Numerical study of pore structure effect on SO2-CaO reactions

doi:10.1016/j.cjche.2014.12.004

Chinese Journal of Chemical Engineering ›› 2015, Vol. 23 ›› Issue (4): 652-658.DOI: 10.1016/j.cjche.2014.12.004

• 催化、动力学与反应工程 • 上一篇下一篇

Numerical study of pore structure effect on SO₂-CaO reactions

Liang Ma¹, Liyong Cao², Rong He¹

1 Department of Thermal Engineering, Tsinghua University, Beijing 100084, China;
2 Dongfang Electric Corporation, Chengdu 611731, China

收稿日期:2013-09-18 修回日期:2014-02-11 出版日期:2015-04-28 发布日期:2015-05-13
通讯作者: Rong He
基金资助:
Supported by the National Natural Science Foundation of China (51176096).

Numerical study of pore structure effect on SO₂-CaO reactions

Liang Ma¹, Liyong Cao², Rong He¹

1 Department of Thermal Engineering, Tsinghua University, Beijing 100084, China;
2 Dongfang Electric Corporation, Chengdu 611731, China

Received:2013-09-18 Revised:2014-02-11 Online:2015-04-28 Published:2015-05-13
Contact: Rong He
Supported by:
Supported by the National Natural Science Foundation of China (51176096).

摘要/Abstract

摘要： The effect of varying pore structures on the kinetics of SO₂-CaO reactions is not fully understood in the previous studies. Combining fractal pore model, gas molecular movement model and two-stage reaction model, a new desulfurization model is established in this paper. Fractal pore model is used to simulate CaO particle and gas molecular movement model is used to simulate gas diffusion in pores. Fractal dimension is used to characterize complexity of pore structure instead of tortuosity factor. It is found that the reaction is significantly affected by pore structures. A modulus ø is introduced to characterize the relationship between varying pore structures and apparent reaction parameters. And this relationship is verified by thermo-gravimetric analysis (TGA) data. Comparing to the previous models, the effect of varying pore structure on the kinetics of the reaction is described more accurately by the desulfurization model.

关键词: Desulfurization model, Gas diffusion, Fractal, Pore structure

Abstract: The effect of varying pore structures on the kinetics of SO₂-CaO reactions is not fully understood in the previous studies. Combining fractal pore model, gas molecular movement model and two-stage reaction model, a new desulfurization model is established in this paper. Fractal pore model is used to simulate CaO particle and gas molecular movement model is used to simulate gas diffusion in pores. Fractal dimension is used to characterize complexity of pore structure instead of tortuosity factor. It is found that the reaction is significantly affected by pore structures. A modulus ø is introduced to characterize the relationship between varying pore structures and apparent reaction parameters. And this relationship is verified by thermo-gravimetric analysis (TGA) data. Comparing to the previous models, the effect of varying pore structure on the kinetics of the reaction is described more accurately by the desulfurization model.

Key words: Desulfurization model, Gas diffusion, Fractal, Pore structure

Liang Ma, Liyong Cao, Rong He. Numerical study of pore structure effect on SO₂-CaO reactions[J]. Chinese Journal of Chemical Engineering, 2015, 23(4): 652-658.

Liang Ma, Liyong Cao, Rong He. Numerical study of pore structure effect on SO₂-CaO reactions[J]. Chin.J.Chem.Eng., 2015, 23(4): 652-658.

参考文献

[1] L. Liu, S. Zhang, X. Lü, X. Yu, S. Zhi, Ozonation of sulfur dioxide in sulphuric acid solution, Chin. J. Chem. Eng. 21 (7) (2013) 808-812.

[2] J. Gao, T.Wang, Q. Shu, N. Zeeshan, Q.Wen, D. Wang, J.Wang, An adsorption kinetic model for sulfur dioxide adsorption by ZL50 activated carbon, Chin. J. Chem. Eng. 18 (2) (2010) 223-230.

[3] J. Xue, L.Meng', B. Shen, S. Du, X. Lan, Study on desorbing sulfur dioxide from citrate solution by ultrasonification, Chin. J. Chem. Eng. 15 (4) (2007) 478-485.

[4] R. Hallaj, M. Nikazar, B. Dabir, Thermogravimetric study and modeling of direct sulfation of limestone by sulfur dioxide, Chin. J. Chem. Eng. 12 (4) (2004) 566-569.

[5] C. Hsia, G.R. St Pierre, K. Raghunathan, L.S. Fan, Diffusion through CaSO4 formed the reaction of CaO with SO₂ and O₂, AIChE J. 39 (4) (1993) 698-700.

[6] C. Hsia, G.R. St Pierre, L.S. Fan, Isotope study on diffusion in CaSO4 formed during sorbent-flue-gas reaction, AIChE J. 41 (10) (1995) 2337-2340.

[7] G.A. Simons, A.R. Garman, Small pore closure and the deactivation of the limestone sulfation reaction, AIChE J. 32 (9) (1986) 1491-1499.

[8] C.Wang, X. Shen, Y. Xu, Investigation on sulfation ofmodified Ca-based sorbent, Fuel Process. Technol. 79 (2) (2002) 121-133.

[9] S.K. Bhatia, D.D. Perlmutter, The effect of pore structure on fluid-solid reactions: application to the SO₂-lime reaction, AICHE J. 27 (1981) 226-234.

[10] R.H. Borgwardt, K.R. Bruce, J. Blake, An investigation of product-layer diffusivity for calcium oxide sulfation, Ind. Eng. Chem. Res. 26 (10) (1987) 1993-1998.

[11] C.N. Satterfield, Mass Transfer in Heterogeneous Catalysis, M.I.T. Press, Cambridge, United States of America, 1970.

[12] O. Levenspiel, Chemical Reaction Engineering, Wiley, New York, United States of America, 1972.

[13] N. Orbey, G. Dogu, T. Dogu, Breakthrough analysis of noncatalytic solid-gas reactions: reaction of SO₂ with calcined limestone, Can. J. Chem. Eng. 60 (2) (1982) 314-318.

[14] J. Szekely, J.W. Evans, A structural model for gas-solid reactions with a moving boundary, Chem. Eng. Sci. 25 (1970) 1091-1107.

[15] P.A. Ramachandran, L.K. Doraiswamy, Modeling of noncatalytic gas-solid reactions, AIChE J. 28 (1982) 881-900.

[16] M. Hartman, R.W. Coughlin, Reaction of sulfur dioxide with limestone and the grain model, AIChE J. 22 (1976) 490-498.

[17] M. Hartman, O. Trnka, Influence of temperature on the reactivity of limestone particles with sulfur dioxide, Chem. Eng. Sci. 35 (1980) 1189-1194.

[18] T. Bardakci, Diffusional study of the reaction of sulfur dioxide with reactive porous matrices, Thermochim. Acta 76 (1984) 287-300.

[19] R.H. Borgwardt, K.R. Bruce, Effect of specific surface area on the reactivity of CaO with SO₂, AIChE J. 32 (1986) 239-246.

[20] P.G. Christman, T.F. Edgar, Distributed pore-size model for sulfation of limestone, AICHE J. 29 (1983) 388-395.

[21] D. Kocaefa, D. Karman, F.R. Steward, Interpretation of the sulfation rate of CaO,MgO, and ZnO with SO₂ and SO₃, AIChE J. 33 (1987) 1835-1843.

[22] S.K. Bhatia, D.D. Perlmutter, A random pore model for fluid-solid reactions: I. Isothermal, kinetic control, AIChE J. 26 (1980) 379-386.

[23] S.K. Bhatia, D.D. Perlmutter, A randomporemodel for fluid-solid reactions: II. Diffusion and transport effects, AIChE J. 27 (1981) 247-254.

[24] B. Lindner, D. Simonsson, Comparison of structural models for gas-solid reactions in porous solids undergoing structural changes, Chem. Eng. Sci. 36 (1981) 1519-1527.

[25] M. Sahimi, G.R. Gavalas, T.T. Tsotsis, Statistical and continuum models of fluid-solid reactions in porous media, Chem. Eng. Sci. 45 (1990) 1443-1502.

[26] P. Pfeifer, D. Avnir, Chemistry in noninteger dimensions between two and three. I. Fractal theory of heterogeneous surfaces, J. Chem. Phys. 79 (7) (1983) 3558-3565.

[27] A.J. Katz, A.H. Thompson, Fractal sandstone pores: implication for conductivity and pore formation, Phys. Rev. Lett. 54 (1985) 1325-1328.

[28] Y. Gefen, A. Aharony, S. Alexander, Anomalous diffusion on percolation clusters, Phys. Rev. Lett. 50 (1983) 77-80.

[29] P. Levitz, From Knudsen diffusion to Levy walks, Europhys. Lett. 39 (1997) 593-598.

[30] M. Costa, A. Araujo, H. Silva, J. Andrade, Scaling behavior of diffusion and reaction processes in percolating porous media, Phys. Rev. E. 67 (2003) 061406.

[31] Z. Liang, R. He, Q. Chen, Fractal generation of char pores through randomwalk, Combust. Sci. Technol. 179 (3) (2007) 637-661.

[32] L. Cao, R. He, Gas diffusion in fractal porous media, Combust. Sci. Technol. 182 (2010) 822-841.

[33] G.A. Bird, Molecular Gas Dynamics and the Direct Simulation of Gas Flows, Oxford University Press, New York, 1994.

[34] R. He, X. Xu, C. Chen, Evolution of pore fractal dimensions for burning porous chars, Fuel 77 (1998) 1291-1295.

[35] J. Jeans, An Introduction to the Kinetic Theory of Gases, Cambridge University Press, Cambridge, 1952.

[36] S. Glasstone, K.L. Ladler, H. Eyring, The Theory of Rate Processes, McGraw-Hill Book Co., New York, 1941.

[37] R.H. Flowler, E.A. Guggenheim, Statistical Thermodynamics, Cambridge University Press, Cambridge, 1967.

[38] R.D. Present, Note on the simple collision theory of bimolecular reactions, Proc. Natl. Acad. Sci. U. S. A. 41 (1955) 415-417.

[39] C.M. Kachhava, Solid State Physics, Tata McGraw-Hill Pub, New Delhi, 1990.

[40] W. Duo, K. Laursen, J. Lim, J. Grace, Crystallization and fracture: Product layer diffusion in sulfation of calcined limestone, Ind. Eng. Chem. Res. 43 (2004) 5653-5662.

[41] D.W. Marsh, D.L. Ulrichson, Rate and diffusional study of the reaction of calcium oxide with sulfur dioxide, Chem. Eng. Sci. 40 (3) (1985) 423-433.

[42] W. He, R. He, L. Cao, T. Ito, T. Suda, J. Sato, Numerical study of the relationships between pore structures and reaction parameters for coal char particles, Combust. Sci. Technol. 184 (12) (2012) 2084-2099.

[43] C.C. Geogakis, W. Chang, J. Szekely, A changing grain size model for gas-solid reactions, Chem. Eng. Sci. 34 (8) (1979) 1072-1075.

Numerical study of pore structure effect on SO₂-CaO reactions

Numerical study of pore structure effect on SO₂-CaO reactions

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