Catalysts Based on High-Vanadium Solutions
of Molybdovanadophosphoric Heteropolyacids: Achievements, Challenges, and Prospects1
E. G. Zhizhinaа, L. L. Goginа, *, Yu. A. Rodikovaа, and V. I. Bukhtiyarovа
а Federal Research Center Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences,
Novosibirsk, 630090 Russia
Correspondence to: *е-mail: gogin@catalysis.ru
1Abbreviations and notation: HPC, heteropoly compound; HPA, heteropolyacid; HPA-x, Мо−V−P heteropoly acid with x vanadium atoms; HPAn, heteropolyanion; Su, substrate; m, degree of reduction of the HPA-х solution; η, viscosity; ρ, density; χ, specific electric conductivity; SHE, standard hydrogen electrode; Е, redox potential; S, selectivity; OS, organic solvent; ∆rH, reaction enthalpy; ∆fH, formation enthalpy; MEK, methylethylketone; NMR, nuclear magnetic resonance; EPR, electron paramagnetic resonance; RS, Raman spectroscopy; MD, menadione, 2-methyl-1,4-naphthoquinone; TMP, trimethylphenol; TMBQ, trimethyl-1,4-benzoquinone; DAP, dialkylphenol; DABQ, dialkyl-1,4-benzoquinone; DMBQ, 2,6-dimethyl-1,4-benzoquinone; DTBQ, di-tert-butyl-1,4-benzoquinone; AQ, 9,10-anthraquinone; NQ, 1,4-naphthoquinone; DFF, 2,5-diformylfuran; HQ, hydroquinone; BQ, 1,4-benzoquinone; HH, hydrazine hydrate; 5-HMF, 5-hydroxymethylfurfurol; НОAc, acetic acid; LA, levulinic acid; FA, formic acid; MIBK, methylisobutylketone; THA, 1,4,4а,9а-tetrahydro-9,10-anthraquinone; DHA, 1,4-dihydro-9,10-anthraquinone; TMAQ, 2,3,6,7-tetramethylanthraquinone; DMB, 2,3-dimethylbutadiene; THNQ, substituted tetrahydro-1,4-naphthoquinone; DHNQ, substituted dihydro-1,4-naphthoquinone.
Received 16 November, 2020
Abstract—A retrospective review based on the authors’ work is devoted to homogeneous catalytic systems based on aqueous solutions of Mo–V–P heteropolyacids (HPA-x, x is the number of vanadium atoms). These catalytic systems were first proposed for oxidative reactions at Boreskov Institute of Catalysis. The properties of HPA-x solutions, methods for their synthesis, promising processes occurring in their presence, problems related to the use of these solutions, and ways of solving these problems are considered. Prospects for the creation of industrial processes based on modified high-vanadium HPA-x solutions of non-Keggin compositions are shown.
Keywords: heteropolyacids, homogeneous catalysis, oxidation, diene synthesis, regeneration
DOI: 10.1134/S0023158421020129