Bulk and supported vanadium-phosphorus oxide VPO catalysts were synthesized by traditional and barothermal methods. It was shown that the use of aerosil as a support for the VPO phase, depending on the time of its introduction into the reaction mixture. It can lead to the formation of catalyst precursor of vanadyl hydrogen phosphate VOHPO4 0.5H2O, or a phase of vanadyl pyrophosphate (VO)2P2O7 as already the catalytically active phase for selective oxidation of n-butane to maleic anhydride. The use of a modified aerosil gel formed from pyrogenic aerosol, as a support for the VPO phase, leads to the formation of VOHPO4∙0.5H2O phase. It has been found that the nature of support affects the features of formation of VOHPO4∙0.5H2O phase, in particular, the ratio of crystallographic planes in resulting VPO phase. The use of aerosil as a support leads to a decrease in the relative content of the basal plane, while use of aerosil gel leads to an increase in the relative content of the basal plane in applied VPO phase. The catalytic properties of bulk and supported VPO samples were studied in the selective oxidation of n-butane to maleic anhydride in standard (1.7 vol.%) and enriched (3.4 vol.%) n-butane mixtures. It has been found that in an enriched n-butane mixture for bulk samples, the n-butane conversion and selectivity for maleic anhydride are sharply reduced. It has been found that supported VPO samples have a higher specific rate of n-butane oxidation and higher productivity compared to bulk samples. It was shown that use of barothermal synthesis and aerosol gel as a support made it possible to increase the selectivity of maleic anhydride, which is associated with an increase in the relative content of the basal plane of VPO phase. The achieved improved catalytic properties of VPO catalysts supported with aerosol gel make recycling technology promising. This can make the production of maleic anhydride more economical.
Patent US3293268A, Bergman R., Frisch N.W. Production of maleic anhydride by oxidation of n-butane 1966.
Mangili P.V., Prata D.M. Preliminary Design of Sustainable Industrial Process Alternatives Based on Eco-efficiency Approaches: The Maleic Anhydride Case Study. Chem. Eng. Sci., 2019, 212, 115313.
Müller M., Kutscherauer M., Böcklein S., Wehinger G.D., Turek T., Mestl G. Modeling the selective oxidation of n-butane to maleic anhydride: From active site to industrial reactor . Catal. Today, 2022, 387, 82-106.
Ballarini N., Cavani F., Cortelli C., Gasparini F., Mignani A., Pierelli F., Trifirò F., Fumagalli C., Mazzoni G. The contribution of homogeneous and non-oxidative side reactions in the performance of vanadyl pyrophosphate, catalyst for the oxidation of n-butane to maleic anhydride, under hydrocarbon-rich conditions. Catal. Today, 2005, 99(1-2), 115-122.
Lorences M.J., Patience G.S., Dı́ez F.V., Coca J. Transient n-butane partial oxidation kinetics over VPO. Appl. Catal., A, 2004, 263(2), 193-202.
Patience G.S., Bockrath R.E. Butane oxidation process development in a circulating fluidized bed. Appl. Catal., A, 2010, 376(1-2), 4-12.
Ballarini N., Cavani F., Cortelli C., Ligi S., Pierelli F., Trifirò F., Fumagalli C., Mazzoni G., Monti T. VPO catalyst forn-butane oxidation to maleic anhydride: A goal achieved, or a still open challenge?. Top. Catal., 2006, 38(1-3), 147-156.
Kamiya Yu., Nishikawa E., Okuhara T., Hattori T. Catalytic property of vanadyl pyrophosphates for selective oxidation of n-butane at high n-butane concentrations. Appl. Catal., A, 2001, 206(1), 103-112.
Patent UA 122421 U Ukraine Diyuk O.A., Zazhyhalov V.O. The method of obtaining vanadium-phosphorus oxide (VPO) catalyst for the oxidation of n-butane of rich concentration in maleic anhydride. [in Ukrainian].
Patent US6174833B1 Bertola A., Cassarino S., Nsunda V., Process for the preparation of improved vanadium-phosphorus catalysts and use thereof for the production of maleic anhydride 2001.
Zazhigalov V.A., Diyuk E.A. Barothermal Synthesis and Catalytic Properties of Vanadium-Phosphorus Oxide Systems in Oxidative Transformations of Butane and Ethane. Theor. Exp. Chem., 2018, 54 (1), 66-72.
Dummer N.F., Weng W., Kiely C., Carley A.F, Bartley J.K., Kiely Ch.J., Hutchings G.J. Structural evolution and catalytic performance of DuPont V-P-O/SiO2 materials designed for fluidized bed applications. Appl. Catal., A, 2010, 376(1-2), 47-55.
Fernández J.R., Vega A., Díez F.V. Partial oxidation of n-butane to maleic anhydride over VPO in a simulated circulating fluidized bed reactor. Appl. Catal., A, 2010, 376(1-2), 76-82.
Blanco R.M., Shekari A., Carrazán S.G., Bordes-Richard E., Patience G.S., Ruiz P. Significant catalytic recovery of spent industrial DuPont catalysts by surface deposition of an amorphous vanadium-phosphorus oxide phase. Catal. Today, 2013, 203, 48-52.
Ballarini N., Cavani F., Cortelli C., Pierelli F. The Oxidation of n-Butane to Maleic Anhydride under Hydrocarbon-rich Conditions: The Role of Homogeneous and of Mixed Homogeneous-heterogeneous Reactions. Proceedings of the DGMK-Conference "C4/C5-Hydrocarbons: Routes to Higher Value-Added Products", (Munich, 2004). - P. 273-280.
Ciambelli P., Galli P., Lisi L., Massucci M.A., Patrono P., Pirone R., Ruoppolo G., Russo G. TiO2 supported vanadyl phosphate as catalyst for oxidative dehydrogenation of ethane to ethylene. Appl. Catal., A, 2000, 203(1), 133-142.
Ciambelli P., Lisi L., Patrono P., Ruoppolo G., Russo G. VOPO4⋅2H2O and Fe(H2O)x(VO)1-xPO4⋅2H2O Supported on TiO2 as Catalysts for Oxidative Dehydrogenation of Ethane. Catal. Lett., 2002, 82(3-4), 243-247.
Lisi L., Patrono P., Ruoppolo G. Comparative study of catalytic behaviour of bulk-like and highly dispersed supported vanadyl orthophosphate catalysts in the oxidative dehydrogenation of ethane. Catal. Lett., 2001, 72(3-4), 207-210.
Casaletto M.P, Lisi L., Mattogno G, Patrono P, Pinzari F, Ruoppolo G Effect of the preparation technique on the catalytic performances of TiO2 supported vanadium phosphate in the oxidative dehydrogenation of ethane. Catal. Today, 2004, 91-92, 271-274.
Lisi L., Patrono P., Ruoppolo G. Vanadyl phosphate dihydrate supported on oxides for the catalytic conversion of ethane to ethylene. J. of Mol.Catal. A: Chem, 2003, 204-205, 609-616.
Li Xiu-Kai, Ji Wei-Jie, Zhao Jing, Zhang Zhi-Bing, Au Chak-Tong n-Butane oxidation over VPO catalysts supported on SBA-15. J. Catal., 2006, 238(1), 232-241.
Xiao C.Y., Chen X., Wang Z.Y., Ji W.J., Chen Y., Au C.T. The novel and highly selective fumed silica-supported VPO for partial oxidation of n-butane to maleic anhydride. Catal. Today, 2004, 93-95, 223-228.
Bueno J.M.C., Bethke G.K., Kung M.C.; Kung H.H. Supported VPO catalysts for selective oxidation of butane III: Effect of preparation procedure and SiO2 support. Catal. Today, 1998, 43(1-2), 101-110.
Sidorchuk V.V., Diyuk E.A., Zazhigalov V.A. Phase evolution in V2O5-H3PO4-organic component systems during barothermal treatment. Inorg. Mater., 2007, 43(4), 406-411.
Griesel L., Bartley J.K., Wells R.P.K., Hutchings G.J. Preparation of vanadium phosphate catalyst precursors using a high pressure method. Catal. Today, 2005, 99(1-2), 131-136.
Sydorchuk V., Zazhigalov V., Khalameida S., Diyuk E., Skubiszewska-Zięba J., Leboda R., Kuznetsova L. Solvothermal synthesis of vanadium phosphates in the form xerogels, aerogels and nesostructures. Mater. Res. Bull., 2010, 45(9), 1096-1105.
Lopez-Sanchez J.A., Griesel L., Bartley J.K., Wells R.P.K., Liskowski A., Su D., Schlogl R., Volta J.-C., Hutchings G.J., High temperature preparation of vanadium phosphate catalysts using water as solvent. Phys. Chem. Chem. Phys., 2003, 5(16), 3525-3533.
Zazhigalov V.A., Diyuk E.A., Sidorchuk V.V. Development of VPO catalysts supported on mesoporous modified material based on an aerosol gel. Kinet. Catal., 2014, 55(3), 399-408.
Spivey J.J., Guliants V.V., Carreon M.A. Vanadium-phosphorus-oxides: From fundamentals of n-Butane oxidation to synthesis of new phases. Catalysis, 2005, 18, 1-45.
Zazhigalov V.O., Kiziun O.V. The obtaining of the anhydride products by oxidation of n-pentane on the VPO catalysts. Catalysis and Petrochemistry 2020, 30, 19-37. [in Ukrainian].
Amorós P., Ibáñez R., Martínez-Tamayo E., Beltrán-Porter A., Beltrán-Porter D., Villeneuve G. New vanadyl hydrogenphosphate hydrates. Electronic spectra of the VO2+ ion in the VO(HxPO4)x·yH2O system. Mat. Res. Bull., 1989, 24(11), 1347-1360.
Ryumon N., Imai H., Kamiya Y., Okuhara T. Effect of water vapor on the transformation of VOHPO4·0,5H2O in to (VO)2P2O7. Appl. Catal., A, 2006, 297, 73-80.
Ledoux M.J, Crouzet C., Pham-Huu C., Turines V., Kourtakis K., Mills P.L, Lerou J.J High-Yield Butane to Maleic Anhydride Direct Oxidation on Vanadyl Pyrophosphate Supported on Heat-Conductive Materials: β-SiC, Si3N4, and BN. J. Catal., 2001, 203(2), 495-508.
Misono M. Selective Oxidation of Butanes. Toward Green/Sustainable Chemistry. Top. Catal., 2002, 21(1-3), 89-96.
Zazhigalov V.A. The role of the geometric factor in the selective oxidation of lower paraffins at VPO catalysts. Theor. Exp. Chem., 1999, 35(5), 247-257.