III International Conference

PP-II-33HYDROTREATING CATALYSTS MODIFIED BY ADDITIVES OF VANADIUMAND HETEROPOLYACIDS OF KEGGIN STRUCTURESEremina Yu.V., Tomina N.N., Nikul’shin P.A., Pimerzin A.A.Samara State Technical University, Samara, RussiaE-mail: tominann@yandex.ruIn the given work influence of additives of heteropolyacid (HPA) of molybdenum andtungsten of 12-th lines and additives of vanadium was studied. It is established, that jointapplication of vanadium and HPA allows increasing activity of the catalyst in a wide intervalof temperatures. The complex of modifying additives in the best way is proved in case of usecobalt as promoter.One of the ways to increase activity of hydrotreating catalysts is their modifying byvarious inorganic additives. It allows to increase hydrodesulfurization (HDS) andhydrogenation activities of catalysts, stability of an active phase, to regulate acid properties ofthe catalyst, etc.In the work influence of additives of heteropolyacid (HPA) of molybdenum and tungstenof 12-th lines and additives of vanadium was studied. Various content of additives, ways oftheir introduction and methods of synthesis of the modified catalysts were studied. Allsynthesized samples contained identical contents of МоО 3 and NiO or СоО. Molybdenumwas introduced from ammonium paramolybdate (NH 4 ) 6 Mo 7 O 24 *4H 2 O (PMA) or fromH 4 [SiMo 12 O 40 ]*nH 2 O (SiMo 12 -HPA). Some samples contained also modifying additives W orV. Tungsten was introduced from ammonium paratungstate (NH 4 ) 10 [H 2 W 12 O 42 ]*4H 2 O (PTA)or from H 4 [SiW 12 O 40 ]*nH 2 O (SiW 12 -HPA).The synthesized catalysts were tested in a bench-scale flow reactor unit in the process ofhydrotreatment of diesel fraction. The tests were conducted at temperatures of 320, 340, 360,and 380 0 C; a pressure of 3.0 MPa; a feed space velocity of 2.5 h -1 ; a hydrogen : feedstockratio of 450 Nl/l; and a catalyst volume of 10 cm 3 .For initial fraction and received hydrogenates contents of sulfur and polycyclic aromaticcompounds (PCAC) was determined, it have allowed to determine HDS and hydrogenationactivity of catalysts.In fig. 1 dependence of HDS degree for Al-Ni-Mo catalysts modified by tungsten withthe additive of vanadium (a sample 10) and without vanadium (a sample 9) is given.Apparently from figure, HDS degree for sample 10 containing of vanadium is higher, than fora sample 9 (without the modifier) on the average on 8 rel %. The catalyst 8 allows to obtainhydrogenates with residual contents of sulfur of 0.002 wt % and hydrogenation PCAC morethan on 40 rel % (fig. 2).223