The preparation method of the catalyst for reforming of gasoline fractions

 

(57) Abstract:

Usage: in the catalytic production, in particular in the preparation method of the catalyst for reforming of gasoline fractions. The inventive method for preparation of the catalyst involves the impregnation of the support in two stages at pH of 8.5 to 12 and a temperature of 25 to 90C in a solution containing a mixture of emmakate platinum compounds promoter and alkali metal salt of sodium, potassium or lithium, in the atomic ratio of alkali metal and platinum, is equal to (1 of 50):1. The impregnated carrier is dried and calcined. As a promoter it is better to use tungsten or molybdenum. 1 C. p. F.-ly, 1 table.

The invention relates to methods for preparing catalysts for reforming of gasoline fractions and can be used at the enterprises of chemical, oil-refining and petrochemical industries.

There is a method of preparation of the catalyst of the reformer, in which the calcined solid media from a metal oxide pour a solution containing chloroplatinates ammonium or chloride terramicina (II) of platinum, and are impregnated with a pH of 3.1 and 6.7 for 2 hours, the Excess solution is drained and the catalyst is dried [1]

UP>aboutC at a pressure of 1 MPa, a temperature of 500aboutC, space velocity of the raw materials 3 h-1, a molar ratio of hydrogen: feedstock 5: 1 the content of the coke on the catalyst is increased from 1.5 wt. after 24 h up to 16 wt. after 240 hours

A known method for preparation of the reforming catalyst by double impregnation, in which the calcined carrier of aluminum oxide impregnated with aqueous solution of tin tetrachloride and hydrochloric acid at pH 1-3, the excess solution is drained, the catalyst is dried and calcined in air flow and re-impregnated with an aqueous solution chloroplatinates and hydrochloric acid at pH 1-3, the excess solution is drained, the catalyst is dried and calcined in air flow [2]

The disadvantage of this method is the high coking ability of the catalyst. So, when reforming a gasoline fraction 85-180aboutC at a pressure of 1 MPa, a temperature of 500aboutC, space velocity of the raw materials 3 h-1, a molar ratio of hydrogen: feedstock 5: 1 the content of the coke on the catalyst is increased from 0.5 wt. after 24 h of work to 8.2 wt. after 240 hours

Closest to the proposed technical essence is a method of preparation of the reforming catalyst in which the zeolite ZSM-4, ZSM-8, ZSM-11, ZSM-12 after procarcinogenic when 150-550aboutWith, then platinochloride zeolite is treated with a salt solution of an alkali metal at room temperature for 8-10 h, decanted, washed with water and dried at 110aboutC.

The disadvantage of this catalyst is its high coking ability. So, when reforming a gasoline fraction 85-180aboutC at a pressure of 1 MPa, a temperature of 500aboutC, space velocity of the raw materials 3 h-1, a molar ratio of hydrogen: feedstock 5:1 the content of the coke on the catalyst increases from 0.31 wt. after 24 h of work to 4.6 wt. after 240 hours

The aim of the invention is to reduce maksuameti catalyst.

This goal is achieved by the fact that the proposed method is carried out by two-stage impregnation of the calcined carrier based on zeolite ZSM-5, ZSM-8, ZSM-11 aqueous solution containing ammicht platinum compound promoter and a salt of an alkali metal in an atomic ratio of alkali metal: platinum (1-50):1, and the impregnation is carried out at the distribution of platinum in the impregnating solution, the steps (1-1,2):1 at pH of 8.5 to 12 and a temperature of 25-90aboutC.

A distinctive feature of the proposed method are two-stage impregnation, the ratio of the alkali metal and platinum Pro is realized as follows.

Heat-resistant zeolite-containing carrier is dipped in a solution having pH of 8.5 to 12 and containing tetraamines of platinum and a salt of an alkali metal (sodium, potassium or lithium), and are impregnated with 25-90aboutC for 3 h, the excess solution is drained and the catalyst is again immersed in a solution having pH of 8.5 to 12 and containing tetraamine platinum compound promoter and a salt of an alkali metal (sodium, potassium or lithium), and are impregnated 25-90aboutC for 3 h, the excess solution is drained, the catalyst is dried and calcined in air flow at 500aboutC. thus, the amount of platinum in the impregnating solution at the first stage impregnation refers to the amount of platinum on the second stage impregnation as (1-1,2): 1.

The implementation of impregnation in two stages in the presence of alkali metal salts forming an optimal catalytic surface of the catalyst, defining its coking ability.

P R I m e R 1. 100 g of calcined heat-resistant media containing 60 wt. zeolite ZSM-5 with a module 35 in the sodium form and 40 wt. aluminium oxide is immersed in 200 ml of an aqueous solution composed of a mixture of emmakate platinum (II), salts of alkali metal and ammonium tungstate containing of 0.13 g of platinum, and 0.46 g of sodium and 0.025 g of tungsten and has a 200 mm aqueous solution, containing 0.12 g of platinum, 0.025 g of tungsten and 0.42 g of sodium and having a pH of 10. The impregnation is carried out at 80aboutC for 3 h, the excess solution is drained, the catalyst was dried for 6 h at 120aboutWith and calcined 4 h at 500aboutWith the current of air.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m m e R 2. The method is carried out as in example 1 except that the impregnating solution contains the first stage 0,016 g of sodium, and the second stage 0.015 g of sodium.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 3. The method is carried out as in example 1 except that the impregnating solution contains the first stage of 0.80 g of sodium, and the second stage to 0.72 g of sodium.

The finished catalyst has a composition, by weight. platinum 025, tungsten 0.05, the carrier 100.

P R I m e R 4. The method is carried out as in example 1 with the difference that the heat-resistant carrier contains a zeolite ZSM-8, and the impregnating solution contains the first stage of 0.32 g of sodium on the second stage of 0.28 g of sodium, and the impregnation is carried out at pH 12

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 5. The method is carried out when the x2">

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 6. The method is carried out as in example 1 with the difference that the impregnation is carried out at 90aboutC.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 7. The method is carried out as in example 1 with the difference that the impregnation is carried out at 25aboutC. the Finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 8. The method is carried out as in example 1 except that the impregnating solution contains in the first and second steps of 0.125 g of platinum and 0.44 g of sodium.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 9. The method is carried out as in example 1 except that the impregnating solution contains on the first stage of 0.14 g of platinum and 0.50 g of sodium, and the second stage 0,117 g of platinum and 0.42 g of sodium.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the media and the rest.

P R I m e R 10. The method is carried out as in example 1 except that the impregnating solution contains instead of sodium on the first stage of 0.82 g of potassium, and the second stage to 0.72 g of potassium.

Goto the are as in example 1 with the difference, what impregnating solution instead of sodium contains the first stage 0,146 grams of lithium, and the second stage 0,128 grams of lithium.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 12. The method is carried out as in example 1 except that the impregnating solution contains ammonium molybdate (0.025 g of molybdenum).

The composition of the obtained catalyst, wt. platinum 0.25 molybdenum 0.05, the carrier 100.

P R I m e p 13 (comparative). The method is carried out according to example 11 with the difference that the impregnating solution has a pH of 7.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 14 (comparative). The method is carried out as in example 1 except that the impregnating solution contains the first stage 0.0005 g of lithium, and the second stage 0.0004 g of lithium.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 15 (comparative). The method is carried out according to example 10, except that the impregnating solution contains the first stage 0,0028 g of potassium, and the second stage 0.0024 g of potassium.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P : first stage 0,0017 g sodium, and the second stage 0.0015 g of sodium.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 17 (comparative). The method is carried out as in example 1 with the difference that the impregnation is carried out at 100aboutC.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 18 (comparative). The method is carried out as in example 1 with the difference that the impregnation is carried out at 15aboutC.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 19 (comparative). The method is carried out as in example 1 except that the impregnating solution contains on the first stage of 0.97 g of sodium, and the second stage of 0.85 g of sodium.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 20 (comparative). The method is carried out according to example 10, except that the impregnating solution contains on the first stage of 1.64 g of potassium, and the second stage 1.44 g of potassium.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 21 (comparative). The method is carried out according to example 11 with the difference that the treatment rastv the composition, wt. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 22 (comparative). The method is carried out according to example 11 with the difference that the impregnating solution contains on the first stage of 0.11 g of platinum and amount of 0.118 g of lithium, and the second stage of 0.14 g of platinum and 0.15 g of lithium.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 23 (comparative). The method is carried out as in example 1 except that the impregnating solution contains on the first stage of 0.14 g of platinum and 0.15 g of lithium, and the second stage of 0.10 g of platinum and 0.11 g of lithium.

The finished catalyst has a composition, by weight. platinum 0.25 tungsten 0.05, the carrier 100.

P R I m e R 24 (prototype). 100 g of zeolite ZSM-5 calcined in a stream of air at 538about10 h and after cooling, suspended with a water solution containing 0.312 g of terramicina platinum, 4 h at room temperature. The solution is decanted and platinochloride zeolite impregnated with a solution of H2IrCl4(at the rate of 0.35 wt.) iridium), subjected to heat treatment at 450aboutWith gradual temperature increase to 2aboutC/min

The resulting zeolite is suspended in a 3% solution of potassium hydroxide at room temperature for 10 h, AHP crystal growth the composition, wt. platinum 0,54, iridium 0,35, zeolite up to 100.

The catalysts prepared according to examples 1 to 24, was tested on a pilot installation in the reforming of gasoline fractions 85-180aboutWith the following conditions: a pressure of 1 MPa, a temperature of 500aboutWith the feed rate 3 h-1, the molar ratio of hydrogen: feedstock 5:1. Each catalyst was tested twice: the first test 24 h, the duration of the second 240 hours After cessation of raw material (after 24 and 240 h) catalysts were otdovali hydrogen for 10 h, cooled in a circulating stream of hydrogen and analyzed for the content of coke (chromatographic method). The resulting produce was debutanizer and determined its octane number by the research method.

The test results presented in the table.

As can be seen from the presented data, the content of the coke on the catalysts prepared by the proposed method is significantly lower than the catalyst prepared according to the method prototype, and is 1.40 and 1.75 wt. against 4.6 wt. While the importance of the conditions of impregnation and the ratio of the components in the impregnating solution. So, by reducing the ratio of the number of platinum on the first and second stages of the ICO metal and platinum less than 1:1 (examples 14-16), the reduction of pH below 8.5 (example 13), the temperature of impregnation below the 25about(Example 18) coking ability of the catalyst increases. When increasing the atomic ratio of the alkali metal and platinum more than 50:1 (examples 19, 20, 21) decreases the activity of the catalyst. The increase in the temperature of saturation above 90aboutimpractical as it does not lead to the improvement of the catalyst, but complicates the process of impregnation (example 17).

1. The PREPARATION METHOD of the CATALYST for reforming of GASOLINE FRACTIONS, comprising a carrier impregnated based on zeolite ZSM-5, ZSM-8, ZSM-11 with a solution of platinum compounds, compound promoter and alkali metal salt, drying and calcining, characterized in that the impregnation is carried out at a pH of 8.5 to 12.0, and at 25 90oWith the solution containing ammicht platinum compound promoter and a salt of an alkali metal in an atomic ratio of alkali metal and platinum 1 50 to 1, and two degrees at a mass ratio of platinum to the first and second stages 1 1,2 1.

2. The method according to p. 1, characterized in that as a promoter use tungsten or molybdenum.

 

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