SU1581375A1 - Method of preparing catalyst for hydraulic purification of petroleum raw material - Google Patents

Abstract

The invention relates to catalytic chemistry, in particular the preparation of a catalyst for hydrotreating petroleum. The goal is to obtain a catalyst with a bidisperse porous structure and increased hydrodesulfurizing and hydrogenating activity. For this, AL (OH) 3 (continuous precipitation with a humidity of 80%) is used, which is peptized with conc. HCL and modified with a solution of chlorine tin [at a rate of 0.2-0.6 wt.% Tin on AL (OH) 3], then dried, calcined, ground and treated with a 1.8-2.5% solution of HNO 3 or HCL and then an aqueous solution of ammonium paramolybdate and nickel nitrate [at the rate of 10-14 wt.% MOO 3 and 3-5 wt.% NIO ], dried again and in a ratio (10-40) :( 60-90) mixed with a binder. As which use peptized AL (OH) 3, modified 0.2-0.6 wt.% Tin. This mixture is dried, calcined and additionally impregnated with an aqueous solution of ammonium paramolybdate and nickel nitrate acidified with HCL to pH 3-5 [at the rate of 10-14 wt.% MOO 3 and 3-5 wt.% NIO]. The new catalyst has a bidisperse porous structure with an effective radius of fine pores of 6-10 nm and a transport pore of 100-130 nm. When hydrotreating a light gas oil catalyst provides for 7.9-14.4% higher activity in hydrodesulfurization and from 5.4-78.4% in the hydrogenation of aromatic hydrocarbons than the known catalyst. 3 tab.

Description

The invention relates to the production of catalysts for hydrotreating petroleum feedstocks and can be used in the refining industry.

The purpose of the invention is to obtain a catalyst with a bidisperse structure with an effective radius of fine pores of 6 to 10 nm and. transport pores of 100-130 nm and with increased hydrogenation and hydro

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desulfurizing activity through the use of aluminum hydroxide continuous precipitation modified with tin and another sequence of operations.

The invention is illustrated by the following examples.

Example 1. 100 g of hydroxide continuous precipitation with a moisture content of 80% by weight peptizugat with continuous stirring of 0.6 ml of concentrated hydrochloric acid with a density of 1.18 g / cm3. Peptized aluminum hydroxide is modified with tin, add 0.27 ml of an aqueous solution of 5H.jO with a tin concentration of 150 mg / ml. The mass is dried at 80-110 ° C for 6 hours, calcined at 550 ° C for 4 hours and ground into pores. Oshka with a particle size of not more than 0.08 mm. 8 g of powder containing 0. m s.% Tin are treated with 1.6 ml of a 1.8 D solution of nitric acid and then 2.56 ml of a solution containing 1.03 g of ammonium paramolybdate and 2.56 ml of solution containing 0.94 g of nickel nitrate. The wet powder is stirred and dried at 80 ° C for an hour and 110 ° L for 6 hours.

360 g of aluminum hydroxide by continuous precipitation is peptised with 0.96 ml of concentrated nitric acid with a density of 1.37 g / cm3. Peptized aluminum hydroxide is modified with tin by adding 0.96 ml of SnCl4 5H.jO solution with a tin concentration of 150 mg / ml. To the prepared mass is added all the previously prepared powder of a nickel-alumino-molybdenum catalyst 9 modified with tin. The mass is stirred, molded by extrusion, dried at 80-110 ° C for 6 4S, calcined at 550 ° C for 4 hours.

15 g of calcined semi-finished catalyst containing 10 wt.% Tin-modified alumino-nickel-molybdenum catalyst powder are placed in 30 ml of an impregnating solution containing 2.60 g of ammonium paramolybdate, 2.37 g of nickel nitrate and Os2 ml of concentrated hydrochloric acid with a density of 1.18 g / cm3. The ratio of the active components in an aqueous solution acidified with hydrochloric acid to pH 4 is 52.31% by weight of ammonium molybdate and 47.69% by weight of nickel nitrate.

The impregnation is carried out for an hour at 60 ° C and a pH of 4. Then catalysis

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The torus is dried at 80-160 ° C for 16 hours and calcined for 2 hours at 350 ° C. Catalyst composition, wt.%: 1o (b 10; NiO 3; Sn. 0.2; Al-aOj 86.8. The catalyst has a total pore volume of 0.63 cm3 / g and is characterized by a bi-dispersed porous structure, the effective radius of the fine pores it is 6-8 nm, and the effective radius of the transport pores is 100-105 nm. The pore volume with a radius of up to 10 nm is 0.52 cm3 / g, and with a radius of more than 10 nm, 0.11 cm3 / g, the ratio of thin and transport pores 83:17.

Example 2. 100 g of aluminum hydroxide continuous precipitation with a humidity of 80% may. peptize with continuous stirring, 0.6 ml of concentrated hydrochloric acid with a density of 1.18 g / cm3. Peptized aluminum hydroxide is modified with tin by adding 0.53 ml of an aqueous solution of chlorine tin with a tin concentration of 150 mg / ml. The mass is dried for 6 hours, calcined for 4 hours at 550 ° C and ground to a powder with a particle size of not more than 0.08 mm.

8 g of powder of AlgCl2 containing O, 4% by weight of tin, are treated with 4 ml of a 2.15% solution of nitric acid, and then 2.56 ml of a solution containing 1.23 g of ammonium paramolybdate and 2.56 ml solution containing 1.25 g of nickel nitrate. The wet powder is stirred and dried for 6 hours at 80 ° C and 110 ° C for 6 hours.

160 g of apyumini hydroxide, continuous precipitation is peptized with 0.85 ml of concentrated nitric acid with a density of 1.37 g / cm3. Peptized aluminum hydroxide is modified with tin, adding 0.85 ml of a solution of chlorine tin with a concentration of tin 150 mg / ml. All prepared powder of a tin-modified nickel-molybdenum catalyst is added to the prepared mass. The mass is stirred, molded by extrusion, dried at 80-110 ° C for 6 h, calcined for 4 h at 550 ° C.

15 g of calcined semi-finished catalyst containing 25% by weight of tin-modified alumino-nickel-molybdenum catalyst powder are placed in 30 ml of an impregnating solution containing 2.6 g of ammonium paramolybdate, 2.63 g of nickel nitrate and O, 2 ml of concentrated hydrochloric acid with a density of 1.18 g / cm3. Masso515

The ammonium paramolybdate to nickel nitrate ratio in the solution acidified to pH 4 is 49.71:

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: 50.29. The impregnation is carried out for 1 hour at 60 ° C and a pH of 4. Then the catalyst is dried for 16 hours at 80-160 ° C and calcined for 2 hours at 350 ° C. The composition of the catalyst, wt.%: Ho03 12; N10 4; Sn 0.4; 83.6. The catalyst has a total pore volume of 0.76 cm3 / g and is characterized by a bidisperse porous structure with an effective radius of fine pores of 7–9 nm, and transport pores of 110–115 nm. The pore volume with a radius of up to 10 km is 0.50 cm3 / g, and with a radius of more than 10 nm it is 0.26 cm3 / g, the ratio of thin and transport pores is 66:34.

PRI me R 3. Powder -A12Oz, containing 0.6% by weight of tin, is prepared as in Example 1. 8 g of this powder is treated with 6.4 ml of a 2.5% solution of nitric acid, and then 2.56 ml of a solution containing 1.44 g of ammonium paramolybdate and 2.56 of a solution containing 1.56 g of nickel nitrate are dried, as in Example 1.

60 g of aluminum hydroxide continuous precipitation is peptized with 0.16 ml of concentrated nitric acid with a density of 1.37 g / cm3, then modified with tin, adding 0.48 ml of a solution of chlorine tin with a concentration of 150 mg / ml of tin. To the prepared mass is added all the previously prepared powder of an alumino-nickel-molybdenum catalyst modified with tin, and then treated as in Example 1.

15 g of calcined semi-finished product containing 40% by weight of tin-modified alumina-molybdenum catalyst powder are impregnated with a joint solution containing 2.43 g of ammonium paramolybdate and 2.63 g of nickel nitrate in 30 ml of the solution acidified with hydrochloric acid to pH 4. The mass ratio of ammonium paramolybdate to nickel nitrate is 48.02: 51.98. The impregnation and heat treatment of the catalyst is carried out as in Example 1. The catalyst has the following composition, wt%: MoO 14; NiO 5; Sn 0.6 80.4. The catalyst has a total pore volume of 0.78 cm3 / g and is characterized by a bi-dispersed porous structure with an effective radius of thin

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pores 8-10 nm and transport pores 120-130 nm. The pore volume with a radius of up to 10 nm is 0.46 cm3 / g, and with a radius of more than 10 nm it is 0.39 cm3 / g, the ratio of thin and transport pores is 60:40.

Example 4 Y-A12Oe powder containing 0.4% by weight of tin is prepared analogously to Example 2, 8 g of this powder is treated with 4 ml of a 2.15% solution of hydrochloric acid, and then 2 , 56 ml of a solution containing 1.23 g of a solution of hydrochloric acid, and then 2.56 ml of a solution containing 1.3 g of paramolybdate ammonium and 2.56 ml of a solution containing 1.25 g of nickel nitrate, and dried as in Example 2 .

160 g aluminum hydroxide continuous precipitation peptides 0.85 ml

hydrochloric acid with a density of 1, 18 g / cm3, modified with tin, mixed with an alumina-nickel-molybdenum catalyst powder, molded, dried and calcined as in example 2, then the calcined semi-finished catalyst is impregnated and thermally treated as in example 2. The composition of the catalyst, wt.%: Moe 12; NiO 4; Sn 0.4; A120e 83.6. The catalyst is characterized by a bidisperse structure with an effective radius of fine pores of 7–8 nm and a transport pore of 110–115 nm.

PRI me R 5. Catalyst activity testing was carried out on a laboratory flow unit in the process of hydrotreating a light gas oil fraction 215-360 C with a sulfur content of 2.06% by weight, bi- and triplic aromatic hydrocarbons 15, 27 wt.%. The comparative hydrodesulfurizing and hydrogenating activities of the basic industrial catalyst 1S-168 W and the catalysts prepared according to Examples 1-4 are presented in Table. one.

AT . 2 presents data on the relative activity of the base catalyst GZ-168 sh and the catalysts prepared according to examples 1-4, as well as those prepared by known methods, taking into account that the activity of the base alumino-nickel-molybdenum catalyst is assumed to be 100%.

In tab. 3 shows a comparative assessment of the activity of the catalysts prepared by the proposed method and the industrial aluminum-cobalt-molybdenum catalyst (ACM) prepared by coextrusion, the degree

the desulfurization of which was 72% ..

Claims (1)

As can be seen from the data in Tables 1–3, the catalysts prepared by the proposed method have a bidisperse porous structure and increased activity in the reactions of hydrodesulfurization and hydrogenation of aromatic hydrocarbons in comparison with the catalysts prepared by known methods. Thus, the proposed catalysts are 7.9-14.4% and 56.4-78.4% more active in the hydrobased securing and hydrogenation, respectively, compared with the known catalyst. Invention Formula A method for preparing a catalyst for hydrotreating petroleum feedstock, including sedimentation, peptization, molding, drying, calcining, thawing aluminum hydroxide, impregnation of ammonium paramolybdate and nickel nitrate with an aqueous solution of active ingredients, followed by drying and calcining 5 that, in order to obtain a catalyst with a bidisperse porous structure with an effective radius of fine pores of 6–10 nm and transport pores of 100–130 nm and with increased hydrogenating and hydroabsorption activity, Use of continuous deposition of aluminum hydroxide, which after peptization impregnated with a solution of stannous chloride calculating 0.2-0.6 wt.% of tin on alumina, then after drying, calcining is treated with a 1.8-2.5% solution of nitric or hydrochloric acid, and then an aqueous solution of paramolybdenum and nickel nitrate at the rate of 10-14 wt.% molybdenum trioxide and 3-5 wt.% nickel oxide on alumina, dried and mixed in ratio (10-40) :( 60-90) with a binder, 0 as which is used peptized aluminum hydroxide, modified with 0.2–0.6 wt.% Tin, dried, calcined, and further impregnated with a common aqueous solution of ammonium paramolybdate and nickel nitrate acidified with hydrochloric acid to pH 3-5. , at the rate of 10-14 wt.% molybdenum trioxide and 3-5 wt.% nickel oxide. Table 1 Desulfurization M 100.0 112.0 114.7 118.8 112.6 Table3 ten Hydrogenation 100.0 158.8 161.6 189.6 164.0