RESEARCH NOTES Chinese Journal of Chemical Engineering, 19(4) 687692 (2011)

Absorption of Sulphur Dioxide with Sodium Citrate Buffer Solution in a Rotating Packed Bed*
JIANG Xiuping ()**, LIU Youzhi () and GU Meiduo ()
Research Center of Shanxi Province for High Gravity Chemical Engineering and Technology, North University of China, Taiyuan 030051, China Abstract Absorption of SO2 from a SO2/air mixture with sodium citrate buffer solution was investigated using a rotating packed bed (RPB) in laboratory scale. The effects of operating parameters, such as the rotation speed of RPB, liquid-gas ratio, inlet gas flow rate, inlet concentration of SO2 in flue gas, sodium citrate buffer concentration and initial pH of absorption solution, on the SO2 concentration in the absorption solution or removal efficiency of SO2 were examined. Incremental rate of sulfate radical ions in the absorption solution was also examined. Experimental results indicate that the efficiency of this regenerative process will be improved by using RPB under appro priate operating conditions, and the generation of SO 2 4 will be restrained in the process in RPB. Keywords SO2 absorption, rotating packed bed, sodium citrate buffer solution

INTRODUCTION

Nowadays, the large amount of SO2 emitted from the combustion of coal leads to severe air pollution and results in great harm to peoples living, production and health, and has to be controlled. Several desulfurization schemes, such as fuel pretreatment, concurrent burning and adsorption, and flue gas post treatment, have been proposed [1]. The flue gas desulphurization (FGD) is the main technology used, and a great number of FGD methods have been developed, such as dry-, semidry- and wet-processes, among which the wet-process is more widely applied, due to lower operating cost and more stable operation, and limestone- or lime-based scrubbing is used. However, many of these FGD methods are not regenerative and pollute the environment. The traditional SO2 absorption process requires a large column packed with various packings [2] or spray tower [3], rotating-stream tray scrubber [4], etc. Since the mass transfer efficiency is poor, the size of columns is large, leading to high capital and operating costs. Therefore, researches have been focused on developing regenerative processes and equipment with process intensification for absorption of SO2 [5-15]. SO2-removal by absorption into sodium citrate buffer solution is generally considered as a fast, safe, green, and economical method with the advantages of non-toxic reagent with negligible losses, simple process, no fouling problem, and low oxidation of SO2. In the process, SO2 in flue gas is absorbed by aqueous sodium citrate solution, and dissolved SO2 is subsequently recovered from the solution by steam stripping or other regenerative method, or the resulting absorbent solution react with H2S to obtain sulphur, which can be separated by flotation [14, 16, 17]. The desulfurization of SO2 with absorption and desorption

in sodium citrate buffer solution is 3NaHSO3 + H3Ci (1) 3SO2 (g) + 3H 2 O + Na 3Ci

This simple equation may be considered as a complex series of chemical and diffusion steps. SO2 first diffuses to and through the gas-liquid interface, then a series of reactions occur. SO 2 (aq) (2) SO 2 (g)
H + + HSO3 SO 2 (aq) + H 2 O + 2 HSO3 H + SO3

(3) (4) (5) (6) (7)

HCi 2 H + + Ci3 H 2 Ci H + + HCi 2 H 3Ci H + + H 2 Ci

where Ci denotes citrate acid radical. The reactions go rightward for absorption and leftward for desorption. The solution is composed of H3Ci, HSO3 and H+ mostly after absorption and H2Ci and HCi2 play major role in absorption and desorption. The rotating packed bed (RPB), which rotates a doughnut-shaped packing element to generate a centrifugal acceleration as high as several hundred folds of g to intensify mass transfer efficiency, plays an important role in process intensification [18]. In RPB, liquid is torn into liquid elements such as droplet, thread or film by the high-speed rotating packing, the flow rate of these liquid elements may be up to ten times higher than that in gravitational field, then the high-speed liquid elements contact counter-currently with the flowing gas compelled by a pressure driving force, which intensifies the interphase mass transfer greatly, the mass transfer efficiency may be up to 1-3

Received 2011-01-20, accepted 2011-05-21. * Supported by the National Natural Science Foundation of China (20572128). ** To whom correspondence should be addressed. E-mail: jiangxiupingzhbuty@163.com

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orders of magnitudes higher than that in a conventional reactor, and the size of the equipment is greatly reduced compared with a conventional packed column. This leads to a significant reduction in capital and operating costs. Now RPB is widely applied in a variety of gas-liquid contacting processes, such as distillation [19, 20], absorption [21, 22], extraction [23], desulfurization [9, 10], deaeration [24], reactive precipitation [25, 26], chemosynthesis [27, 28], removal of dust [29], and making nano-material [30, 31]. Dutta et al. [6] investigated the absorption characteristics of SO2 in citric acid-sodium citrate buffer solution using a continuous flow stirred vessel with flat gas-liquid interfaces. The solution enhanced the absorption in water considerably. The absorption rate was independent of the concentration of feed solution and weakly dependent on pH in the range 3-5, while it increased with the gas concentration and liquid stirring rate. Previous study revealed that the liquid-side mass transfer coefficient in the RPB was greatly increased, about 3-7 times that in the conventional columns under appropriate operation conditions [32]. Ramshaw and Mallinson [33] found that KGa for NH3 absorption was 4-9 times higher in RPB systems than that in conventional packed beds. In this work, the rotating packed bed is used to investigate the SO2 absorption with sodium citrate process and appropriate conditions are determined for an efficient SO2-removal. The new technology for FGD will provide theoretical and experimental basis for industrial applications. This paper focuses on the absorption, and the regenerative process will be reported later.
2 2.1 EXPERIMENTAL Materials

Figure 1 Schematic diagram of the experimental setup 1 circulation tank of absorption solution; 2 pump; 3 vacuum pump; 4,13,16 valve; 5 liquid flowmeter; 6 RPB; 7liquid inlet; 8gas outlet; 9gas inlet; 10liquid outlet; 11motor; 12buffer tank; 14,15gas flowmeter; 17SO2 steel container

gas and a rotary packed bed. The rotor in the RPB had an inner diameter of 59 mm, an outer diameter of 132 mm and a height of 40 mm. The stainless wire mesh was packed in the bed as the packing. It had a specific surface area of 650.2 m2m3 and a void fraction of 0.925, and the diameter of stainless wire mesh was 0.25 mm.
2.3 Experimental method

The simulated-flue gas used in experiments was a mixture of air from a vacuum pump and SO2 from a steel container. The sodium citrate buffer solution was used as absorbent, which was made in the laboratory with analytical purity. SO2 concentrations in the inlet and outlet gas streams were measured with chemical analysis and a flue automatic analysis apparatus (Model KM9106, Kane Quintox Co., UK). The pH value of absorption liquid was measured with digital pH meter (Model PHS-3C, RIDAO instruments Co., Shanghai). The mass concentration of SO2 in absorption liquid was analyzed by using the iodometric method. The concentration of sulfate radical was analyzed with gravimetric method after denoised by boiling in dilute hydrochloric acid. Deionized water was used in the experiments.
2.2 Setup

In the experiments, the simulated flue gas stream flowed inwardly from the outer edge of the RPB by a pressure driving force, and the sodium citrate buffer solution was pumped from the storage tank to the inner edge of the RPB via a distributor. The velocities of the absorbent solutions were high enough to avoid the entrainment in the flue gas stream. The absorbent solutions moved outwardly and left from the outer edge of the RPB via a centrifugal force. Both gas and liquid streams contacted counter-currently in the RPB, in which SO2 in the gas stream was dissolved and reacted with the absorbent. The cleaned gas leaving the RPB was discharged through the vacuum pump from the top of the RPB, while the SO2-rich aqueous solution was discharged from the side of the RPB into the circulation tank and circulated through the RPB. In all operations, the circulated liquid was 4 L and kept invariant.
3 RESULTS AND DISCUSSION

For SO2 absorption process, the SO2 removal efficiency in the RPB is defined as

= ( cSO

2 ,in

cSO2 ,out ) ( cSO2 ,in ) 100%

(8)

Figure 1 schematically depicts the experimental apparatus including a system to make simulated flue

where is the efficiency of SO2 removal (%), and cSO2 ,in and cSO2 ,out are the SO2 concentrations in the

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inlet and outlet air streams (mgm3), respectively.

3.1 Relationship between cSO 2 and

Figure 2 shows that SO2 concentration in the absorption solution cSO2 increases with absorption time while the removal efficiency drops. For the reversible reactions expressed by Eqs. (3)-(7), the concentration of H+ increases as the absorption proceeds, restraining the reactions and increasing the mass transfer resistances in both gas and liquid, so that drops. Thus it is necessary to control the concentration of SO2 in the solution to keep higher removal efficiency of SO2. Moreover, the concentration of SO2 in the last step must be strictly controlled in order to meet discharge requirement, or using fresh absorption solution in the last step as much as possible.

absorption. High cl results in higher absorption efficiency, so higher citrate concentration is favorable to increase the absorption rate and absorption capability. However, because the absorption process is regenerative, the desorption process must be considered. Since high citrate concentration results in lower desorption efficiency [34], the concentration of citrate acid should be appropriate.
3.3 Effects of pHinitial on cSO 2

SO2 is an acidic gas, so the increase of pH of absorption solution is favorable to the absorption. Citric acid is a multivalent weak acid, its pH may affect the absorption process significantly. Fig. 4 shows that cSO2 with different pHinitial values. At 480 min, the SO2 concentration with pHinitial of 3.5 is 23 gL1, while that with pHinitial of 5.5 is 37 gL1. The reason can be explained from Eq. (3). H+ is produced in the absorption of SO2 and the decomposed H+ is associated with citrate acid radial. With the consumption of citrate acid radials, the ability to associate H+ is lower in low pH absorption solution, while the high pH solution maintains higher ability to associate H+. Thus higher citric acid pH enhances the absorption. However, it should also be noted that the increase of citric acid pH will make the later desorption more difficult and reduces the recycle rate of desorption, so pHinitial should be reasonable.

Figure 2

Relationship between cSO 2 and

( cSO2 ,in = 5085 mgm3, Ql/Qg = 7 Lm3, Qg = 3 m3h1, cl =1.0 molL1, pHinitial = 4.5, N = 1000 rmin1) SO2-removal; SO2 concentration in absorption solution

3.2

Effects of cl on cSO 2

Figure 3 shows that the concentration of sodium citrate buffer solution cl has an important effect on the
Figure 4 Effects of pHinitial on cSO 2

( cSO2 ,in = 5085 mgm3, Ql/Qg = 7 Lm3, Qg = 3 m3h1, cl = 1.0 molL1, N = 700 rmin1) initial pH of absorption solution (pHinitial): 3.5; 4.5; 5.5

3.4

Effects of N on cSO 2

Figure 3

Effects of cl on cSO2

( cSO2 ,in = 5085 mgm3, Ql/Qg = 7 Lm3, Qg = 3 m3h1, pHinitial = 4.5, N = 700 rmin1) concentration of sodium citrate buffer solution (cl)/molL1: 0.5; 1.0; 1.5

Figure 5 illustrates the effects of rotation speed of RPB N on the absorption. Higher N is favorable to increase the absorption rate, resulting in higher absorption efficiency and absorption capability of solution, and shorter operation time. At higher rotating speed, larger centrifugal force enhances the micromixing in the RPB. The relative velocity between liquid elements (e.g. droplet, thread and film) and packing is higher. Vigorous impingement and uniform dispersion of the

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Figure 5

Effects of N on cSO2

( cSO2 ,in = 5085 mgm3, Ql/Qg = 7 Lm3, Qg = 3 m3h1, cl = 1.0 molL1, pHinitial = 4.5) rotating speed/rmin1: 500; 700; 900; 1100

liquid will occur, resulting in excellent mixing and higher mass transfer rate. However, it is well known that higher rotating speed will cause higher costs, which must be considered in industrial applications. In this experiment, the SO2 removal is above 97.30% at rotating speed of 700 rmin1 and above 98% at 900 rmin1, so the rotating speed of 700-900 rmin1 is appropriate.
3.5 Effects of Qg on cSO 2

ing the RPB performance. Therefore, the ratio should be appropriate. With the other conditions essentially the same, the experiments are carried out at a fixed gas flow rate, Qg, while liquid flow rate, Ql, is changed according desired Ql/Qg. The effect of Ql/Qg on the SO2 concentration is shown in Fig. 7. For the absorption process controlled by diffusion through gas film, large interface area is favorable, while this, to a large extent, depends on Ql/Qg. However, large Ql/Qg leads to higher power consumption and operation cost. In Fig. 7, for Ql/Qg<7 Lm3, cSO2 increases considerably as the liquid gas ratio increases, while for Ql/Qg>7 Lm3, the change of cSO2 is smaller. At a fixed Qg, an increase in the liquid flow rate would increase the effective wetting of packing, and, consequently, the effective surface areas for mass transfer, which is favorable to SO2 absorption. However, the increase in the liquid flow rate will reduce the contact time of gas and liquid, which is unfavorable to SO2 absorption. The SO2-removal efficiency, , obtained in the range of 5-7 Lm3 is high enough to meet the requirement of environment protection. Therefore, the range can be considered appropriate, which is lower than 5-10 Lm3 in packed column [34].

As shown Fig. 6, with the increase of gas flow rate Qg, cSO2 drops. At certain liquid flow rate, increase in the inlet gas rate will decrease the gas film thickness, and gas-liquid mass transfer area and coefficient increase a little, which is favorable to absorption. On the other hand, increase in the inlet gas rate decreases the gas-liquid contact time, which is harmful to the absorption. The later effect is dominant.

Figure 7

Effects of Ql/Qg on cSO 2

( cSO2 ,in = 5085 mgm3, Qg = 3 m3h1, cl = 1.0 molL1, pHinitial = 4.5, N = 700 rmin1) liquid gas ratio (Ql/Qg)/Lm3: 3; 5; 7; 9; 11

3.7 Incremental rate of sulfate radical ions in absorption solution

In the absorption, with O2 contained in low concentration SO2 flue gas, the oxidization reaction of 2 SO3 to SO 2 4 can not be ignored. Alkali in the soluFigure 6 Effects of inlet gas flow rate Qg on cSO 2
2 is oxition is consumed for generation of H+ as SO3 2 dized to SO 2 4 . The oxidization reaction SO3 is
2 2 2SO3 + O 2 2SO 4

( cSO2 ,in = 5085 mgm3, Ql/Qg = 7 Lm3, cl = 1.0 molL1, pHinitial = 4.5, N = 700 rmin1) inlet gas flow rate (Qg)/m3h1: 1; 3; 5

(9)

3.6

Effects of Ql/Qg on cSO 2

From the economic point of view, the liquid gas ratio is one of the most important criteria for evaluat-

When a large amount of SO 2 4 forms, the absorption solution may be invalidated, causing sodium sulfate to crystallize. In serious case, the tubes are blocked and the process stops. Thus it is important to examine the

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generation rate of sulfate radicals in the absorption solution. Xue et al. [35] studied the generation rate of sulfate radicals in liquid-containing microporous membrane and concluded that the concentration of SO 2 4 in the absorption solution increased with absorption time, which is almost a linear relationship at a rate of 0.192 g(Lh)1. Hong et al. [36] obtained similar conclusion, a rate of 0.2 g(Lh)1 in packing columns. These re2 sults indicate that SO3 is oxidized to SO 2 4 when the SO2 flue gas contains much oxygen. 2 In order to examine the stability of SO3 in the RPB, the absorption solution was recycled many times and the content of SO 2 4 in the absorption solution was analyzed at regular intervals. The concentration of SO 2 4 in the absorption solution increases at a rate of 0.136 g(Lh)1, which is lower than the values in literature [35, 36]. It indicates that RPB may restrain reaction (9). The reason may be that both operation time and retention time are shorter in the RPB, reducing the 2 and O2 and the production of contact time of SO3
SO 2 4 .

5 6

10

11

12

13

NOMENCLATURE
14 cl concentration of sodium citrate buffer solution, molL SO2 concentration in absorption solution, gL1 inlet concentration SO2 in flue gas, mgm3 outlet concentration SO2 in flue gas, mgm3 gravity acceleration , ms2 overall gas-phase volumetric mass transfer coefficient, s1 rotation speed of RPB, rmin1 initial pH of absorption solution inlet gas flow rate, m3h1 inlet liquid flow rate, Lh1 liquid gas ratio, Lm3 removal efficiency of SO2 gas inlet liquid outlet
1

cSO2 cSO2 ,in cSO2 ,out

g KGa N pHinitial Qg Ql Ql/Qg g in l out

15 16 17

18 19

Subscripts

20 21

22

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