mass transfer 0 coefcient for physical absorption of CO2 (kL ; m/s) is dened as:
0 kL = 2

D1

4 d

D1 L h

(34)

The local CO2 absorption rate per unit area (N; kmol/m2 s) is given as: N = D1 Cj t
x=0

absorption surface area can be calculated by measurement of liquid jet diameter and height using the two dimensional microscope). Then, experimental enhancement factor (Eexp ) can be calculated 0 using Eq. (37), where kL can be calculated by Eq. (34), C1 , which is equilibrium concentration of CO2 at interface can be calculated via Henrys law relationship as mentioned in Sema et al. (2012b), and C1 can be obtained from the developed VLE model. The predicted enhancement factor (Epred ) can also be calculated from Eq. (37). In this case, the rate of CO2 absorption per unit area is the predicted value from Eq. (36) by integrating (C1 /t)x=0 over the contact time ( ). (C1 /t)x=0 can be obtained from solving Eqs. (14), (15) and (17) and (21)(24) simultaneously using FEM based on COMSOL 4.1 software with 1D time-dependent mode under initial and boundary conditions mentioned in Eqs. (29)(32). In this calculation process, the second order forward rate coefcient for reaction 4 or k24 or kDEAB was considered as an adjusting parameter. For each experiment (at different initial DEAB concentrations, temperatures, initial CO2 loadings, and contact times), the value of kDEAB was adjusted until (Eexp Epred )/Eexp 1% (Hagewiesche et al., 1995). Then the forward reaction rate constant, kDEAB , was correlated with the reaction rate constant expression as shown in Eq. (38). kDEAB = A exp B T (38)

(35)

Thus, the average CO2 absorption rate per unit area (Nave ; kmol/m2 s) is obtained by integrating Eq. (35) over the contact time : Nave = D1
0

C1 (0, t) dt t

(36)

The effect of chemical reaction in terms of the enhancement factor, E, which is dened as the ratio of the absorption rate of CO2 into a reacting liquid to that if there was no reaction, is given by: E= Nave
0 0 kL (C1 C1 )

COMSOL is a commercial FEM software, which is widely accepted to be a very powerful and adequate for solving the partial differentialnon linear algebraic equations for chemical engineering application (Zimmerman, 2006; Pryor, 2009). The numerical treatment based on COMSOL software used in the present work has been proven to be adequate for developing the CO2 absorption rate/kinetics model for aqueous amine solutions as reported by our previous works (Idem et al., 2009; Edali et al., 2009, 2010; Edali, 2010), where CO2 absorption rate/kinetics models for aqueous amine solutions of MEA, blended MEAMDEA, and blended MDEAPZ were successfully developed. 4. Results and discussion 4.1. Vaporliquid equilibrium model The VLE model for aqueous DEAB solution was developed in order to predict the bulk concentrations of all chemical species

(37)

For each experimental CO2 absorption rate (kmol of CO2 /s) measured by the laminar jet absorber at various DEAB concentrations, CO2 loadings, temperatures, and contact times, one value of CO2 absorption rate per unit area (N; kmol/m2 s) can be obtained (the

Fig. 2. Liquid phase speciation and concentration in aqueous DEAB solutions as a function of CO2 loading () at initial DEAB concentration of 2.0 kmol/m3 and 298 K (dots are experimental data measured by 13 C NMR obtained from Shi et al. (2012b); solid lines are simulated data obtained from vaporliquid equilibrium model developed in this study).

T. Sema et al. / International Journal of Greenhouse Gas Control 12 (2013) 390398 Table 1 Species bulk concentration in aqueous DEAB solution of 2 kmol/m3 at 318 K and CO2 loading of 0.10 mol CO2 /mol amine. Species
0 C1 , 0 C2 , 0 C3 , 0 C4 , 0 C5 , 0 C6 , 0 C7 ,

395

Concentration (kmol/m3 ) 6.96 106 8.27 102 1.22 105 8.27 102 7.60 1013 1.682 0.317

[CO2 ] [HCO ] 3 [OH ] [CO2 ] 3 [H+ ] [DEAB] [DEABH+ ]

The experimental absorption rate data were then interpreted by the numerical solved CO2 absorption rate/kinetics model using FEM based on COMSOL 4.1 software with 1D time-dependent mode by considering kDEAB as an adjustable parameter. The kDEAB results were correlated with the reaction rate constant expression of Eq. (38) as: kDEAB = (4.01 1013 )exp 7527.7 T (39)

0 0 (C1 C7 ), which required for the CO2 absorption rate/kinetic modeling. Some simulated results for the bulk concentrations obtained from the VLE model developed in the present work are shown in Fig. 2 and Table 1. The comparison of the simulated results and the experimental values measured by 13 C NMR obtained from the work of Shi et al. (2012b) are shown in Fig. 2. This gure shows the species concentrations at 01 CO2 loading for 2.0 M (or kmol/m3 ) of aqueous DEAB solution at 298 K. It can be seen from Fig. 2 that the simulated bulk concentrations of all chemical species correspond well with the experimental values. Thus, it can be inferred that the VLE model developed in this work is applicable for predicting the bulk concentration of all species, and the predictions can then be used for establishing a CO2 absorption rate/kinetics model. Moreover, it can be observed from Fig. 2 that the DEAB concentration decreases as CO2 loading increases. This due to the DEAB protonation and the CO2 DEABwater reaction as shown in Eqs. (3) and (4), respectively. As a result, the protonated DEAB concentration, DEABH+ , increases as CO2 loading increases. One of the major products, which is HCO , is found to increase as CO2 loading increases. 3 As CO2 loading increases (which means more CO2 is introduced to the system), the HCO is formed due to CO2 reacts with DEAB3 water, water, and OH as shown in Eqs. (4)(6), respectively. At CO2 loading less than 0.4, [CO2 ] is found to increase due to the 3

CO2 formation by HCO as shown in Eq. (7). However, the [CO2 ] 3 3 3 decreases when CO2 loading is higher than 0.4. This is because of the acidity of the solution increases as CO2 loading increases. Then Eq. (7) is reversed to form HCO from CO2 . 3 3 4.2. CO2 absorption rate/kinetics model The CO2 absorption rate in aqueous DEAB solutions was measured by laminar jet absorber at atmospheric pressure over temperature range of 298318 K, DEAB concentration range of 1.02.0 M, and CO2 loading range of 0.0010.18 mol CO2 /mol amine. These operating conditions were selected because (i) DEAB was found to have lower heat of absorption than that from MDEA, DEA, and MEA; thus, lower absorption temperature is applicable in the case of DEAB (Sema et al., 2011), (ii) DEAB provides very high CO2 absorption capacity (competitive with PZ); thus, low DEAB concentration can achieve the satised CO2 absorption capacity (Tontiwachwuthikul et al., 2008; Maneeintr et al., 2009; Sema et al., 2011), and (iii) the ideal solution assumption is applicable at low CO2 loading (Edali, 2010).

The predicted kDEAB at 298 K compares with that of MDEA, AMP, DEA, MEA, and PZ are shown in Table 2. By comparing kDEAB and kMDEA (both DEAB and MDEA are considered as tertiary amine), it can be seen that the kDEAB is much higher than kMDEA , which means that the reaction kinetics of CO2 absorption into DEAB is much faster than that into MDEA. Moreover, it can also observed that the kDEAB is comparable with kAMP and kDEA . It is generally accepted that AMP and DEA are considered to be reactive with CO2 since they are primary sterically hindered amine and secondary amine, respectively (Sartori and Savage, 1983; Kohl and Nielsen, 1997). However, the kDEAB is much smaller than kMEA and kPZ , since MEA is primary amine, which is very reactive with CO2 , and PZ is very fast accelerator. Therefore, it can be summarized that the CO2 absorption reaction with DEAB is faster than that with MDEA, also comparable with those with AMP and DEA, but slower than those with MEA and PZ, respectively. This observation is found to be in good agreement with the mass transfer performance studies by Naami et al. (2012). They have found that the mass transfer performance of CO2 absorption in DX structured packed column in terms of KG av and CO2 absorption performance can be ranked as MEA > DEAB > MDEA. The activation energy can be used for simply prediction of the kinetics behavior of amine. This due to the fact that the lower activation energy, the easier the reaction can proceed. It can be seen from Table 2 that PZ, which is the most reactive amine, is found to have low activation energy. MEA, which found to have lower reaction kinetics than PZ, has higher activation energy than PZ. Lastly, DEA and MDEA, which are slower than MEA and PZ, are found to have higher activation energy that that of MEA and PZ. The experimental enhancement factors, which represent the ratio of the absorption rate of CO2 into a reacting liquid to that if there is no reaction, for CO2 absorption into aqueous DEAB solutions over temperature range of 298318 K, DEAB concentration range of 1.02.0 M, and CO2 loading range of 0.0010.18 mol CO2 /mol amine are shown in Figs. 3 and 4. It can be seen from these gures that the enhancement factor increases as DEAB concentration increases over the range of 1.02.0 M. This is because at higher DEAB concentration, more DEAB molecules (which are chemically reactive with CO2 ) are introduced to the solutions. Fig. 3 also shown that the enhancement factor decreases as CO2 loading increases due to the fact that as CO2 loading increases, the amount of active amine decreases, causing the enhancement factor to decrease. It can be observed from Fig. 4 that the enhancement factor increases as temperature increases because the reaction rate constant increases as temperature increases as can be predicted using Eq. (39).

Table 2 Forward second order reaction rate constant (k) and activation energy of MDEA, AMP, DEA, DEAB, MEA, and PZ at 298 K. k (m3 /kmol s) kMDEA kAMP kDEA kDEAB kMEA kPZ 2.33 6.71 473 570 412 576 429 5939 6209 65,460 70,000 References (for forward second order reaction rate constant) Haimour et al. (1987) and Rinker et al. (1995) Saha et al. (1995) and Mandal and Bandyopadhyay (2005) Rinker et al. (1996) and Zhang et al. (2002) This work Versteeg et al. (1996) and Edali et al. (2009) Derk et al. (2006) and Edali et al. (2010) Activation energy (kJ/mol) 47.9 41.7 53.1 62.6 41.2 35.5 References (for activation energy) Rangwala et al. (1992) Alper (1990) Hikita et al. (1977) This work Hikita et al. (1977) Samanta and Bandyopadhyay (2007)

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Fig. 3. Experimental enhancement factor of DEAB obtained from laminar jet absorber at 298 K over concentration and CO2 loading ranges of 1.02.0 M and 0.0010.18 mol CO2 /mol amine, respectively.

Fig. 4. Experimental enhancement factor of DEAB obtained from laminar jet absorber at CO2 loading of 0.1 mol CO2 /mol amine over concentration and temperature ranges of 1.02.0 M and 298318 K, respectively.

In addition, the CO2 absorption rate/kinetics model developed in this study is also able to predict the CO2 absorption rate in aqueous DEAB solutions at various temperatures, initial DEAB concentrations, initial CO2 loadings, and contact times. The predicted CO2

absorption rate (mol/s) can be obtained from the predicted CO2 absorption rate per unit area (N; kmol/m2 s) since the absorption surface area was known by measurement of liquid jet diameter and height using the two dimensional microscope. The predicted CO2 absorption rate per unit area (N; kmol/m2 s) can be calculated using Eq. (36) by integrating (C1 /t)x=0 over the contact time ( ). (C1 /t)x=0 can be acquired as the results of solving partial differentialnonlinear algebraic equations of Eqs. (14), (15), (17) and (21)(24) simultaneously by COMSOL software. At this calculation state, the kDEAB was obtained from the predictive correlation developed in the present work, which is Eq. (39). Also, the integration over contact time was done by integration function in COMSOL software. The predicted CO2 absorption rates compared with the experimental values are shown in Fig. 5 as a parity chart with an AAD of 6.5%, which is favorably acceptable. Thus, it can be said that the numerical comprehensive CO2 absorption rate/kinetics model for aqueous DEAB solution, which is developed in this work, is adequate and provides accurate results. The maximum uncertainty of CO2 absorption rates measured from the laminar jet absorber was found to be 1.8%. By comparing the difference between the prediction of the model and the experiment (which is 6.5%) with the maximum uncertainty of CO2 absorption rates (which is 1.8%), it can be seen that the difference between the prediction of the model and the experiment is larger than the maximum uncertainty of CO2 absorption rates. This

Fig. 5. Parity chart comparing experimental and predicted CO2 absorption rate in aqueous DEAB solution.

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is because of the error caused by (i) the assumptions for simplifying the CO2 absorption rate/kinetics model, (ii) the deviation of the predicted bulk concentrations of chemical species created by the VLE model, (iii) the predictive correlations for physiochemical properties, and (iv) the numerical error from numerical treatment. However, the maximum uncertainty of 1.8% and the absolute average deviation percentage of predicted and experimental CO2 absorption rates of 6.5% were found to be in the acceptable range of less than 10%. 5. Conclusions 1. The comprehensive numerically solved CO2 absorption rate/kinetics model for aqueous DEAB solutions was developed. The second order reaction rate constant for CO2 absorption into DEAB, kDEAB , can be predicted over a temperature range of 298 K to 318 K as: kDEAB = (4.01 1013 )exp(7527.7/T ) 2. Regarding to the reaction rate constant (k), it can be summarized that the reaction kinetics of CO2 absorption into DEAB is faster than that into MDEA, also competitive with those into AMP and DEA, but slower than those into MEA and PZ, respectively. 3. The predicted CO2 absorption rates obtained for the developed CO2 absorption rate/kinetics model favorably t with the experimental results with an AAD of 6.5%. Acknowledgements The nancial support from National Natural Science Foundation of China (NSFC No. 21276068 and 212111111), Ministry of Science and Technology of the Peoples of Republic of China (MOST No. 2012BAC26B01), Ministry of Hunan Provincial Science and Technology (No. 2010SK2001), Chinas State Project 985 in Hunan UniversityNovel Technology Research and Development for CO2 Capture as well as Hunan University to the Joint International Center for CO2 Capture and Storage (ICCS) 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 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). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/ 10.1016/j.ijggc.2012.11.023. References
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