The catalytic hydrogenation of aromatic hydrocarbons in petroleum fractions and method thereof

 

(57) Abstract:

The invention relates to the production of catalysts for hydrogenation of aromatic hydrocarbons, petroleum fractions and can be used in the refining industry. The catalyst composition, wt.%: Nickel oxide 10 to 15, the oxide of tungsten, 4 to 8, tin 0,4-2, zeolite type CC 3 - 7, chlorine 1 5 aluminum oxide 63 - 81,6, obtained by successive modifications of aluminum hydroxide continuous deposition of chlorine, tin, silicon oxide, tungsten oxide, triethylene glycol, molding, extrusion, drying, calcination, the subsequent impregnation of the modified zeolite-containing oxide carrier with an aqueous solution of Nickel nitrate, further drying and calcination. The use of the catalyst in the hydrogenation of petroleum fractions increases the activity in the hydrogenation of mono-, bi-and polycyclic aromatic hydrocarbons. 2 S. p. f-crystals, 2 tab.

The invention relates to the production of catalysts for hydrogenation of aromatic carbohydrates petroleum fractions with the aim of reducing the content of mono-, bi - and polycyclic aromatic hydrocarbons and can be used in the oil industry.

UB the Nations, where as the active hydrogenating components used Nickel and tungsten, as well as media - type zeolite V and aluminosilicate (E. D. Radchenko. getting jet fuels using hydrogenation processes. M Tsniiteneftehim, 1980. S. 48).

Closest to the proposed technical solution is the method of cooking alumonickelsilicate catalyst with the addition of 2 to 15% wt. tin, introduced by impregnation of the calcined catalyst (U.S. Pat. USA N 3836453, CL 208 143 from 17.09.74,)

The disadvantage of these methods is low activity in the hydrogenation of mono-, bi - and polycyclic aromatic hydrocarbons.

The invention consists in the following: the invention is directed to solving the tasks of receiving highly active catalyst for the hydrogenation of mono-, bi - and polycyclic aromatic hydrocarbons in the composition of petroleum fractions.

The solution indirectly new technical result. This technical result is achieved by obtaining a catalyst of the following composition, wt. Nickel oxide 10 15; tungsten 4 8; tin 0,4 2; type zeolite include basically 3 7; 1 5 chlorine; aluminum oxide expenses 63.81, a method of producing a catalyst, comprising the sequential modity and an aqueous solution of a pentahydrate of tin tetrachloride), tin (to be paid in the form of an aqueous solution of a pentahydrate of tin tetrachloride), silicon oxide (to be paid in the form of a zeolite of type DCM), tungsten oxide (to be paid in the form of an aqueous solution cremaboldrini acid), triethylene glycol, molding, extrusion, calcination, impregnation of modified zeolite-containing oxide carrier with an aqueous solution of Nickel nitrate, drying and calcination.

The essential features of the invention are the catalyst composition, the ratio of its components, and how to obtain it.

Distinctive features of this invention are the composition and ratio of catalyst components, wt.

Nickel oxide 10 15

Tungsten 4 8

Tin 0,4 2

The zeolite of type CC 3 7

Chlorine 1 5

Aluminum oxide 63 81,6

as well as its manufacturing method, comprising the sequential modification of aluminum hydroxide continuous deposition of chlorine (to be paid in the form of concentrated hydrochloric acid and an aqueous solution of a pentahydrate of tin tetrachloride, tin (to be paid in the form of an aqueous solution of a pentahydrate of tin tetrachloride), silicon oxide (to be paid in the form of a zeolite of type DCM), tungsten oxide (to be paid in the form of an aqueous solution of crennelated Nickel, drying and calcination.

The novelty of the invention lies in the introduction of alumonickelsilicate catalyst hydrogenation tin, chlorine and zeolite-type computers, and method thereof, comprising the sequential modification of aluminum hydroxide continuous deposition of chlorine, tin, silicon oxide, tungsten oxide and triethylene glycol. New in the proposed technical solution is to obtain high-grade impregnating zeolite-containing catalysts on the carrier, a modified tin that holds to the formation of highly dispersed metal structure and preserve it during the reaction.

The invention is illustrated by the following examples.

Example 1. 408 g of aluminum hydroxide continuous deposition with a humidity of 80% wt. modify with continuous mixing 2.5 ml of concentrated hydrochloric acid with a density of 1.18 g/cm3. The modified aluminum hydroxide additives modify tin, adding 2.7 ml of an aqueous solution of a pentahydrate of tin tetrachloride with a concentration of tin of 150 mg/ml. Then this mass is added 5.7 g of zeolite powder of type DCM, humidity 47% wt. and 4.5 ml of an aqueous solution cremaboldrini acid with conc is Alenia each of the modifying component mass is stirred under heating for 15 min, then the mass is evaporated on a water bath to a moisture content of 65 to 70% by weight, molded by extrusion, dried in the temperature range 60 - 110oC for 6 h and calcined at 550oC for 4 h

90 g of calcined semi-finished catalyst is placed in 63 ml of impregnating solution containing 40 g of uranyl nitrate Nickel impregnation was carried out by the FC for 1 h at a temperature of 70 85oC until complete absorption of the carrier of the impregnating solution. After impregnation the catalyst is dried in the temperature range 110 170oC for 6 hours and calcined at 550oC for 4 h

The composition of the catalyst, wt. NiO 10, WO34, Sn 0,4, Cl 1, zeolite 3, Al2O381,6.

Example 2. 361,5 g of aluminum hydroxide continuous deposition with a humidity of 80% wt. modifiziert with continuous stirring and 2.3 ml of concentrated hydrochloric acid with a density of 1.18 g/cm3. The modified aluminum hydroxide additives modify tin, adding 8 ml of an aqueous solution of a pentahydrate of tin tetrachloride with a concentration of tin of 150 mg/ml. Then this mass is added 9.4 g of zeolite powder of type DCM, humidity 47% wt. and 6.7 ml of an aqueous solution cremaboldrini acid of a concentration trioxide wolfrace and calcination of the zeolite modified aluminum hydroxide carried out analogously to example 1.

of 87.5 g of calcined semi-finished catalyst is placed in a 61.5 ml of impregnating solution containing 50 g of uranyl nitrate Nickel. The impregnation, drying and calcination carried out analogously to example 1.

The composition of the catalyst, wt. NiO 12,5, WO36; Sn 1,2; Cl 3, 5 zeolite, Al2O372,3.

Example 3. 315 g of aluminum hydroxide continuous deposition with a humidity of 80% wt. modify with continuous stirring 2 ml of concentrated hydrochloric acid with a density of 1.18 g/cm3. The modified aluminum hydroxide additives modify tin, adding a 13.3 ml of an aqueous solution of a pentahydrate of tin tetrachloride with a concentration of tin of 150 mg/ml and Then with stirring to this mass is added to 13.2 g of zeolite powder of type DCM, humidity 47% 9 ml of an aqueous solution cremaboldrini acid with a concentration of tungsten trioxide 890 mg/ml and 13.6 ml of concentrated triethylene glycol.

Mixing, evaporation mass, shaping, drying and calcining the modified aluminum hydroxide carried out analogously to example 1.

85 g of calcined semi-finished catalyst is placed in 59,5 ml of impregnating solution containing 60 g of uranyl nitrate Nickel. The impregnation, drying and use the and CBM 7, Al2O363,0.

The catalytic activity of the catalyst synthesized in example 3 was evaluated in the hydrogenation process of naphtha with boiling within 51 169oC, the content of monocyclic aromatic hydrocarbons of 4.4 wt.%. The results are shown in table. 1.

Test the activity of the catalysts was conducted on a laboratory flow-through installation hydrogenation process light gas oil fraction boiling within 215 360oC content of bi - and tricyclic aromatic hydrocarbons 15,27% wt

Comparative hydrogenating activity of the industrial base catalyst contact 8376" and catalysts prepared according to examples 1 to 3, and the catalyst prepared in a known manner, taking into account the fact that the activity base nikolvandrakus catalyst taken as 100% are shown in table. 2.

The results show that the hydrogenation activity of the catalysts prepared according to the present invention, a mono-, bi - and polycyclic hydrocarbons higher than that of the base catalyst and the catalyst prepared according to the prototype.

1. The catalytic hydrogenation of aromatic hydrocarbons in the oil fra is positive contains zeolite type computers with the following content of components, wt.

Nickel oxide 10 15

Tungsten 4 8

Tin 0,4 2

The zeolite of type CC 3 7

Chlorine 1 5

Alumina Rest

2. The method of producing catalyst for the hydrogenation of aromatic hydrocarbons, petroleum fractions, including deposition of aluminum hydroxide, the introduction of modifying additives, forming, drying, calcination, impregnation with an aqueous solution of Nickel nitrate, followed by drying and calcination, wherein the aluminum hydroxide continuous deposition consistently modify concentrated hydrochloric acid, then with an aqueous solution of a pentahydrate of tin tetrachloride with intermediate stirring under heating after making each component is mixed with cremaboldrini acid, zeolite type DCM and triethylene glycol, followed by stirring under heating.

 

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