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Mass Transfer and Reaction Kinetics of PH3 Absorption with Pd()-Cu() in Double-Stirred Cell
Guangfei Qu, Yixing Ma, Junyan Li, Yilu Lin, and Ping Ning*
Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500, China #Email: ningping58@sina.com
Abstract
The solution of Pd()-Cu() was used as a self-screened catalyst of liquid phase catalytic oxidation to remove phosphine. Mass transfer and reaction kinetics were studied in a double-stirred cell. The results indicated that the system was an interfacial instantaneous reaction. Gas-side and liquid-side mass transfer coefficient were 3.88 10-7 mol(m2Pas)-1 and 6.74 10-7 mol(m2Pas)-1 (303.15 K) respectively. The rate constants of the first-order reaction were over the order of 105 under the experiment temperatures. Ha number was 552.56, and practical enhancement factor was 593.63. Keywords: Posphine; Catalytic Oxidation; Kinetics
1 INTRODUCTION
Phosphine (PH3) is a colourless, highly toxic, cancerogenic gas, with characteristic of stench and highly reactive activity, whose emission will cause air pollution and be harmful to environment and human health. At present, there are some removal methods of low concentration PH3, including adsorption and chemi-adsorption mostly. Impregnated activated carbon catalytic oxidation method [1-4] and the temperature and pressure swing adsorption method [5] are typical adsorption methods. The former has several disadvantages that activated carbon consumption is large and the reuse of the catalyzer is difficult. While the disadvantages of the temperature and pressure swing adsorption are that it needs complex process, huge investment and energy cost. Chemical absorption is mainly based on the methods of chemical oxidation absorption, which utilizes sodium hypophosphite, potassium permanganate sulfuric acid and hydrogen peroxide [6, 7] reacting with PH3 for removal. However, chemical oxidate adsorption method has some disadvantages, for instance, consumption of huge oxidants, difficulty in operation, and the fluctuating efficiency evident with the change of oxidant concentration. In our perliminary study [8, 9], one Pd ()-Cu() catalyst, qualified with a good effect for removing PH3, has been selected from transition metal ions. The experiment results showed that the catalyst can remove PH3 from yellow phosphorus tail gas at atmospheric pressure, in low temperature and in microaerobic conditions. It was also demonstrated that the catalyst only needs simple equipments and its consumption is low. What's more, the catalyst holds good quality characters, such as strong selectivity, high purification efficiency, longer stability time, lower reaction temperature, without additional heating equipment, lower energy consumption and separateness of reaction products. While it still lacks the kinetics of mass transfer and reaction for this method to remove PH3, resulting in the limited role in enlarging pilot-plant test. Our thesis attempts to make a study on mass transfer and reaction kinetics of PH3 absorption in double-stirred cell, including regional of kinetics, gas-side and liquid-side mass transfer, reaction rate constant, characteristic number of macrokinetics, etc, in order to provide basic kinetics datas for application of industrial.
* Corresponding author: Ping Ning, Professor, Doctoral Tutor, E-mail: ningping58@sina.com This research was funded by the National Natural Science Foundation of China (51008147) and the Yunnan Natural Science Foundation (2009ZC026M) - 30 www.sjfcd.org
7 12 4 5 1 2 3 5 5 10 6 5 9 8 13 11 9 8
Parameters instruction concentration of reactant B in bulk of liquid intensity of pressure of A in bulk of gas interfacial areas liquid volume liquid-side mass-transfer coefficient
Symbols
C
BL
P A
V k
k
L L
A + + + +
H + + +
second-order rate constant + + + + ? ? + G Note: regional of dynamic Ainstantaneous reaction; Binterface instantaneous reaction; Crapid reaction; Dpseudo-m order rapid reaction; Emedium speed reaction; Fpseudo-n order medium speed reaction; Gslow reaction; Hextremely slow reaction of liquid phase; "+" means being effected by the factor; "-" means not being effected by the factor; "?" means being effected by the factor probably with the same rate equation.
It was demonstrated in Table 2 that the volume variation of absorption solution had no effects on absorption rates of gases. Therefore, E~H can be excluded based on Table 1. By changing the stirring speed of liquid phase, it can be discovered that liquid-side mass transfer coefficients didn't affect the reaction rate k1. So A and C region could be ruled out. Depending on the earlier work, in the process of Pd()-Cu() catalytic oxidizing PH3, Pd() reacted with PH3 to remove PH3, and the reaction between Cu() and O2 achieved the regeneration of Pd(). It can be seen
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from Fig. 2, when the catalysts proportion of CPd() and CCu() were firmly maintained as 1:10, and the concentration of Pd() was improved from 1.0 10-3 mol/L to 2.0 10-2 mol/L, the absorption of PH3 ratio had no remarkable change with the different concentration catalysts of PH3. That is, the absorption of PH3 with catalysts is zero-order reaction. It can be found from the results that the concentration of liquid phase has no effect on reaction ratio. Thus the D region could be excluded as well. From all above, the reaction that PH3 was absorbed by Pd()-Cu() solution belongs to interface instantaneous reaction.
TABLE 2 THE FCATORS INFUENCES THE ABSORPTION OF PH3 BY PD()-CU()
Parameters Date of parameters Absorbing rate/mol (m2 s)-1 100 1.490 10-5
VL /ml
nL r m in1
50 1.506 10-5
For double-stirred cell, the perfect mixing coefficient was closed to 1 when the stirring speeds of gas phase were 120~800 rmin-1 and 100~187 rmin-1 for liquid phase. In the investigation, the stirring speed of gas phase and liquid phase were 300 rmin-1 and 150 rmin-1 respectively. So the concentration of outlet PH3 can be regarded as the concentration of main reaction. The catalysts concentration was fixed as 5 10-3 mol/L, and the input concentration of PH3 changed and then the output concentration of PH3 was measured, thus relevant absorption rate can be gained by means of material balance calculation, the interface concentration of PH3 could be calculated by formula (3). Experiments above were repeated with different temperatures and results were represented in Fig. 5. From the picture, the interface concentration of PH3 varied directly as reaction rate in range of temperature. That is, for the PH3, absorption reaction was first order reaction. The slope of the line in the Fig. 5 was the rate constant of the pseudo-first order reaction. According to the Arrhenius formula (4)by taking different temperatures and corresponding reaction constants to form equation, the activation energy Ea=14.35 kJ/mol and the pre-exponential factor k0=1.99 108 can be calculated. [14] The activation energy of activated carbon catalytic oxidation of PH3 is 63.1 kJ/mol , therefore, the energy of gas-liquid phase absorption process was far lower than that of gas-solid absorption process.
k ko e Ea / RT
(4)
(5)
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According to data of experiment stated previously, Ha was 552.56 when T was 303.15 K. For Ha>3, the intrinsic chemical reaction rate was so fast that the mass transfer rate was promoted by up to 552.56 times. 2) Study on Chemical Enhancement Factors Practical enhancement factor E of mass transfer efficiency accompanied with chemical reaction can be expressed as formula (6). Combined with the experiment data, a certain practical enhancement factor derived from formula (6) was 593.63. Moreover, different enhancement factors could be acquired according to the application of different gas-liquid reaction mass transfer models. For membrane model, the relation between E and Ha is as (7). The enhancement factor in theory was 536.37 combining formula (6).
N PH 3 k L C A*
Ha tanh Ha
(6)
(7)
The deviation between theory enhancement factor and practical enhancement was 9.65% based on membrane model. It's 2.88% between theory enhancement and Ha number.
5 CONCLUSIONS
In conclusion, the results of the experiment indicated that the gas-liquid reaction, PH3 absorbed by Pd()-Cu() solution, belongs to interfacial reaction. The reaction can be confirmed as zero order reaction for Pd and pseudo-first order reaction for absorption of PH3. The rate constant for the first-order reaction was over the order of 105. Characteristic numbers of macrokinetics were confirmed as well. These base data will be very useful for application of industrial. In follow-up work, mechanism study and analysis will be studied in details. Its important to gain better result of PH3 removal.
SYMBOL DESCRIPTION
T thermodynamic temperature, K P partial pressure of solute A in gas phase, Pa CPD(II) concentration of palladium() ion , molL-1 Ccu(II) concentration of ion, molL-1 VL volume of holding of liquid phase, mL nG stirring speed of gas phase, rmin-1 nL stirring speed of liquid phase, rmin-1 CPD(II) concentration of palladium() ion , molL-1 Ccu(II) concentration of ion, molL-1 A interfacial area, m2 kL liquid phase mass transfer coefficient, ms-1 kG gas phase mass transfer coefficient, molm-2Pa-1s-1 O 2 volume fraction of O2 in gas phase Ci concentration of interfacial PH3, molL-1 H solubility coefficient, molm-3Pa-1 k0 pre-exponential factor N PH 3 absorption rate of PH3, molm-2s-1 Ha H a number Ea intrinsic chemical reaction activation energy, kJmol-1 D diffusion coefficient of PH3 in the liquid phase, m-2s-1 kL liquid phase mass transfer coefficient, ms-1
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AUTHORS
1Guangfei
Qu,
Yunnan,
1978.6, of
2Yixing
professor. and
Doctorate
mayixing99@163.com
3Junyan
124169474@qq.com
pollution control of solid waste, cyclic economy, cleaner production. E-mail: qgfljy@126.com
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