In situ Synthesis of SAPO-34 Zeolites in Kaolin Microspheres for a Fluidized Methanol or Dimethyl Ether to Olefins Process

Abstract

Abstract: SAPO-34 zeolite is considered to be an effective catalyst for methanol or dimethyl ether conversion to olefins. In this study,we developed the In situ synthesis technology to prepare SAPO-34 zeolite in kaolin microspheres as a catalyst for fluidized methanol or dimethyl ether to olefins process. The silicoaluminophosphate zeolite was first time reported to be synthesized in kaolin microspheres. The SAPO-34 content of synthesized catalyst was about 22% as measured by three different quantitative methods(micropore area,X-ray fluorescence and energy dispersive spectroscopy element analysis). Most of the SAPO-34 zeolites were in nanoscale size and distributed uniformly inside the spheres. The catalytic performance was evaluated in fixed bed and fluidized bed reactors. Compared with the conventional spray-dry catalyst,SAPO/kaolin catalyst showed superior catalytic activities,better olefin selectivities(up to 94%,exclusive coke),and very good hydrothermal stability. The In situ synthesis of SAPO-34 in kaolin microspheres is a facile and economically feasible way to prepare more effective catalyst for fluidized MTO/DTO(methanol to olefins/dimethyl ether to olefins) process.

Key words: SAPO-34, In situ synthesis, kaolin, fluidized bed, methanol to olefins

摘要： SAPO-34 zeolite is considered to be an effective catalyst for methanol or dimethyl ether conversion to olefins. In this study,we developed the In situ synthesis technology to prepare SAPO-34 zeolite in kaolin microspheres as a catalyst for fluidized methanol or dimethyl ether to olefins process. The silicoaluminophosphate zeolite was first time reported to be synthesized in kaolin microspheres. The SAPO-34 content of synthesized catalyst was about 22% as measured by three different quantitative methods(micropore area,X-ray fluorescence and energy dispersive spectroscopy element analysis). Most of the SAPO-34 zeolites were in nanoscale size and distributed uniformly inside the spheres. The catalytic performance was evaluated in fixed bed and fluidized bed reactors. Compared with the conventional spray-dry catalyst,SAPO/kaolin catalyst showed superior catalytic activities,better olefin selectivities(up to 94%,exclusive coke),and very good hydrothermal stability. The In situ synthesis of SAPO-34 in kaolin microspheres is a facile and economically feasible way to prepare more effective catalyst for fluidized MTO/DTO(methanol to olefins/dimethyl ether to olefins) process.

关键词: SAPO-34, In situ synthesis, kaolin, fluidized bed, methanol to olefins

ZHU Jie, CUI Yu, NAWAZ Zeeshan, WANG Yao, WEI Fei. In situ Synthesis of SAPO-34 Zeolites in Kaolin Microspheres for a Fluidized Methanol or Dimethyl Ether to Olefins Process[J]. , 2010, 18(6): 979-987.

朱杰, 崔宇, NAWAZ Zeeshan, 王垚, 魏飞. In situ Synthesis of SAPO-34 Zeolites in Kaolin Microspheres for a Fluidized Methanol or Dimethyl Ether to Olefins Process[J]. , 2010, 18(6): 979-987.

References

1 Stocker, M., “Methanol-to-hydrocarbons: Catalytic materials and their behavior”, Microporous Mesoporous Mater., 29, 3-48(1999).
2 Bjorgen, M., Svelle, S., Joensen, F., Nerlov, J., Kolboe, S., Bonino, F., Palumbo, L., Bordiga, S., Olsbye, U., “Conversion of methanol to hydrocarbons over zeolite H-ZSM-5: On the origin of the olefinic species”, J. Catal., 249(2), 195-207(2007).
3 Haw, J.F., Song, W.G., Marcus, D.M., Nicholas, J.B., “The mechanism of methanol to hydrocarbon catalysis”, Acc. Chem. Res., 36(5), 317-326(2003).
4 Arstad, B., Kolboe, S., “The reactivity of molecules trapped within the SAPO-34 cavities in the methanol-to-hydrocarbons reaction”, J. Am. Chem. Soc., 121, 8137-8138(2001).
5 Song, W., Fu, H., Haw, J.F., “Supramolecular origins of product selectivity for methanol-to-olefin catalysis on HSAPO-34”, J. Am. Chem. Soc., 123, 4749-4754(2001).
6 Song, W.G., Marcus, D.M., Fu, H., Ehresmann, J.O., Haw, J.F., “An oft-studied reaction that may never have been: Direct catalytic conversion of methanol or dimethyl ether to hydrocarbons on the solid acids HZSM-5 or HSAPO-34”, J. Am. Chem. Soc., 124(15), 3844-3845(2002).
7 Aguayo, A.T., Gayubo, A.G., Vivanco, R., Olazar, M., Bilbao, J., “Role of acidity and microporous structure in alternative catalysts for the transformation of methanol into olefins”, Appl. Catal. A Gen., 283(1-2), 197-207(2005).
8 Song, W.G., Haw, J.F., “Improved methanol-to-olefin catalyst with nanocages functionalized through ship-in-a-bottle synthesis from PH3”, Angew. Chem. Int. Ed., 42(8), 892-894(2003).
9 Chen, D., Grlnvold, A., Moljord, K., Holmen, A., “Methanol conversion to light olefins over SAPO-34: Reaction network and deactivation kinetics”, Ind. Eng. Chem. Res., 46(12), 4116-4123(2007).
10 Bos, A.N.R., Tromp, P.J.J., Akse, H.N., “Conversion of methanol to lower olefins—Kinetic modeling, reactor simulation, and selection”, Ind. Eng. Chem. Res., 34(11), 3808-3816(1995).
11 Keil, F.J., Hinderer, J., Garayhi, A.R., “Diffusion and reaction in ZSM-5 and composite catalysts for the methanol-to-olefins process”, Catal. Today, 50(3-4), 637-650(1999).
12 Zhou, H.Q., Wang, Y., Wei, F., Wang, D.Z., Wang, Z.W., “In situ synthesis of SAPO-34 crystals grown onto α-Al₂O₃ sphere supports as the catalyst for the fluidized bed conversion of dimethyl ether to olefins”, Appl. Catal. A-Gen., 341(1-2), 112-118(2008).
13 Chen, Y.J., Zhou, H.Q., Zhu, J., Zhang, Q., Wang, Y., Wang, D.Z., Wei, F., “Direct synthesis of a fluidizable SAPO-34 catalyst for a fluidized dimethyl ether-to-olefins process”, Catal. Lett., 124(3-4), 297-303(2008).
14 Basaldella, E.I., Bonetto, R., Tara, J.C., “Synthesis of nay-zeolite on preformed kaolinite spheres—Evolution of zeolite content and textural properties with the reaction-time”, Ind. Eng. Chem. Res., 32(4), 751-752(1993).
15 Zhu, J., Cui, Y., Wang, Y., Wei, F., “Direct synthesis of hierarchical zeolite from a natural layered material”, Chem. Commun.,(22), 3282-3284(2009).
16 Caballero, I., Colina, F.G., Costa, J., “Synthesis of X-type zeolite from dealuminated kaolin by reaction with sulfuric acid at high temperature”, Ind. Eng. Chem. Res., 46(4), 1029-1038(2007).
17 Chandrasekhar, S., Pramada, P.N., “Investigation on the synthesis of zeolite NaX from kerala kaolin”, J. Porous Mat., 6(4), 283-297(1999).
18 Wei, Y.X., Zhang, D.Z., Chang, F.X., Liu, Z.M., “Direct observation of induction period of MTO process with consecutive pulse reaction system”, Catal. Commun., 8(12), 2248-2252(2007).
19 Lin, D.C., Xu, X.W., Zuo, F., Long, Y.C., “Crystallization of JBW, CAN, SOD and ABW type zeolite from transformation of meta-kaolin”, Microporous Mesoporous Mater., 70(1-3), 63-70(2004).
20 Liu, H.H., Ma, J.T., Gao, X.H., “Synthesis, characterization and evaluation of a novel resid FCC catalyst based on in situ synthesis on kaolin microspheres”, Catal. Lett., 110(3-4), 229-234(2006).
21 Tan, Q.F., Bao, X.J., Song, T.C., Fan, Y., Shi, G., Shen, B.J., Liu, C.H., Gao, X.H., “Synthesis, characterization, and catalytic properties of hydrothermally stable macro-meso-micro-porous composite materials synthesized via in situ assembly of preformed zeolite Y nanoclusters on kaolin”, J. Catal., 251, 69-79(2007).
22 Mintova, S., Olson, N.H., Valtchev, V., Bein, T., “Mechanism of zeolite A nanocrystal growth from colloids at room temperature”, Science, 283, 958-960(1999).
23 Wu, X.C., Abraha, M.G., Anthony, R.G., “Methanol conversion on SAPO-34: Reaction condition for fixed-bed reactor”, Appl. Catal. A-Gen., 260(1), 63-69(2004).
24 Popova, M., Minchev, C., Kanazirev, V., “Methanol conversion to light alkenes over SAPO-34 molecular sieves synthesized using various sources of silicon and aluminium”, Appl. Catal. A-Gen., 169(2), 227-235(1998).
25 Chen, D., Moljord, K., Fuglerud, T., Holmen, A., “The effect of crystal size of SAPO-34 on the selectivity and deactivation of the MTO reaction”, Microporous Mesoporous Mater., 29(1-2), 191-203(1999).
26 Lee, Y.J., Baek, S.C., Jun, K.W., “Methanol conversion on SAPO-34 catalysts prepared by mixed template method”, Appl. Catal. A-Gen., 329, 130-136(2007).
27 Smit, B., Maesen, T.L.M., “Towards a molecular understanding of shape selectivity”, Nature, 451(7179), 671-678(2008).
28 Yilmaz, B., Muller, U., “Catalytic applications of zeolites in chemical industry”, Top. Catal., 52(6-7), 888-895(2009).
29 Mei, C.S., Wen, P.Y., Liu, Z.C., Liu, H.X., Wang, Y.D., Yang, W.M., Xie, Z.K., Hua, W.M., Gao, Z., “Selective production of propylene from methanol: Mesoporosity development in high silica HZSM-5”, J. Catal., 258(1), 243-249(2008).

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