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Investigation on the rate of reaction between gas (CO2) and liquor (NaOH) phases1
CHEN Bin()LI Xiao-bin*LIU Gui-huaPENG Zhi-hong
ZHOU Qiu-shengXU Xiao-huiLIU Xiang-min
( School of Metallurgical Science and Engineering ,Central South University, Changsha 410083, P.R.China)

AbstractThe neutralization of sodium hydroxide by carbon dioxide occurring during the process of
carbonization precipitation of sodium aluminate solution was investigated. Firstly, the effects of those
main factors such as CO2 concentrationtemperatureinitial concentration of NaOH were investigated.
Then the kinetics equation concerning this reaction was obtained after proper data treatment. The results
showed that it assumes an apparent activation energy of 8.06 kJ/mol which indicated a diffusion-controlled
process. Furthermore, based on the principles governing diffusion-controlled process, the dependence of
neutralization rate on gas flow was deduced theoretically with a form as: rd=KDKCA(Q/VL)2/3 whose
plausibility was validated by those experimental research thereafter.
Key wordsreaction between gas & liquor phasesodium hydroxidecarbon dioxidediffusion
controlkinetics
CLC number: TF801
Document code: A

1INTRODUCTION
Presently in China, about 40% of alumina was produced by sintering process, where carbonization
decomposition, that is, CO2 is ventilated into desilicated sodium aluminate solution to obtain Al(OH)3,
holds a crucial procedure during alumina production[1]. Hitherto the mechanism of carbonization
decomposition remains ambiguous for its a multiphase reaction involving series of complicated
physicochemical processes such as crystallization, heat and mass transport, etc[2]. Thermodynamic and
kinetic research[3,4] indicated that the essential of this process lies in the precipitation of Al(OH)3 resulting
from the elevation of supersaturation with OH- being neutralized by CO2. So the ventilation profile of CO2
exerts a remarkable influence on the rate of the reaction and quality of the product. Generally speaking, it
includes following steps: 1) transport of CO2 towards the gas-liquor phase interface; 2) chemical reaction
between NaOH and CO2 at the interface; 3) removal of product from and transport of fresh reagents to the
interface; 4) Mass transport relating to the production and growth of crystalline embryos on the seed
surface[5].
As described above, the neutralization of NaOH by CO2 holds a vital step during carbonization
process. For the sake of controlling the process effectively, theres every necessity to obtain the
quantitative relationship between reaction rate and gas flow rate. However, related researches on this issue
havent been reported so far. Though recently in consideration of the environmental protection which
requires enterprises to reduce the emission of industrial gas resulting in greenhouse effect, the reaction
behavior of CO2 in alkaline solution has been particularly studied[6-11], some influential factors such as air
column height, configuration, gas pressure and interface area etc have been discussed at length and
corresponding mathematical models established, yet the effect of gas flow rate was not singled out and
whats more, those systems were quite different from that of carbonization process.
So a systematical study on the reaction process between CO2(g) and NaOH(L) was performed in this
1

Foundation item: Project (50274076) supported by the National Natural Science Foundation of China.
* Correspondence: LI Xiao-bin, professor;. Tel: +86-731-8830454; E-mail: X.B.Li@mail.csu.edu.cn.

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paper in the hope of realizing an effective control on carbonization and other similar processes.

2EXPERIMENTAL
Devices used in the experiments include a carbonizer as illustrated in Fig.1, a CYSE-II type O2/CO2
aerometer (XueLian meter company of Jia Ding, Shanghai), a thermostat with stirrer (Nanjing Timing
electromotor Co., Ltd)and a LZB-6 type vitreous rotor flowmeter (Yuyao meter factory, Zhejiang).
NaOH solution was prepared by dissolving chemical pure NaOH in distilled water and feeding gas by
blending air and pure CO2. The carbonizer served as a cylindrical reactor with a diameter of 16.5cm and a
height of 20cm where certain amount of solution was poured and feeding gas (air and CO2) continuously
ventilated through the orbicular porous vent-pipe located in its bottom. CO2 concentration was measured
with the CYSE-II type O2/CO2 aerometer and gas flow rate with the LZB-6 type vitreous rotor flowmeter.
At controlled temperature and stirring speed, small amount of solution samples were taken at specified
intervals for measuring the NaOH concentration with chemical titration method.

1. Lift Tank; 2.Electromotor; 3. Pulleys;

4. Reactor; 5.Thermostatic oil bath

Fig.1 Schematic diagram of carbonizer

3RESULTS AND DISCUSSION

3.1 Establishment of the kinetics equation concerning CO2(g)NaOH(L) reaction
3.1.1 Influence of main factors on the reaction rate
The variation of NaOH concentration with reaction time at different experimental conditions was
plotted in Fig.2Fig.4, which shows the influence of CO2 concentration, temperature and initial NaOH
concentration on the reaction rate respectively. Under all circumstances, the liquors volume is 2 liter. As
shown in Fig.2 theres a linear relationship between NaOH concentration and reaction time; that is, the
time that NaOH is completely neutralized decreases with the raise of CO2 concentration, or to say, the
reaction rate climbs up rapidly with the increase of CO2 concentration. While the influence of temperature
is not remarkable as the four curves in Fig.3 are nearly overlapped within the temperature range of 7595
, the initial NaOH concentration either exerts little influence on the reaction rate as the three curves in
Fig.4 are almost parallel. All these results are consistent well with those from literatures[12,13].

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3.5

C(NaOH) /mol.L-1

C(NaOH) /mol.l-1

3.5

(CO2)=23%
(CO2)=30%
(CO2)=33%
(CO2)=37%

3
2.5
2
1.5
1
0.5

Tem=75
Tem=80
Tem=85
Tem=95

3
2.5
2
1.5
1
0.5
0

0
0

20

40

60

80

100

120

140

160

10

20

Time/min

30

40

50

60

70

80

90 100 110

Time/min

Fig.2 Variation of NaOH concentration

with reaction time at different CO2 concentrations
(temperature 85, flow rate 0.22Nm3.h-1,

Fig.3 Variation of NaOH concentration

with reaction time at different temperatures
(concentration of carbon dioxide 31%, flow rate

-1

0.22Nm3.h-1,stirring speed 250r.min-1)

stirring speed 250r.min )

C(NaOH) /mol.L -1

4
3.5
3
2.5
2
1.5
1
0.5
0
0

20

40

60

80

100

120

140

Time/min

Fig.4 Variation of NaOH concentration with time

at different initial NaOH concentrations
(temperature 85, flow rate 0.22 Nm3.h-1, stirring speed 250 r.min-1, concentration of carbon dioxide 30%)

3.1.2 Establishment of the kinetics equation

The reaction that NaOH solution is neutralized by CO2 can be expressed as an equation as follows:
2NaOH+CO2=Na2CO3+H2O
(1)
According to the principles of chemical kinetics [14], the kinetics equation of reaction (1) can be
defined as:
Ea

(
r= dc ( NaOH ) =A e RT
d

c( NaOH ) n1 c(CO2 ) n 2

(2)

As discussed above, the influence of NaOH concentration on the reaction rate can be neglected in
Eq.(2); Since the pressure of the system is 105 Pa as the feeding gas is ventilated into the unsealed reactor,
the volume percent of CO2 equals to its partial pressure according to Henrys law on the premise that
feeding gas meets the behavior characteristics of those idea ones at given temperatureThe ratio of CO2
which participated in reaction to whole CO2 can be calculated using the data in Fig.2Fig.4, its value is in
the range of 70100% (The highest approached 98.7%). So we can consider that most of CO2 was
absorbed. Thus comes following equation:
r=A e

Ea
)
RT

(CO2 ) n

Taking natural logarithm at both sides of Eq. (3) yields:

(3)

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ln r = ln A

Ea
RT

+ n ln (CO 2 )

(4)

Where: rreaction rate,mol.L-1.min-1 Apreexponential factor Eaactivation

energy,J.mol-1 ( CO 2 ) CO2 concentration,%reaction time,minRgas constant,8.314
J.mol-1.K-1TtemperatureK

As there exists a linear relationship between NaOH concentration and reaction time, a linear
equation was fitted and its slope corresponds to the reaction rate r. Relevant parameters were obtained
as follows after a multi-linear regression according to Eq.(4) was carried out with all experimental
data:
lnA=10.5984Ea/R=969.1051n=1.26
So, macro-kinetics equation can be given as:
r=2.495610-5 e

8057.1398
)
RT

(CO2 )1.26

(5)

Formula (5) is similar to the rate equation of reaction that CO2 is absorbed by NaOH[15].It can
be seen from formula (5) that this reactions activation energy is very small (less than 10 KJ.mol-1),
which indicates that this process is probably controlled by diffusion process. Because the order of
( CO ) is 1.26 in the equation (close to 1), the conclusion is implied further. It is identical with the
2

conclusion[16] (Liquid film diffusion is main determining steps in the absorption process of CO2 to
alkaline solutions). However the equation given above doesnt involve the relationship between
reaction rate and gas flow rate. Its essential to investigate the relationship between reaction rate and
gas flow rate.

3.2 Relationship between reaction rate and gas flow rate

3.2.1 Theoretical analysis
The mass transport equation of a diffusion-controlled process like the reaction discussed above
can be described as[17]:
N= rdVL= D k S (CA-CA*)

(6)

Where: Nmass transport ratemol.min-1rdreaction ratemol.L-1.min-1VLliquors

volumeDkdiffusion coefficientSarea of reaction interfacethickness of diffusion
layerCACA*CO2 concentration and its equilibrium concentration in the liquor phase,
respectively.
Considering that reaction (1) can be seen as an irreversible one with high reaction rate[16], weve
got CA-CA* CA, thus:
rd= D

CA

(7)

Several assumptions as follows can be made as the gas flow rates are overloaded under all
experimental conditions (most exceeded 2000 mL.min-1the highest approached 5000 mL.min-1):
1) Feeding gas can fill the whole reaction system in no time and the gas phase with a flow
rate of Q can be evenly mixed up with the liquor phase with a volume of VL;
2) As shown in Fig.5, the liquor phase with a volume of VL can be deemed as composed of n
spherical micro-components with a diameter of dL and each contains only one gas bubble
with average diameter of dg;

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3) The process claims a steady state after a well mixing of gas and liquor phase, i.e., the state
of micro-component remains untouched. The disappearing rate of gas bubble is
proportionate to the amount of micro-component with a coefficient of K, and the amount
of mixed gas ventilated in unit time equals to the disappearing amount of the gas in
gas-liquor-mixed phase (including those overflowed and exhausted due to reaction).

gas

dg

liquor

dL

Fig.5 The schematic diagram of the hypothetic micro-component

Thus it holds that:

Kn[ 4 ( d g ) 3 ]=Q
3
2

(8)

Where: time intervals.

VL =n 4 ( d L ) 3
3

(9)

Thickness of diffusion layer()can be assumed as ( d L d g ) . Postulating that dgdLwe

2

get:
1

= ( d L d g ) d L = 1 ( KV L ) 3 dg
2

(10)

From the viewpoint of Double Membrane Theory[17], the interface of two phases is located
between gas film and liquor film. So, the area of reaction interface is approximately equal to the total
surface area of that part whose diameter is quarter of that of the micro-component, thus:
Sn4 ( d L )
4

(11)

Substituting Eq.(10) and (11) into Eq.(7) yields:

rd= 3 D k C
K

2
3

A
2

Q
VL

2
3

(12)

In view of the assumption (3) above, the average diameter of gas bubble dg can be considered
as a constant. Meanwhile, Dk is also deemed as a constant in the premise that the other conditions are
fixed. This treatment method was also adopted in the paper[18]. So Eq.(12) evolves into a form as:
rd= k ' D k C A ( Q )

2
3

(13)

VL

3.2.2 Experimental Justification

In order to verify Eq.(13) deduced theoretically, the influence of gas flow rate on reaction

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C(NaOH) /mol.L -

process was investigated experimentally. As the effect of NaOH concentration on reaction rate is
negligible, the initial NaOH concentration was not specified. The experimental results were shown in
Fig.6.
As seen from Fig.6, the reaction rate rises with the increase of gas flow while the amplitude
decreases gradually after a threshold.
3
2.5
2
1.5
1
0.5
0
0

20

40

60

80

100 120

Time/min
Flow
Flow
Flow
Flow
Flow

rate=0.06Nm3/h
rate=0.12Nm3/h
rate=0.18Nm3/h
rate=0.24Nm3/h
rate=0.29Nm3/h

Fig.6 Variation of NaOH concentration with time at different CO2 flow rates
(temperature 80agitation rate 250r.min-1concentration of carbon dioxide 32%)
Taking natural logarithm at both sides of Eq.(13) where a power index of n is supposed to replace
the theoretical value of 2/3 yields:
ln rd=lnK+n ln Q

(14)

VL

Results of linear regression on all experimental data were as follows:

lnK=-3.21, n=0.61
R=0.99, F=140.39 > 10F(k,N-k-1)=10F0.05(1,3)=101,
Where: Rcorrelation coefficient; FF test value; confidence interval; kvariable
number; Ntotal number of samples.
The high F test value indicates a highly significant regression and the power index of (Q/VL) in
Eq.(14) obtained (0.61) is exceedingly close to the results deduced theoretically0.667, So it can
be concluded without reservation that the assumptions made above are all reliable.
The results of Eq.(13) indicate a possibility to determine the influence level of gas flow rate
with theoretical aids to meet the requirement of precipitation ratio in carbonization process, which,
therefore exerts a vital guiding significance on alumina production practice.

4 CONCLUSIONS
1) The experimental results show that NaOH concentration decreases linearly with reaction time;
the reaction rate climbs up rapidly with the increase of CO2 concentration; While the influence of
temperature is not remarkable, the effect of initial NaOH concentration on reaction rate is either
negligible.
2) Apparent activation energy of this process is only 8.06 KJ.mol-1, which implies that it is
controlled by diffusion step.
3) The quantitative relationship between gas flow rate of CO2 and reaction rate deduced

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theoretically indicates that the reaction rate is proportionate with the 2/3 power of the ratio of gas
flow rate to liquor phases volume, which accords well with experimental results.

REFERENCES
[1] Yang Zhong-yu. The technology of alumina production[M]. Metallurgical Industry Press, 1993, 268~270. (In Chinese)
[2] Vadim A L, Viktor I D, Andrey A K. Special requirements to aluminium hydroxide of non-metallurgical application[A].
see: Anon. Light Metals[C]. Pennsylvania:TMS, 2002, 169173.
[3] LI Xiao-bin, LIU Xiang-min, GOU Zhong-ru, et al. The thermodynamics of carbonization precipitation of sodium
aluminate solution[J]. The Chinese Journal of Nonferrous Metals, 2003, 13(4): 10061007. (In Chinese)
[4] LI Xiao-bin, CHEN Bin, ZHOU Qiu-sheng, et al.

Study on the kinetics of carbonation decomposition of sodium

aluminate solution[J]. The Chinese Journal of Nonferrous Metals, 200414(5)848853. (In Chinese)
[5] Chen Qian-de, Tang Xian-liu, Huang Ji-fen et al. The physical and chemical principle of synthetically treating aluminium
material with basic process[M]. CSUT Press, 1988, 8485. (In Chinese)
[6] LUO Pei-Cheng, JIAO Zhen, WANG Zhi-Xiang et al. CO2 removal from polluted air using alkaline solutions in
packed tower[J]. Journal of Chemical Industry and Engineering (China), 2003,54(6):824829. (In Chinese)
[7] Fleischer C, Becker S and Eigenberger G. Detailed modeling of the chemisorption of CO2 into NaOH in a bubble
column[J]. Chemical Engineering Science,1996,51(10):17151724.
[8] Maalej S, Benadda B and Otterbein M. et al. Interfacial area and volumetric mass transfer coefficient in a bubble
reactor at elevated pressures [J]. Chemical Engineering Science,2003,58(11):23652376.
[9] Maalej S, Benadda B and Otterbein M.

Influence of pressure on the hydrodynamics and mass transfer parameters

at an agitated bubble reactor [J]. Chemical Engineering and Technology, 2001,24(1):7784.

[10] Aroonnilas A, Chakma A and Tontiwachwuthikul P. et al. Mathematical modeling of mass-transfer and
hydrodynamics in CO2 absorbers packed with structured packings [J]. Chemical Engineering Science,
2003,58(17):40374053.
[11] Aroonnilas A and Tontiwachwuthikul P. Mechanistic model for prediction of structured packing mass transfer
performance in CO2 absorption with chemical reactions [J]. Chemical Engineering Science, 2000,55:36513663.
[12] ZHU Zhong-liang, L Bing-liang and CHEN Rong-mei. Determination of carbon dioxide in gaseous phase by
kinetic analysis[J]. Chinese Journal of Analytical Chemistry,1994,22(12):12561258.

(In Chinese)

[13] LIU Run-jing, Li Xiao-yun. Reaction orders of absorbing carbonyl sulphide in sodium hydroxide aqueous
solution[J]. Journal of Hebei Institute of Chemical Technology and Light Industry, 1997,18(1):4952. (In
Chinese)
[14] ZHANG Ya-RU. Chemical reaction dynamics[M]. Tianjin: Nankai University Press, 1995, 144145.

(In

Chinese)
[15] Bi Li-qun, Ma De-xian. Effect of gas-rate and hold-up time on selective absorption of H2S with high CO2
component [J]. Journal of BeiJing Institute of Chemical Technology , 1994,21(4):9196.

(In Chinese)

[16] YANG Ren-chun, HE Li-hui, LI Zuo-hu, ZHANG Yi. Preliminary study on the carbonation of K2CrO4 for recovery
of potassium alkali in alkaline solution[J]. The Chinese Journal of Process Engineering, 2001,1(4):422426.

(In

Chinese)
[17] ZHU Jia, DU Hong, WANG Jia-yin. Application of gas-liquid reaction theories to ozone contactors[J].Journal of
Harbin University of Architecture and Engineering, 1997,30(6):6367.

(In Chinese)

[18] WANG Zhong-min, HUANG Guo-xiang, ZHU Dong-sheng, et al. The determination of diffusion coefficients for
sparingly soluble gases in liquid by laminar flow Jet absorption[J]. Journal of South China University of
Technology, 1994,22(2):1825.

(In Chinese)