Genesis and structure of Mo. O 3/Zr. O 2 solid acid catalysts of isobutane alkylation Introduction A promising direction in the development of alkylation processes is the transition from liquid-phase catalysts such as HF and H 2 SO 4 to heterogeneous catalysis thus avoiding problems related to chemical corrosion of equipment, toxicity of waste acids and their disposal. One example of such catalysts are various oxide systems based on Zr. O 2, Al 2 O 3, Ti. O 2 etc. One of such systems are the catalysts based on tungsten and zirconium oxide. In the same time WO 3 and Mo. O 3 have a similar properties. Therefore, the study of Mo. O 3/Zr. O 2 in the alkylation process is also of interest and possibility. However, from the point of view of preparation of these catalysts, little attention is paid to the mixing method as a method for their preparation. The purpose of this work consisted in studying of physicochemical characteristics of Mo. O 3/Zr. O 2 systems preparing by mixing method and to assessment of possibility of them application in isobutane alkylation. Preparation methods Preparation Zr(OH)4 from 10% Zr. OCl 2 solution and NH 4 OH at p. H=9 Fig. 5 – Pyridine concentration [3] on LAC and BAC for mixed samples with Si. Mo Fig. 1 – XRD for mixed samples with Si. Mo (1, 4 – 500°C; 2, 5 – 600°C; 3, 6 – 700°C) Fig. 6 – Pyridine concentration [3] on LAC and BAC for mixed and impregnated samples Fig. 2 – The dependence of Vm on the calcination temperature of mixed and impregnated samples • Structural characteristics Preparation method Zr. O 2 -400 Zr. O 2 -600 • DTA SSA, m 2/g 87 26 Vmes at p/ps≈1, cm 3/g 0, 13 3, 8 and 9, 5 d, nm 4. 2 PMo-600 86 0, 15 4 and 4, 5 4. 2 Mo(NH 4)-600 imp 44 - - 4. 2 PMo-600 mix 57 0, 16 3, 8 and 6, 5 4. 2 PMo-600 Mechanical mixing Zr(OH)4 with 12 -HPA (Si, P), molybdic acid (Mo(H)) or HMA (Mo(NH 4)) imp mix 41 - - 95 0, 18 6, 6 52 0, 15 3, 6 and 7, 7 59 0, 18 3, 9 and 4, 8 82 0, 14 4 45 0, 13 3, 8 and 7, 6 58 0, 14 3, 8 and 4, 7 6, 6 Si. Mo-400 Powder pressing at 130 atm 2 min and fragmentation (granules 1 -2 mm) 6, 6 Si. Mo-600 13, 2 Si. Mo-600 6, 6 PMo-400 6, 6 PMo-600 Step heat treatment at 100°C, 250°C, 400°C, 500/600/700°C Containing Mo. O 3 in mixing samples = 4. 2, 6. 6 and 13. 2% wt. For comparison, samples by impregnation method [1] were prepared (wt. % Mo. O 3 = 4. 2). Characterization method 13, 2 PMo-600 Fig. 3 – DTA of mixed and impregnated samples • Adsorption of acid-base indicators XRD (Shimadzu XRD-7000); DTA (Shimadzu DTA-60 A); adsorption of acid-base indicators; pyridine adsorption + FTIR (Shimadzu IRTracer-100); • pore structure and surface area (Quantachrome 6 i. SA). • Phase composition and volume fraction m-Zr. O 2 Vm [2] mix mix mix Conclusions • • Results mix In this work it is shown that the greatest influence on physicochemical properties Mo. O 3/Zr. O 2 -catalysts renders a preparation method. Their further investigation represents a particular perspective. Among the factors that could affect the properties of the catalyst, it has the greatest effect of preparation method, less – of Mo. O 3 content and the weakest – type molybdenum oxide precursor. References [1] Sun W. et al. Ind. Eng. Chem. Res. – 2000. – V. 39. – № 10. – PP. 3717 -3725. [2] Toraya H. et al. J. Comm. Am. Chem. Soc. – 1984. – V. 67. – № 6. – PP. 119 -121. [3] Emeis C. A. J. Catal. – 1993. – V. 141. – № 2. – PP. 347 -354. Acknowledgements Fig. 4 – Functionalized composition of impregnated and mixed samples • Pyridine adsorption + FTIR This work was executed at the Laboratory of Catalytic Technologies at St. Petersburg State Institute of Technology supported by the mega-grant (№ 14. Z 50. 31. 0013) of the Government of the Russian Federation. Omarov Shamil Omarovich Saint-Petersburg State Institute of Technology (Technical University), Research laboratory “Catalytic Technology”, Saint-Petersburg, Moscovsky Pr. 26, Russia, 190013 E-mail: sham-omarov@live. com/. Tel. : +7 -904 -556 -45 -54