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Electrolytic Regeneration of Decarbonising Potassium Carbonate Solution

Article  in  Chinese Journal of Chemical Engineering · August 2010

DOI: 10.1016/S1004-9541(10)60256-X

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SEPARATION SCIENCE AND ENGINEERING
Chinese Journal of Chemical Engineering, 18(4) 538ü543 (2010)

Electrolytic Regeneration of Decarbonising Potassium Carbonate

Solution*

LIU Na (ঞઋ), ZHAO Xinglei (ვ໶ढ), WANG Yundong (ฆၮՊ)** and FEI Weiyang (‫׎‬ปླྀ)
State Key Laboratory of Chemical Engineering, Department of Chemical Engineering, Tsinghua University, Beijing
100084, China

Abstract In this work, the regeneration mechanism of potassium carbonate solution after absorption of CO2 using
ion-exchange membrane electrolysis was presented. The solutions of potassium carbonate (K2CO3) and potassium
bicarbonate (KHCO3) were used to simulate the solution after absorbing CO2. Experiments were carried out at
various electrodes, temperatures and current densities. The results indicate that the membrane electrolysis can in-
crease concentration ratio of K2CO3 and KHCO3, and achieve 100% conversion. In this process, not only CO2 is
desorbed from carbonate solution, but also hydrogen, as a byproduct, is generated at the cathode, which is the main
contributor to reduce energy consumption. Thus, the membrane electrolysis is valuable in the regeneration of the
K2CO3 absorbent.
Keywords membrane electrolysis, Benfield, regeneration, carbon dioxide

1 INTRODUCTION chemical absorption process is very high [7].

Among those non-organic based chemical sol-
Environmental problems due to the emissions of vents including potassium, sodium carbonate and
pollutants from consumption of solid, liquid and aqueous ammonia, potassium carbonate (K2CO3) is
gaseous fuels in various stationary and mobile energy the most effective, economical and traditional solvent.
systems as well as in manufacturing plants have be- The hot aqueous solution of potassium carbonate has
come the major global problems involving not only been widely used in the process of removing carbon
the pollutants such as SOx, NOx and particulate matter, dioxide such as natural gas sweetening or the produc-
but also the greenhouse gases (GHG) such as carbon tion of pure hydrogen for ammonia synthesis [8]. The
dioxide (CO2) and methane (CH4) [1]. More than 140 Benfield process uses 20% to 30% (by mass) aqueous
countries have ratified the Kyoto Protocol, which was K2CO3 solutions for CO2 removal. However, these
validated on February 16, 2005 [24]. The Intergov- processes are limited by selectivity and slow rates of
ernmental Panel on Climate Change (IPCC) has con- absorption under the conditions present in coal-fired
cluded that it is unequivocal that the climate system is power plants. The performance of Benfield process is
getting warm. It is widely accepted that CO2 is the usually improved by adding the amine catalyst such as
main contributor to the global warming and it is ur- piperazine, diethanolamine (DEA), monoethanol amine
gent to cut CO2 emissions. However, the high capital (MEA) and other amines [9]. In Benfield process, the
and operation cost makes it very difficult to imple- flue gas is passed through a column in which K2CO3
ment CO2 capture technologies. The CO2 volume selectively absorbs CO2 (Fig. 1) [10]. The CO2-rich
concentration in the flue gas of coal-fired power plants solution is pumped into the regenerator tower in which
is in the range of 12%15% (wet) and the flue gas is thermodynamic conditions are manipulated to release
discharged at atmospheric pressure. Many technolo- the CO2. High pressure and low temperature favor
gies are available for the separation of CO2 from flue absorption, while low pressure and high temperature
gas streams, such as chemical and physical absorption, result in regeneration of the solvent.
solid adsorption, membrane separation and other The basic reaction between hot potassium car-
novel methods [5]. Since the partial pressure of CO2 in bonate solution and CO2 is represented by the follow-
the flue gas is relatively low, most technologies such ing overall reaction:
as physical solvents or membranes are not efficiently CO 2  K 2 CO3  H 2 O 
o 2KHCO3 (1)
applicable for capture. Due to the low CO2 concentra-
tions in flue gas, only chemical solvents show an ab- Reaction (1) can be more realistically represented
sorption capacity large enough to be applicable for in the ionic terms as:
CO2 capture [6]. The chemical absorption process is o H   OH 
H 2 O  (2)
the only method that has been industrially adopted in
many processes and has more recently been consid- CO 2  OH  
o HCO3 (3)
ered as a mechanism to control greenhouse gas emis-
sions. However, the capital cost for CO2 capture via CO32  H  
o HCO3 (4)

Received 2009-12-08, accepted 2010-03-29.

* Supported by the Specialized Research Fund for Doctoral Programme of Higher Education of MOE (200700033154,
200800030095) and the National Natural Science Foundation of China (20836008).
** To whom correspondence should be addressed. E-mail: [email protected]
 Chin. J. Chem. Eng., Vol. 18, No. 4, August 2010 539

Figure 1 Typical chemical absorption system

Figure 2 Experimental apparatus for electrolytic regeneration

1üanode chamber; 2—cathode chamber; 3—exchange membrane; 4—electrode; 5—flowmeter; 6—thermometer; 7—drain sleeve;
8—recycled water

When a small proportion of diethanolamine (DEA)

[usually less than 3% (by mass)] is added into the so- CO 2  3H 2 
o CH3OH  H 2 O (7)
lution, the absorption rate of CO2 is enhanced signifi- In this article, the blended solutions of potassium
cantly according to the following reactions [9]: carbonate (K2CO3) and potassium bicarbonate (KHCO3)
CO 2  R 2 NH 
o R 2 NCOOH (5) were used to simulate the solution after absorbing CO2.
The regeneration mechanism of potassium carbonate
R 2 NCOOH  OH  
o R 2 NH  HCO3 (6) solution after absorption of CO2 using ion-exchange
membrane electrolysis and the effects of various op-
DEA reacts with CO2 to form carbamate eration parameters including temperature, current
(R2NCOOH), a zwitterion intermediate, which is fol- density and electrolysis time have been studied.
lowed to regenerate DEA by reacting with OH  . Re-
action (5) is much faster than Reaction (6) at ambient
temperature [11]. 2 EXPERIMENTAL
Martin and Kubic Jr. in Los Alamos National
Laboratory of US have developed a low-risk trans- The electrolysis experiments were carried out
formational concept, called Green Freedom [12]. The using a membrane electrolysis unit with an active vol-
heart of this technology is a new process for stripping ume of 150 cm3. The anode and cathode of the cells
process by using ion-exchange membrane electrolysis were separated by the Nafion 324 membrane (DuPont).
technology, which produces useful hydrogen as a by- Fig. 2 depicts the experimental apparatus for electro-
product. Carbon dioxide and hydrogen can be done lytic regeneration. Before the gas and liquid entered
via catalytic reaction to form methanol according to the electrolytic cell, they were preheated to the same
the reaction [13]: temperature. The nitrogen gas stream flowed inward
540 Chin. J. Chem. Eng., Vol. 18, No. 4, August 2010

from the inlet of the electrolytic cell by a pressure-

driving force and the K2CO3 and KHCO3 solution was
directly fed to the membrane electrolyser, where CO2
and K2CO3 were regenerated by the electrolysis process.
In the present study, the pressure of inlet gas was
maintained at 0.1 MPa. Temperature of the inlet liquid
and gas streams was ranged from 303 to 353 K. The
mass fraction of K2CO3 and DEA in the inlet aqueous
absorbent was 30% and 3%, respectively. The CO2
concentration in the outlet gas streams was measured
by the infrared gas analyzer (GXH-3011, Huayun
Analytical Instrument Institution, CO2 mole fraction
ranged from 0 to 5%). The concentrations of K2CO3
and KHCO3 in the electrolytic solution were determined
by acid base titration method. The concentration changes
in the electrolyte solutions were monitored by drawing Figure 4 Cation exchange membrane cell for electrolytic
samples at regular intervals and analyzing by titration. regeneration of K2CO3
The electrolysis reactions were carried out at constant
current density (usually 1250 A·m2). DEA was pur-
chased from Sinopharm Chemical Reagent Co. Ltd, replacement of the potassium ions by hydronium
and potassium carbonate was purchased from Beijing formed at the anode by water oxidation is taking place.
Jingqiu Chemical Industry Co. Ltd. These chemicals
have a purity of 99% and were used in the experi- o1/ 2O 2 n 2H 
H 2 O  2e  (8)
ments without further purification. N2 with a purity of
99.9% were bought from Beijing Qianxi Co. When the H   CO32  
o HCO3 (9)
concentration of bicarbonate in the electrolytic solu-
tion was approaching zero, which usually takes about H   HCO3 
o H 2 CO3 (10)
4 h, a batch experiment was terminated.
H 2 CO3 
o CO 2 n  H 2 O (11)

3 RESULTS AND DISCUSSION This ion exchange in the anolyte leads to the
formation of HCO3 in a first step, and eventually of
3.1 Regeneration mechanism H2CO3 with subsequent stripping of the CO2 in the
oxygen stream.
H2 is generated in the cathode compartment.
A similar concept using KOH as the absorbent
has been proposed by Stucki et al [14]. Fig. 3 shows an o H   OH 
H 2 O  (12)
electrochemical membrane cellˈwhich can be used for
the regeneration of the KOH absorbent and for simul- 2H   2e 
o H2 n (13)
taneous hydrogen generation at the cathode.
K   OH  
o KOH (14)

Figure 3 Cation exchange membrane cell for electrolytic Figure 5 Anion exchange membrane cell for electrolytic
regeneration of absorption solution by KOH regeneration of K2CO3

Figure 4 shows a cation electrochemical mem- The overall reaction of the cell can be summa-
brane cell for regeneration. In the anode chamber, a net rized as follows:
 Chin. J. Chem. Eng., Vol. 18, No. 4, August 2010 541

H 2 O  2KHCO3 
o
H 2 n 1/ 2O 2 n 2KOH  2CO 2 n (15)
The reaction of anion electrochemical membrane
cell is the same as what happens in the cation electro-
chemical membrane cell (Fig. 5). The difference is
that CO32 and HCO3 (not K  ) are migrated to the
anode compartment through the selection membrane.
The overall reaction of the cell is summarized as follows:
2KHCO3 
o H 2 n 1/ 2O 2 n  K 2 CO3  CO 2 n
(16)

3.2 Mechanism validation

Figure 7 Composition change during anion exchange
Figures 6 and 7 are the diagonal plots of the membrane electrolysis
composition change during ion exchange membrane (Anode: Ti, cathode: Ni, anolyte: 70 ml 1.65 mol·L1 KHCO3 +
0.77 mol·L1 K2CO3, catholyte: 70 ml 1.5 mol·L1 KHCO3,
electrolysis. It can be found that the concentration of T 303 K)
potassium carbonate in the catholyte rises, but the Ƶ[K2CO3]anode;ƽ[KHCO3]anode; ź [K2CO3]cathode;
concentration of potassium bicarbonate drops. While Ÿ[KHCO3]cathode
it drops to zero, KOH can be detected in the catholyte.
The results indicate that the membrane electrolysis
can increase the concentration ratio of K2CO3 and
KHCO3. Thus, the membrane electrolysis can be used
in the regeneration of the K2CO3 absorbent.

Figure 8 Different current density on desorbed rate of CO2

(Anode and cathode: Fe, anolyte and catholyte: 70 ml 1.74
mol·L1 KHCO3 + 0.32 mol·L1 K2CO3, T 343 K)
current density/A·m2: Ƶ 0;ͩ1000

Figure 6 composition change during cation exchange mem- 3.4 Effect of current density
brane electrolysis
(Anode and cathode: Fe, anolyte and catholyte: 70 ml 2.04
mol·L1 K2CO3 + 0.32 mol·L1 K2CO3, current density 500 Figure 9 shows ion-exchange membrane elec-
A·m2, T 343 K) trolysis technology has an advantage over the thermal
Ƶ [K2CO3]anode; ƽ [KHCO3]anode;Ʒ [K2CO3]cathode; decomposition process (current density/A·m2: 0).
ͩ[KHCO3]cathode;ƹ[KOH]cathode Along with current density increasing, the CO2 sepa-
ration speed is higher and higher, and the H2 produc-
3.3 Energy consumption tion quantity and the current density are proportional.
Therefore, high current density favors regeneration of
the potassium bicarbonate solvent.
Figure 8 shows that contrasting with the tradition
thermal desorption process, the electrolytic process
has the obvious energy conservation and economical 3.5 Effect of the temperature
benefits. The reaction of CO2 in the anode chamber
and H2 generated in the cathode compartment to syn- The important parameters for the overall effi-
thesize the methyl alcohol makes the membrane elec- ciency optimization are the current efficiencies and the
trolysis method be more economical. cell voltage, which depend on the membrane material,
542 Chin. J. Chem. Eng., Vol. 18, No. 4, August 2010

Figure 11 Influence of temperature on desorbed rate of

Figure 9 Influence of current density on desorbed rate of CO2 (anion exchange membrane electrolysis)
CO2 (Anode: Ti, cathode: Ni, anolyte and catholyte: 70 ml 1.74
(Anode and cathode: Fe, anolyte and catholyte: 70 ml 1.74 mol·L1 KHCO3 + 0.32 mol·L1 K2CO3, current density 1250
mol·L1 KHCO3 + 0.32 mol·L1 K2CO3, T 343 K) A·m2)
current density/A·m2:Ƶ0;ƽ500;Ʒ750;ͩ1000;ƻ1250 T/K:Ƶ343;Ʒ323;ƻ303

4 CONCLUSIONS

By contrasting with the tradition thermal desorp-

tion process, the electrolytic process has the obvious
energy conservation and economical benefits. The
processes using membrane electrolysis can enable the
KHCO3 conversion rate to achieve 100% in the recy-
cling fluid, and H2 generated in the cathode compart-
ment makes this method be more economical. Addi-
tionally, the effects of various operation parameters
including the temperature, the current density, and the
electrolysis time have been studied. The proposed
method is a long term option suited for the large scale
application of carbon dioxide capture by chemical
absorbents, where the regeneration cost needs to be
reduced. The systematic economic analysis needs fur-
ther investigation.
Figure 10 Influence of temperature on desorbed rate of
CO2 (cation exchange membrane electrolysis)
(Anode: Ti, cathode: Ni, anolyte and catholyte: 70 ml 3 mol·L1
KHCO3 + 1.5 mol·L1 K2CO3, current density 1250 A·m2) REFERENCES
T/K:ƽ343;ƻ333;ƶ323;Ƶ353
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