The method of preparation of zeolite-containing catalyst

 

(57) Abstract:

The invention relates to the field of chemistry, and in particular to methods of preparation of catalysts for converting light hydrocarbons into high-octane components of motor fuels. The method comprises mixing 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 and boron oxide, drying and calcination. The mixture was further added a solution of zirconium acetate, and after annealing the pellets processed at 450-550oC for 5-10 h of gas mixture composition, wt.%: carbon monoxide 4-8; 4-12 carbon dioxide; hydrogen 6-8; oxygen 2-6; water vapor 2-4; nitrogen - rest. This results in a longer period of stable activity of the catalyst.

The technical field to which the invention relates

The invention relates to the field of chemistry, and in particular to methods of preparation of catalysts for converting light hydrocarbons into high-octane components of motor fuels.

Art

Known method of preparing zeolite-containing catalyst (US A1, 4157293, 1979), vklyuchitel solution, rinse in water to remove the ions CL), evaporation to the desired moisture content, to allow molding, molding granules with a binder Al2ABOUT3, drying at a temperature of 100-120oC for 10 h and calcination at 540oC. 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, such as Ge, si. 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.

Closest to the present invention is a method for preparing zeolite-containing catalyst for conversion of hydrocarbons in the motor fuel (EN 2024305, 1994). The known method includes mixing 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 and after calcination of the pellets processed at 450550oIn R>
Oxygen - 2-6

Water vapor - 5-15

Nitrogen - Rest

There is a method allows to increase the period of stable activity made with the use of the catalyst. However, to improve technical and environmental performance of the process of converting light hydrocarbons into high-octane components of motor fuels requires a prolonged period of stable activity of the catalyst.

The invention

The present invention is the development and creation of a method of preparing zeolite-containing catalyst for conversion of hydrocarbons in motor oil with improved parameters.

The solution of this task is possible to obtain a technical result consists in increasing the period of stable activity of the catalyst.

This technical result is achieved in that in 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 SWAT after annealing the pellets processed at 450550oC for 5-10 h of gas mixture composition, wt. %:

Carbon monoxide - 4-8

Carbon dioxide - 4-12

Hydrogen - 6-8

Oxygen - 2-6

Water vapor - 2-4

Nitrogen - Rest

Comparative analysis of the solution with the closest analogue shows that the method in accordance with the present invention differs from the known fact that when mixed powder of zeolite ZSM-5 in the ammonium form with Zn salt solution and the salt solution NH4in the suspension is further added a solution of Zr acetate, and the pellet was processed at a temperature of 450-550oC for 5-10 h of a gas mixture containing, by weight. %: carbon monoxide 4-8; 4-12 carbon dioxide; hydrogen 6-8; oxygen 2-6; water vapor 2-4; nitrogen - rest.

Moreover, it was experimentally found that the strongest influence on the period of stable activity of the catalyst containing in addition to zinc, zirconium, changes in the content of oxygen and water vapor in the gas mixture.

Thus, in comparison with the closest analogue, the effect is to increase the period of stable activity have lower concentrations of these substances. The nearest analogue of the gas mixture, which was treated catalyst contained 10-20 wt.% hydrogen and 5-15 wt.% water vapour. For zirconium is).

Thus, the described method corresponds to the condition of patentability "novelty."

The essence of the method lies in the fact that after treatment of the catalyst with a gas mixture of the composition significantly reduced side coking process using a catalyst in the reaction of aromatization of light hydrocarbons. This results in a longer period of stable activity of the catalyst. The introduction of the catalyst in addition to the zinc zirconium increases the period of stable activity.

In the basis of these findings are an experimental study on 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 the processes of destruction of active sites and structure of the catalyst is the shadow

The implementation of the present invention is confirmed by the following examples.

Example 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 5060oC and maintained at this temperature for 2 hours, the Suspension of zeolite drain on notchfilter and after extraction of the mother liquor is washed in 12,45 l condensate (per 1 kg of dry matter). The resulting pellet unloaded notchfilter 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 solution of Zn (CH3COOH)2. The treatment is carried out for 2 h at a temperature of 60oIn the resulting suspension is added a solution of acetate of Zr in amounts corresponding content in the catalyst 0,20,5% Zr. After a suspension of the zeolite was filtered and direction (1245 g), Al2ABOUT3of 36.5 wt.% (757 g)2O33.5 wt.% (to 72.6 g). IN2ABOUT3enter to reduce the acidity of the binder. The procedure for preparation of the masses for molding: 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 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 500550oWith over 6 hours the Temperature is raised to the desired speeds of no more than 150oWith in the hour. The resulting catalyst has the following composition: high-silica zeolite ZSM-5 (with a ratio of SiO2/Al2ABOUT339) 57,0; Al2ABOUT336,3;2ABOUT33,5; Zn 3,0; Zr 0,2.

Then carry out the treatment of the catalyst with a gas mixture containing, by weight. %: carbon monoxide 5; carbon dioxide 6; water vapor 2; 6 hydrogen; oxygen 5; nitrogen - else if 500oC for 6 hours After acoumeter. Then the granules are discharged into the hopper, then scatter from dust and fall asleep in a plastic bag, inserted in the barrel.

When tested in the reactor was loaded with 50 g of catalyst a density of 0.7 g/see the quality of raw material used light hydrocarbons WITH2-C5. The process was carried out at a temperature of 500oC, flow rate 1.5 h for liquid raw materials. Under these conditions, the yield of aromatic hydrocarbons amounted to (C6-C9) 64.1%, and aliphatic hydrocarbons of 3.1%, gases and 32.3% (including hydrogen of 2.5% methane to 4.0%, WITH2OF 7.5%, WITH3+C418,3%), coke 0,5%.

The catalyst prepared in this way preserves stable activity in the reaction of transformation of broad fraction of light hydrocarbons over 260 hours, and in making gasoline for 500 hours, the parameters of the control catalyst, prepared in accordance with the method of the analog (catalyst contained 3.0 wt. % Zn), up to 100 h 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.

Example 2. The catalyst was prepared in accordance with example 1 except that the processing catalyticsoft 5; nitrogen - rest. Time gas treatment catalyst 6 hour Period of steady activity in the transformation of broad fraction of light hydrocarbons is 260 h, and straight-run gasoline 520 hours

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 8; 6 hydrogen; oxygen 5; nitrogen else. Time gas treatment catalyst 6 hour Period of steady activity in the process of transformation of broad fraction of light hydrocarbons amounted to 230 h, and for gasoline 460 h

The influence of processing time samples of the catalysts shown in examples 4, 5 and 6. It should be noted that treatment of the catalyst with a gas mixture of less than 3 h did not allow the catalyst to achieve operational activity. High activity (conversion of at least 70% and the selectivity for yield of aromatic hydrocarbons of not less than 60%) was achieved after treatment with gases in the range of 5-10 hours

When this processing time of the catalyst gas mixture was influenced for the period of stable activity of the catalyst.

Example 4. The catalyst prepared in accordance with example 1-rayed the od 5; nitrogen - rest. Processing time 5 hour Period of steady activity in the transformation of broad fraction of light hydrocarbons 180 h, and straight-run gasoline 290 h

Example 5. The catalyst prepared in accordance with example 1 was processed gas mixture, whose composition is similar to example 2 for 8 hour Period of steady activity in the transformation of broad fraction of light hydrocarbons 250 h, and straight-run gasoline 480 hours

Example 6. The catalyst prepared in accordance with example 1 was processed gas mixture, whose composition is similar to example 2 for 10 hours At this period of stable activity of the catalyst in the transformation of broad fraction of light hydrocarbons was 180 h, and straight-run gasoline 290 h

Processing gas mixture over 10 h resulted in a decrease of the period of stable activity of the catalyst.

The influence of temperature during processing of the samples of catalyst a gas mixture are given in examples 7, 8, 9.

It should be noted that treatment of the catalyst at temperatures below 450oWith did not allow to achieve high catalyst activity. At temperatures over 550oSince there was a decrease in the catalyst activity.

oC. During this period of steady activity in the transformation of broad fraction of light hydrocarbons 170 h, and straight-run gasoline 300 hours However, under these conditions the yield of aromatic hydrocarbons reached 38.4 per cent.

Example 8. The catalyst was prepared in accordance with example 1 except that the processing gas mixture was carried out at 550oC. under these conditions, the yield of aromatic hydrocarbons made up 48.2%, a period of steady activity in the transformation of broad fraction of light hydrocarbons 200 h, and straight-run gasoline 390 h

Example 9. The catalyst was prepared in accordance with example 1 except that the processing gas mixture was carried out at a temperature of 600oC. under these conditions, the yield of aromatic hydrocarbons decreased to 20.1%, and a period of steady activity in the transformation of broad fraction of light hydrocarbons 100 h, and straight-run gasoline 190 h

The most successful of the invention can be used in the processes of conversion of light hydrocarbons to high octane components of motor fuels. The implementation of the method requires no special equipment and is carried out in any known equipment.

The method of preparation ceritaku 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 and boron oxide, drying and calcination, wherein the mixture further added a solution of zirconium acetate, and after annealing the pellets processed at 450-550oC for 5-10 h of gas mixture composition, wt.%:

Carbon monoxide - 4-8

Carbon dioxide - 4-12

Hydrogen - 6-8

Oxygen - 2-6

Water vapor - 2-4

Nitrogen - Ostalnoe

 

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