Abstract
This paper analyzes results obtained in studies of K/W/Mn/SiO2 composite catalysts for the oxidative coupling of methane (OCM) and examines phase transformations involving melts that form in the K2O–WO3–Mn2O3–SiO2 system at typical temperatures of the heterogeneous OCM process.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Li, S., Reaction chemistry of W–Mn/SiO2 catalyst for the oxidative coupling of methane, J. Nat. Gas Chem., 2003, vol. 12, no. 1, pp. 1–9.
Usachev, N.Ya., Kharlamov, V.V., Belanova, E.P., Starostina, T.S., and Krukovskii, I.M., Oxidative processing of light alkanes; state-of-the-art and prospects, Russ. J. Gen. Chem., 2009, vol. 79, no. 6, pp. 1251–1263.
Erdöhelyi, A., Németh, R., Hancz, A., and Oszkó, A., Partial oxidation of methane on potassium-promoted WO3/SiO2 and on K2WO4/SiO2 catalysts, Appl. Catal., A, 2001, vol. 211, no. 1, pp. 109–121.
Palermo, A., Varquez, J.P.H., and Lambert, R.M., New efficient catalyst for the oxidative coupling of methane, Catal. Lett., 2000, vol. 68, nos. 3–4, pp. 191–196.
Lapeña-Rey, N. and Middleton, P.H., The selective oxidation of methane to ethane and ethylene in a solid oxide electrolyte reactor, Appl. Catal., A, 2003, vol. 240, nos. 1–2, pp. 207–220.
Seimanides, S., Tsiakaras, P., Verykios, X.E., and Vayenas, C.G., Oxidative coupling of methane over yttriadoped zirconia solid electrolyte, Appl. Catal., 1991, vol. 68, no. 1, pp. 41–53.
Ji, S., Xiao, T., Li, S., Chou, L., Zhang, B., Xu, C., Hou, R., York, A.P.E., and Green, M.L.H., Surface WO4 tetrahedron: the essence of the oxidative coupling of methane over M–W–Mn/SiO2 catalysts, J. Catal., 2003, vol. 220, no. 1, pp. 47–56.
Gholipour, Z., Malekzadeh, A., Ghiasi, M., Mortazavi, Y., and Khodadadi, A., Structural flexibility under oxidative coupling of methane; main chemical role of alkali ion in [Mn + (Li, Na, K or Cs) + W]/SiO2 catalysts, Iran. J. Sci. Technol., 2012, vol. 36, no. A2, pp. 189–211.
Nipan, G.D., Dedov, A.G., Loktev, A.S., Ketsko, V.A., Kol’tsova, T.N., Tyunyaev, A.A., and Moiseev, I.I., SiO2-based composites in the catalysis of methane oxidative coupling: role of phase composition, Dokl. Phys. Chem., 2008, vol. 419, no. 2, pp. 73–76.
Tyunyaev, A.A., Nipan, G.D., Kol’tsova, T.N., Loktev, A.S., Ketsko, V.A., Dedov, A.G., and Moiseev, I.I., Polymorphic Mn/W/Na(K,Rb,Cs)/SiO2 catalysts for oxidative coupling of methane, Russ. J. Inorg. Chem., 2009, vol. 54, no. 5, pp. 664–667.
Dedov, A.G., Nipan, G.D., Loktev, A.S., Tyunyaev, A.A., Ketsko, V.A., Parkhomenko, K.V., and Moiseev, I.I., Oxidative coupling of methane: influence of the phase composition of silica-based catalysts, Appl. Catal., A, 2011, vol. 406, nos. 1–2, pp. 1–12.
Kou, Y., Zhang, B., Niu, J.-Z., Li, S.-B., Wang, H.-Li., Tanaka, T., and Yoshida, S., Amorphous features of working catalysts: XAFS and XPS characterization of Mn/Na2WO4/SiO2 as used for the oxidative coupling of methane, J. Catal., 1998, vol. 173, no. 2, pp. 399–408.
Wang, S., Zheng, H., Zhang, Q., Li, Lin., Wu, H., Li, G., and Feng, C., Effects of polyaniline coating of cryptomelane-type KMn8O16 on electrochemical performance for lithium-ion batteries, J. Nanopart. Res., 2014, vol. 16, no. 2, paper 2232.
Nipan, G.D., Artukh, V.A., Yusupov, V.S., Loktev, A.S., Spesivtsev, N.A., Dedov, A.G., and Moiseev, I.I., Effect of pressure on the phase composition of Li(Na)/W/Mn/SiO2 composites and their catalytic activity for oxidative coupling of methane, Inorg. Mater., 2014, vol. 50, no. 9, pp. 912–916.
Herbstein, F.H., Ron, G., and Weissman, A., The thermal decomposition of potassium permanganate and related substances. Part I. Chemical aspects, J. Chem. Soc. A, 1971, part II, pp. 1821–1826.
Liu, Z.-X., Che, M.-W., Baeg, J.-O., and Lee, C.W., Removal of ethylene over KMnO4/Al2O3–SiO2, Bull. Korean Chem. Soc., 2006, vol. 27, no. 12, pp. 2064–2066.
Gelsing, R.J.H., Stein, H.N., and Stevels, J.M., The phase diagram K2WO4–WO3, Rec. Trav. Chim., 1965, vol. 84, no. 11, pp. 1452–1458.
Zimmerl, T., Schubert, W.-D., Bicherl, A., and Bock, A., Hydrogen reduction of tungsten oxides: alkali additions, their effect on the metal nucleation process and potassium bronzes under equilibrium conditions, Int. J. Refr. Met. Hard Mater., 2017, vol. 62, part B, pp. 87–96.
Kazenas, E.K., Termodinamika ispareniya dvoinykh oksidov (Thermodynamics of Binary Oxide Vaporization), Moscow: Nauka, 2004.
Spitsyn, V.I., Thermal stability and volatility of normal alkali tungstates, Zh. Obshch. Khim., 1950, vol. 20, no. 3, pp. 550–552.
Yamdagni, R., Pupp, C., and Porter, R.F., Mass spectrometric study of the evaporation of lithium and sodium molybdates and tungstates, J. Inorg. Nucl. Chem., 1970, vol. 32, no. 11, pp. 3509–3523.
Nipan, G.D., Buzanov, G.A., Zhizhin, K.Yu., and Kuznetsov, N.T., Phase states of Li(Na,K,Rb,Cs)/W/Mn/SiO2 composite catalysts for oxidative coupling of methane, Russ. J. Inorg. Chem., 2016, vol. 61, no. 14, pp. 1689–1707.
Nipan, G.D., Melt-assisted phase transformations of A/W/Mn/SiO2 (A = Li, Na, K, Rb, Cs) composite catalysts, Inorg. Mater., 2017, vol. 53, no. 6, pp. 553–559.
Nipan, G.D., Phase states of Na/W/Mn/SiO2 composites at temperatures of catalytic oxidative coupling of methane, Inorg. Mater., 2014, vol. 50, no. 10, pp. 1012–1018.
Nipan, G.D., Phase states of Li/W/Mn/SiO2 composites in catalytic oxidative coupling of methane, Inorg. Mater., 2015, vol. 51, no. 4, pp. 389–395.
Scholder, R. and Protzer, U., Uber Alkalomanganate( III) bis (V), Z. Anorg. Allg. Chem., 1969, vol. 369, nos. 3–6, pp. 313–326.
Delano, P.H., Classification of manganese dioxides, Ind. Eng. Chem., 1950, vol. 42, no. 3, pp. 523–527.
De Carvalho, A.J.C., Stages in the preparation of potassium manganate from pyrolusite, J. Appl. Chem., 1957, vol. 7, no. 4, pp. 145–151.
Delmas, C. and Fouassier, C., Les phase K x MnO2 (x = 1), Z. Anorg. Allg. Chem., 1976, vol. 420, no. 2, pp. 184–192.
Brachtel, G. and Hoppe, R., K6[Mn2O4] und K6[Fe2O4]–ein Verleich, Z. Anorg. Allg. Chem., 1978, vol. 446, no. 1, pp. 64–76.
Seipp, E. and Hoppe, R., Ein neues oxomanganat(II): K2Mn2O3, Z. Anorg. Allg. Chem., 1985, vol. 530, no. 11, pp. 117–126.
Jansen, M., Chang, F.M., and Hoppe, R., Zur Kenntnis von KMnO2, Z. Anorg. Allg. Chem., 1982, vol. 490, no. 1, pp. 101–110.
Endo, T., Kume, S., Shimada, M., and Koizumi, M., Synthesis of potassium manganese oxides under hydrothermal conditions, Mineral. Mag., 1974, vol. 39, no. 3, pp. 559–563.
Allendorf, M.D. and Spear, K.E., Thermodynamic analysis of silica refractory corrosion in glass-melting furnaces, J. Electrochem. Soc., 2001, vol. 148, no. 2, pp. B59–B67.
Chang, L.L.Y. and Sachdev, S., Alkali tungstates: stability relations in the systems A2O · WO3–WO3, J. Am. Ceram. Soc., 1975, vol. 58, nos. 7–8, pp. 267–270.
Xue, L., Lin, Z., Chen, D., Huang, F., and Liang, J., Subsolidus phase relations in the systems K2O–ZnO–AO3 (A = Mo, W), J. Alloys Compd., 2008, vol. 452, no. 2, pp. 263–267.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © G.D. Nipan, 2018, published in Neorganicheskie Materialy, 2018, Vol. 54, No. 1, pp. 104–109.
Rights and permissions
About this article
Cite this article
Nipan, G.D. Specific Phase Transformations of K/W/Mn/SiO2 Composite Catalyst. Inorg Mater 54, 96–101 (2018). https://doi.org/10.1134/S0020168518010119
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0020168518010119