Preparation and Characterization of Tungsten-substituted Molybdophosphoric Acids and Catalytic Cyclodehydration of 1,4-Butanediol to Tetrahydrofuran

Abstract

Abstract: A series of tungsten-substituted molybdophosphoric acids(H₃PMo_12-nWnO₄₀·xH₂O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy(ICPAES),thermal gravimetry and differential scanning calorimetry(TG-DSC),Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),and FTIR pyridine adsorption.The as-prepared heteropoly acids have a Keggin type structure.The synthesis of tetrahydrofuran by reactive distillation and cyclodehydration of 1,4-butanediol was studied using the tungsten-substituted molybdophosphoric acids as catalysts.The results of catalytic test indicated that the catalytic activity increased with the increase in the substitution number(n) of tungsten atom in H₃PMo_12-nWnO₄₀·xH₂O and was constant as the substitution number(n) was more than 8.The catalytic activity increased with the increase in the catalyst loading and the selectivity of tetrahydrofuran was nearly 100%.

Key words: tungsten-substituted molybdophosphoric acid, 1,4-butanediol, tetrahydrofuran, reactive distillation

摘要： A series of tungsten-substituted molybdophosphoric acids(H₃PMo_12-nWnO₄₀·xH₂O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy(ICPAES),thermal gravimetry and differential scanning calorimetry(TG-DSC),Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),and FTIR pyridine adsorption.The as-prepared heteropoly acids have a Keggin type structure.The synthesis of tetrahydrofuran by reactive distillation and cyclodehydration of 1,4-butanediol was studied using the tungsten-substituted molybdophosphoric acids as catalysts.The results of catalytic test indicated that the catalytic activity increased with the increase in the substitution number(n) of tungsten atom in H₃PMo_12-nWnO₄₀·xH₂O and was constant as the substitution number(n) was more than 8.The catalytic activity increased with the increase in the catalyst loading and the selectivity of tetrahydrofuran was nearly 100%.

关键词: tungsten-substituted molybdophosphoric acid, 1,4-butanediol, tetrahydrofuran, reactive distillation

WU Huixiong, ZHOU Mei, QU Yixin, LI Haixia, YIN Hengbo. Preparation and Characterization of Tungsten-substituted Molybdophosphoric Acids and Catalytic Cyclodehydration of 1,4-Butanediol to Tetrahydrofuran[J]. Chin.J.Chem.Eng., 2009, 17(2): 200-206.

吴慧雄, 周梅, 屈一新, 李海霞, 殷恒波. Preparation and Characterization of Tungsten-substituted Molybdophosphoric Acids and Catalytic Cyclodehydration of 1,4-Butanediol to Tetrahydrofuran[J]. Chinese Journal of Chemical Engineering, 2009, 17(2): 200-206.

References

1 Hunter, S.E., Ehrenberger, C.E., Savage, P.E., “Kinetics and mechanism of tetrahydrofuran synthesis via 1,4-butanediol dehydration in high-temperature water”, J. Org. Chem., 71, 6229-6239 (2006).
2 Kanetaka, J., Asano, T., Masamune, S., “New process for production of tetrahydrofuran”, Ind. Eng. Chem., 62, 24-32 (1970).
3 Müller, S.P., Kucher, M., Ohlinger, C., Kraushaar-Czarnetzki, B., “Extrusion of Cu/ZnO catalysts for the single-stage gas-phase processing of dimethyl maleate to tetrahydrofuran”, J. Catal., 218, 419-426 (2003).
4 Igarashi, A., Sato, S., Takahashi, R., Sodesawa, T., Kobune, M., “Dehydration of 1,4-butanediol over lanthanide oxides”, Catal. Commun., 8, 807-810 (2007).
5 Aghaziarati, M., Kazemeini, M., Soltanieh, M., Sahebdelfar, S., “Evaluation of zeolites in production of tetrahydrofuran from 1,4-butanediol:Performance tests and kinetic investigations”, Ind. Eng. Chem. Res., 46, 726-733 (2007).
6 Yamamoto, N., Sato, S., Takahashi, R., Inui, K., “Synthesis of homoallyl alcohol from 1,4-butanediol over ZrO₂ catalyst”, Catal. Commun., 6, 480-484 (2005).
7 Devassy, B.M., Lefebvre, F., Halligudi, S.B., “Zirconia-supported 12-tungstophosphoric acid as a solid catalyst for the synthesis of linear alkyl benzenes”, J. Catal., 231, 1-10 (2005).
8 Kumbar, S.M., Shanbhag, G.V., Lefebvre, F., Halligudi, S.B., “Heteropoly acid supported on titania as solid acid catalyst in alkylation of p-cresol with tert-butanol”, J. Mol. Catal. A:Chem., 256, 324-334 (2006).
9 Pizzio, L.R., Vázquez, P.G., Cáceres, C.V., Blanco, M.N., “Supported Keggin type heteropolycompounds for ecofriendly reactions”, Appl. Catal. A:General, 256, 125-139 (2003).
10 Lim, S.S., Park, G.I., Choi, J.S., Song, I.K., Lee, W.Y., “Heterogeneous liquid-phase lactonization of 1,4-butanediol using H3+x PMo12-xVxO40 (x=0-3) catalysts immobilized on polyaniline”, Catal. Today, 74, 299-307 (2002).
11 Li, H., Yin, H., Jiang, T., Hu, T., Wu, J., Wada, Y., “Cyclodehydration of 1,4-butanediol to tetrahydrofuran catalyzed by supported silicotungstic acid”, Catal. Commun., 7, 778-782 (2006).
12 Wu, Y., Ye, X., Yang, X., Wang, X., Chu, W., Hu, Y., “Heterogenization of heteropolyacids:A general discussion on the preparation of supported acid catalysts”, Ind. Eng. Chem. Res., 35, 2546-2560 (1996).
13 Newman, A.D., Lee, A.F., Wilson, K., Young, N.A., “On the active site in H3PW12O40/SiO₂ catalysts for fine chemical synthesis”, Catal. Lett., 102, 45-50 (2005).
14 Devassy, B.M., Halligudi, S.B., “Zirconia-supported heteropoly acids:Characterization and catalytic behavior in liquid-phase veratrole benzoylation”, J. Catal., 236, 313-323 (2005).
15 Timofeeva, M.N., “Acid catalysis by heteropoly acids”, Appl. Catal. A:General, 256, 19-35 (2003).
16 Kozhevnikov, I.V., “Ctalysis by heteropoly acids and muticomponent in liquid-phase reactions”, Chem. Rev., 98, 171-198 (1998).
17 Casuscelli, S.G., Crivello, M.E., Perez, C.F., Ghione, G., Herrero, E.R., Pizzio, L.R., Vázquez, P.G., Cáceres, C.V., Blanco, M.N., “Effect of reaction conditions on limonene epoxidation with H₂O₂ catalyzed by supported Keggin heteropolycompounds”, Appl. Catal. A:General, 274, 115-122 (2004).
18 Deusser, L.M., Petzoldt, J.C., Gaube, J.W., “Kinetic model for methacrolein oxidation-Influence of cesium and vanadium on heteropolyacid catalysts CsxH3-x+y [PMo12-yVyO40]”, Ind. Eng. Chem. Res., 37, 3230-3236 (1998).
19 Inumaru, K., Ono, A., Kubo, H., Misono, M., “Catalysis by heteropoly compounds Part 39 The structure and redox behaviour of vanadium species in molybdovanadophosphoric acid catalysts during partial oxidation of isobutane”, J. Chem. Soc. Faraday Trans., 94, 1765-1770 (1998).
20 Khenkin, A.M., Weiner, L., Neumann, R., “Selective ortho hydroxylation of nitrobenzene with molecular oxygen catalyzed by the H5PV2Mo10O40 polyoxometalate”, J. Am. Chem. Soc., 127, 9988-9989 (2005).
21 Zhang, F., Guo, M., Ge, H., Wang, J., “Hydroxylation of benzene with hydrogen peroxide over highly efficient molybdovanadophosphoric heteropoly acid catalysts”, Chin. J. Chem. Eng., 15, 895-898 (2007).
22 Shan, Y., Wu, G., Yu, R., Xu, J., Wang, B., Kou, X., “Catalysis of heteropoly acids (H3PMo12-xWxO40) in glutaraldehyde synthesis by phase transfer reative extraction process”, Chin. J. Mol. Catal., 13, 54-58 (1999).
23 Ding, Y., Ma, B., Gao, Q., Li, G., Yan, L., Suo, J., “A spectroscopic study on the 12-heteropolyacids of molybdenum and tungsten (H3PMo12-xWxO40) combined with cetylpyridinium bromide in the epoxidation of cyclopentene”, J. Mol. Catal. A:Chem., 230, 121-128 (2005).
24 Yu, Z., Li, S., Han, F., Wang, S., Zhou, G., Zhang, S., “Physicochemical property of H3PMo12-xWxO40 heteropoly acid”, Chinese Science Bulletin, 31, 1478-1482 (1986). (in Chinese)
25 Yang, J., Janik, M.J., Ma, D., Zheng, A., Zhang, M., Neurock, M., Davis, R.J., Ye, C., Deng, F., “Location, acid strength, and mobility of the acidic protons in Keggin 12-H3PMo12-xWxO40:A combined solid-state NMR spectroscopy and DFT quantum chemical calculation study”, J. Am. Chem. Soc., 127, 18274-18280 (2005).
26 Rao, P.M., Wolfson, A., Kababya, S., Vega, S., Landau, M.V., “Immobilization of molecular H3PMo12-xWxO40 heteropolyacid catalyst in alumina-grafted silica-gel and mesostructured SBA-15 silica matrices”, J. Catal., 232, 210-225 (2005).
27 Jalil, P.A., Tabet, N., Faiz, M., Hamdan, N.M., Hussain, Z., “Surface investigation on thermal stability of tungstophosphoric acid supported on MCM-41 using synchrotron radiation”, Appl. Catal. A:General, 257, 1-6 (2004).
28 Micek-Ilnicka, A., “Characterization of acid catalysts by thermometric titration”, Catal. Lett., 81, 233-236 (2002).
29 Cai, X., Du, D., Ni, J., Jin, Y., Zhu, J., Qian, Y., “Enthalpies of formation and DSC and TG results of heteropoly acids containing tungsten and molybdenum”, Thermochimica Acta, 292, 45-50 (1997).
30 Ressler, T., Timpe, O., Girgsdies, F., Wienold, J., Neisius, T., “In situ investigations of the bulk structural evolution of vanadium-containing heteropolyoxomolybdate catalysts during thermal activation”, J. Catal., 231, 279-291 (2005).
31 Niu, J., Wang, J., Introduction of Heteropoly Compound, 1st ed., Henan University Press, Kaifeng (2000). (in Chinese)
32 Kim, H., Kim, P., Lee, K.Y., Yeom, S.H., Yi, J., Song, I.K., “Preparation and characterization of heteropolyacid/mesoporous carbon catalyst for the vapor-phase 2-propanol conversion reaction”, Catal. Today, 111, 361-365 (2006).
33 Yang, L., Qi, Y., Yuan, X., Shen, J., Kim, J., “Direct synthesis, characterization and catalytic application of SBA-15 containing heteropolyacid H3PW>SUB>12O40”, J. Mol. Catal. A:Chem., 229, 199-205 (2005).
34 Dimitratos, N., Pina, C.D., Falletta, E., Bianchi, C.L., Santo, V. D., Rossi, M., “Effect of Au in Cs2.5H1.5PVMo11O40m and Cs2.5H1.5PVMo11O40m/Au/TiO 2 catalysts in the gas phase oxidation of propylene”, Catal. Today, 122, 307-316 (2007).
35 Zhong, L.F., Zhang, Y.M., Tang, Y., Bai, Y., “Synthesis and characterization of Keggin P-Mo-V heteropolyanion and its LangmuirBlodgett film”, Polyhedron, 22, 2647-2653 (2003).
36 Misono, M., Mizuno, N., Katamura, K., Kasai, A., Konishi, Y., Sakata, K., Okuhara, T., Yoneda, Y., “Catalysis by heteropoly compounds”, Bull. Chem. Soc. Jpn., 55, 400-406 (1982).
37 Okumura, K., Yamashita, K., Hirano, M., Niwa, M., “The active and reusable catalysts in the benzylation of anisole derived from a heteropoly acid”, J. Catal., 234, 300-307 (2005).

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