The method of preparation of zeolite-containing catalyst for conversion of hydrocarbons

 

(57) Abstract:

The method of preparation of the zeolite catalyst provides an operation step of annealing granules and processing at a temperature of 450-550oC 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, the rest is nitrogen.

The invention relates to the synthesis of catalysts for the conversion of light hydrocarbons to aromatic hydrocarbons and may find wide application in the processing of associated petroleum gas, wide fraction of light hydrocarbons and compressit obtaining aromatic hydrocarbons and motor fuels.

Known methods of preparing catalysts for the conversion of light hydrocarbons to aromatic hydrocarbons using zeolite powder [1]

Closest to the technical nature of the method, selected as a prototype is a method for preparing zeolite-containing catalyst described in [2]

Prototype method includes mixing a powder of zeolite ZSM-5 in the ammonium form with 0.5 N solution of ZnCl2and 0.5 N solution of NH4Cl, filtering the solution, rinsing in water for UD is named Al2O3, drying at 100-120oC for 10 h and calcination at 540oC. the resulting product has a residue 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 does not usually exceed 1%

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

In the present invention has the aim of increasing the time a stable activity of the catalyst. This problem is solved in the method of preparation ceritadewasa catalyst for conversion of hydrocarbons into aromatic hydrocarbons comprising a mixture of a powder of zeolite ZSM-5 in the ammonium form with Zn salt solution and the salt solution NH4Cl, filtering the mixture, washing the precipitate in water to remove anions, evaporation, formation of granules with linking Al2O3the drying and annealing step, in which the granules after subjected to annealing treatment at 450-550oC for 5-10 h of a gas mixture containing, by weight. the oxide of plerixafor in the gas mixture the proposed composition significantly reduces the side coking process using a catalyst in the reaction of aromatization of light hydrocarbons. As a result of this additional operations increases the period of stable activity of the catalyst.

Experimental studies of samples of the catalyst obtained with the use of additional processing in the gas mixture of the above-mentioned composition and mode of thermal treatment, has shown that going beyond the stated ranges leads to decrease the time of its stable activity. When exceeding the lower limits of the ranges is reduced due to a decrease in the efficiency of the flow of topochemical reactions leading to the formation of active centers with a long period of steady activity. If the upper limit of the temperature and concentration ranges begin to dominate the processes of destruction of active sites and structure of the catalyst in thermal processing.

Example 1. In a vessel with a stirrer to prepare 11 l of a solution of ammonium sulfate in the condensate with a concentration of 30 g/l in an amount to provide 5 EQ (NH4)2SO41 equiv of Na2O in the zeolite. In the prepared solution with stirring download 1245 g high zeolite in sodium form, the resulting suspension is heated to 50-602O in the zeolite is not more than 01% After washing the pellet and conducting cation-exchange with ammonium sulfate spend processing of zeolite powder 6,8 l of 0.5 N solution of Zn(CH3COOH)2. The treatment is carried out for 2 h at 60oC. then a suspension of the zeolite is filtered and sent to the granulation. Zeolite granularit with a binder with the following ratio of components, wt. (g): zeolite 60 (1245), Al2O336,5 (757)2ABOUT33,5 (72,6). IN2ABOUT3enter to reduce the acidity of the binder.

The procedure for preparation of the masses for the formation. In the mixer load estimated number of cakes (1245 g), Al2O3757 g2ABOUT3to 72.6 g and are peptization mass with addition of NGO3to pH 3. The mass is stirred until homogeneous and evaporated to the desired granulating humidity (40-48%).

Ready for the formation of 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 graded calcined in an electric furnace up to 500-550oWith over 10 hours the Temperature is gradually raised to the desired speeds of no more than 150oWith h the congestion has the following composition: high-silica zeolite ZSM-5 (with a ratio of SiO2/Al2O339) 57,0% Al2O336.5% IN2ABOUT3a 3.5% Zn, 3.0% of

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 rest at a temperature of 500oC for 6 h

Prepared by the proposed method, the catalyst was pilot-tested at the facility for processing of light hydrocarbons into aromatic hydrocarbons.

When tested in the reactor conversion was loaded with 50 g of catalyst a density of 0.7 g/cm3. The raw material used light hydrocarbons WITH2-C5. The process was carried out at a temperature of 500oC, flow rate 1.5 h-1for liquid raw materials. Under these conditions, the yield of aromatic hydrocarbons (C6-C9) was 58.2% aliphatic hydrocarbons 7.2% of gases 33,0% including hydrogen 2.5% methane by 4.0% TO 7.2% WITH3+C419%coke 1,6%

The catalyst prepared by the proposed method, maintains stable activity in the reaction of transformation of broad fraction of light hydrocarbons for 170 h, and in making gasoline for 400 including the parameters of the control catalyst, prepared according to revovles the yield of aromatic hydrocarbons. The criterion for stability was 20% drop in output.

Example 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 and 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

Example 3. The catalyst was prepared in accordance with example 1 except that used to process the gas mixture composition, wt. carbon monoxide 8, carbon dioxide 10, water vapor 11, oxygen and 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 h

Prepared by the proposed method, the catalyst can be widely used in catalytic obtaining aromatic hydrocarbons from waste oil.

The method of preparation of the zeolite catalyst for conversion of hydrocarbons into aromatic hydrocarbons comprising a mixture of a powder of zeolite ZSM-5 in the ammonium form with a salt solution Nie, the formation of granules with a binder, aluminum oxide, drying and calcination, wherein the granules after stepwise annealing processed at 450 550oC for 5-10 h of a gas mixture containing, by weight.

Carbon monoxide 4 8

Carbon dioxide 4 12

Hydrogen 10 20

Oxygen 2 6

Water vapor 5 15

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