The method of preparation of zeolite-containing catalyst

 

(57) Abstract:

Use: conversion of hydrocarbons to high octane motor catalyst. The inventive solution of ammonium salt load high-silica zeolite ZSM-5 in the sodium form. The suspension is heated to 50-60°C. and maintained under these conditions for 2 hours Filtered and washed with condensate. Spend cationite exchange with ammonium sulfate to a residual content of Na2O in the zeolite is not more than 0.1%. Then treated with a solution of zinc salts at 60°C for 2 hours, the Suspension is filtered and granularit with a binder, aluminum oxide. Granules provalivajut on the air for 20 h and dried. The obtained granules were calcined in an electric furnace at 500-550°C. Then, the pellet is treated with a gas mixture composition, wt.%: carbon monoxide 4-8; 4-12 carbon dioxide; hydrogen 10-20; oxygen 2-6; water vapor 5-15; nitrogen - rest.

The invention relates to the synthesis of catalysts for the conversion of light hydrocarbons with a high octane components of motor fuels.

Known method of preparing zeolite-containing catalyst (1) includes offset powder of zeolite ZSM-5 in the ammonium form with 0.5 N. the solution of ZnCL2and 0.5 N. a solution of NH42O3, drying at a temperature of 100-120aboutC for 10 h and calcination at 540aboutC. the resulting product has a residual content of Zn 1% by weight. As of promoting additives in the synthesis of catalyst added salts of various metals, for example, Ge, Cu. The number of promoters is usually not more than 1%.

The disadvantage of this method is the relatively short period of stable activity prepared in this way catalyst due to the formation thereon during operation of the coke deposits.

The aim of the invention is the prolonged period of stable activity of the catalyst.

This goal is achieved by a method comprising mixing a powder of zeolite ZSM-5 in the ammonium form with Zn salt solution and the salt solution NH4, filtering the mixture, washing the precipitate in water to remove anions, evaporation, forming granules with a binder Al2O3the drying and calcination after calcination of the pellets treated at a temperature of 450-550aboutC for 5-10 h of a gas mixture containing, wt.%: Carbon monoxide 4-8 4-12 carbon Dioxide Hydrogen 10-20 Oxygen 2-6 Water pawleny method differs from the known the granules are subjected to processing at a temperature of 450-550aboutC for 5-10 h of a gas mixture containing, wt.%: carbon monoxide 4-8; 4-12 carbon dioxide; hydrogen 10-20; oxygen 2-6; water vapor 5-15; nitrogen else.

Thus the claimed method meets the criterion of the invention of "novelty."

The essence of the method lies in the fact that after treatment of the catalyst in the gas mixtures of such compounds significantly reduced side coking process using a catalyst in the reaction of aromatization of light hydrocarbons, as a result of increasing the period of stable activity of the catalyst.

In the basis of these findings are experimental studies of the influence of gas mixture composition and mode of thermal treatment, which showed that outside the stated ranges leads to a reduction of the period of steady activity, which is associated with one side (the outlet for the lower limits of the ranges) reduce the efficiency of the flow of topochemical reactions leading to the formation of active centers with a long period of steady activity. On the other hand (in the case of the upper limits of the ranges) begin to dominate">

P R I m e R 1. In a vessel with a stirrer to prepare 11 l of a solution of ammonium sulfate in the condensate (water with low salt content) with a concentration of 30 g/l in an amount to provide 5 EQ (NH4)2SO41 EQ. Na2O in the zeolite. In the prepared solution with stirring download 1245 g high zeolite in sodium form, the resulting suspension is heated to 50-60aboutC and maintained at this temperature for 2 hours, the Suspension of the zeolite is drained on a suction filter and after wringing the mother liquor was washed with 12, 45 l of condensate (per 1 kg of dry matter). The resulting pellet is discharged from the suction filter and subjected to subsequent processing (cation exchange) to a residual content of Na2O in the zeolite is not more than 0.1%. After washing the pellet and conducting cation-exchange with ammonium sulfate spend processing of zeolite powder 6,8 l of 0.5 N. a solution of Zn(CH3COOH)2. The treatment is carried out for 2 h at a temperature of 60aboutC. then a suspension of the zeolite is filtered and sent to the granulation. Zeolite granularit with a binder in the following ratio of components: zeolite 60 wt.% (1245 g), Al2O3of 36.5 wt.% (757 g), B2O33.5 wt.% (to 72.6 g). B2O3enter for the number of cakes (1245 g), Al2O3757 g, B2O3to 72.6 g and are peptization mass with addition of HNO3to pH 3. The mass is stirred until homogeneous and evaporated to the desired granulating humidity (40-48%).

Ready to moldable mass plastificator on rollers and is then formed on the screw granulator. Granules provalivajut on the air for 20 h and then dried in a chamber dryer for 10 hours Obtained granules are calcined in an electric furnace at a temperature of 500-550aboutWith over 6 hours the Temperature is raised to the desired speeds of no more than 150aboutWith in the hour. The resulting catalyst has the following composition: high-silica zeolite ZSM-5 (with a ratio of SiO2/Al2O3= 39) 57,0, Al2O336,5, B2O33,5, Zn 3,0.

Then carry out the treatment of the catalyst with a gas mixture containing, by weight. % : carbon monoxide 5; carbon dioxide 6; water vapor 15; 15 hydrogen; oxygen 5; nitrogen else if 500aboutC for 6 hours After completion of the gas treatment catalyst pellet rinsed with air and cooled in air to room temperature. Then the granules are discharged into the hopper, then scatter from dust and fall asleep in plastic bags inserted into BOC the used light hydrocarbons WITH2-C5. The process was carried out at a temperature of 500aboutC, flow rate 1.5 h-1 for liquid raw materials. Under these conditions, the yield of aromatic hydrocarbons amounted to (C6-C9) 58.2% , and aliphatic hydrocarbons of 7.2%, gas 33,0% (including hydrogen - 2,5%, methane - 4,0%, WITH2- 7,5%, WITH3+C4- 19%), Cox - 1,6%.

The catalyst prepared in this way maintains a stable activity in the reaction of transformation of broad fraction of light hydrocarbons for 170 h, and in making prjamogonnogo gasoline within 400 including the parameters of the control catalyst, prepared in accordance with the method prototype is 100 and 280 h, respectively. Evaluation of the stability of the catalyst was carried out on the yield of aromatic hydrocarbons. The criterion for stability was a 30% decrease in output.

P R I m m e R 2. The catalyst was prepared in accordance with example 1 except that the processing of the catalyst used, the gas mixture composition, wt.%: carbon monoxide 6; carbon dioxide 7; water vapor 12; 10 hydrogen; oxygen 5; nitrogen else. A period of steady activity in the transformation of broad fraction of light hydrocarbons is 180 h, and straight-run gasoline 420 h

P R gas mixture composition, wt. % : carbon monoxide 8; carbon dioxide 10; water vapor 11; oxygen 5; nitrogen else. A period of steady activity in the process of transformation of broad fraction of light hydrocarbons was 160 h, and for gasoline 380 hours

The METHOD of PREPARATION of ZEOLITE-containing CATALYST for conversion of hydrocarbons in the motor fuel comprising a mixture of a powder of zeolite ZSM-5 in the ammonium form with a solution of zinc salts and ammonium salt solution, filtering the mixture, washing the precipitate in water, evaporation, forming granules with a binder, aluminum oxide, drying and calcination, wherein after annealing the pellets treated at 450 - 550oC for 5 to 10 h of gas mixture composition, wt.%:

Carbon monoxide 4 - 8

Carbon dioxide 4 - 12

Hydrogen 10 - 20

Oxygen 2 - 6

Water vapor 5 - 15

Nitrogen Else

 

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SUBSTANCE: proposed zeolites have AAI of at least 1,2. Method of obtaining zeolite includes removal of tetraethyl ammonium standard agent at temperature not above 550°C under conditions when zeolite has AAI of at least 1, 2 after removal of standard specimen. Zeolite is selected from group consisting of beta-zeolite, TEA-mordenite and TEA-ZSM-12. Proposed zeolites are effective for aromatic alkylation processes.

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