A method of obtaining a zeolite-containing catalyst

 

(57) Abstract:

The invention relates to the synthesis of the catalysts used, in particular, for the conversion of hydrocarbons into high-level components of motor fuels, aromatic hydrocarbons. Zeolite-containing catalyst was prepared by mixing powder of zeolite ZSM-5 in Ammonites form with salts of zinc, ammonium, promoting additives, which are used orthosilicate neodymium (in suspension), acetates rhenium and potassium (in the form of aqueous solutions). The method includes filtering the mixture, washing the precipitate, evaporation, formation of granules with a binder, aluminum oxide with the addition of boron oxide, drying, calcining at 500-550oWith subsequent processing at 450-550oGas mixture composition, wt.%: carbon monoxide 4-5, 4-12 carbon dioxide, hydrogen 10-20, oxygen 2-6, water vapor 5-15, nitrogen else, when the throughput rate of the gas mixture of 1.0-200 h-1. The formation of granules with a binder is carried out at the ratio, wt.%: zeolite 58-62, aluminium oxide in 35.5 to 37.5, boron oxide of 2.5 to 4.5. The method allows to increase the period of stable activity of the catalyst, and hence to increase the efficiency of obtaining aromatic hydrocarbons of the paraffin is vodorodnogo raw materials into high-octane components of motor fuels, in particular aromatic hydrocarbons.

To synthetic zeolites that can be used to produce aromatic hydrocarbons, include zeolites ZSM-5, ZSM-12, ZSM-21 with different ratio of SIO, SIS2and Al2O3. From the original zeolite advisable to remove part of the contained alkali metal; a consequence of this exchange is the replacement of alkali metal ions by hydrogen ions or ammonium ions.

A known method of producing zeolite-containing catalyst, which consists in the fact that the zeolite composition of Al2ABOUT3- the 3.65 wt.%, SIO, SIS2- 90,4 wt.%, Na2O - 3,32 wt. % H2O - 2.6 wt.% and the ratio of SIO, SIS2/Al2ABOUT3=42,1 subjected to ion exchange in a solution of ammonium chloride (NH4Cl) (three-time processing with subsequent washing with water); then add the gel Al(Oh)3, formed into pellets by extrusion, dried, calcined and impregnated with a solution of nitric acid lanthanum. The catalyst was dried, calcined, and impregnated with a solution of nitric acid lanthanum. The catalyst was dried, calcined at 500oWith pressed. Get the catalyst composition of the high-silica zeolite - and 99.8 wt. %, Al2J3- 0.1 wt.% (the link is P> This catalyst is used mainly for the alkylation of toluene with ethylene.

There are various ways to obtain a zeolite-containing catalyst based on zeolite ZSM for obtaining aromatic hydrocarbons, promoted With or Ni (SU 1416482, 15.08.88), gallium ions (SU 1147246, 23.03.1985) platinum and rhenium (US 4347394, 1982) containing zeolite ZSM-5 with a ratio of SiO2/A12ABOUT3= 39 (to 57.0 wt.%), Al2ABOUT3(of 36.5 wt.%), IN2(3.5%) and Zn (3 wt.%), [EN 2030376, 10.03.1995].

Known method of preparing 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, formation of granules with a binder, aluminum oxide (Al2ABOUT3mixed with the oxide of boron (2ABOUT3), drying and calcination and after calcination of the catalyst pellet is subjected to heat treatment at 450-550oC for 5-10 h of a gas mixture of carbon monoxide 4-5 wt.%, carbon dioxide - 4-12 wt.%, hydrogen - 10-20 wt.%, oxygen - 2-6 wt.%, water vapor is 5-15 wt.%, nitrogen - rest.

However, known is Oh and petrochemical industries, because it does not have the necessary stable activity.

The closest in technical essence to the claimed invention is a method of obtaining 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 solution of zinc (Zn) and ammonium chloride (NH4Cl), filtering the mixture, washing the precipitate in water to remove anions, evaporation, formation of granules with a binder, aluminum oxide and promoting additives Ge and si is not more than 1 wt.%, drying and annealing step at 500-550oWith 10 g with the speed of temperature rise not exceeding 150oWith an hour and subsequent processing at 450-550oC for 5-10 h of a gas mixture of carbon monoxide - 4-5 wt.%, carbon dioxide - 4-12 wt.%, N - 10-20 wt.%, oxygen - 2-6 wt.%, water vapor is 5-15 wt.%, nitrogen - rest (EN 2084283, 20.07.1997).

The disadvantage of this method is that the obtained thereon the catalyst has a relatively short period of stability due to the formation thereon during operation of the coke deposits.

The technical objective of the claimed invention is to increase per the treatment 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 aqueous solutions of zinc salts and ammonium, promoting additives, filtering the mixture, washing the precipitate in water to remove anions, evaporation, formation of granules with a binder containing alumina, drying, (step) annealing at 500-550oWith, and then processing it at 450-550oWith gas mixture composition (wt.%): carbon monoxide - 4-5, carbon dioxide - 4-12, hydrogen - 10-20, oxygen - 2-6, a steam - 5-15, nitrogen - the rest, as promoting additives used orthosilicate neodymium 7 Nd2ABOUT3*9Si2in the form of suspensions and acetate rhenium and potassium in the form of aqueous solutions, the formation of granules carried out with a binder containing alumina with the addition of boron oxide (2ABOUT3), with a ratio of zeolite 5-6 wt.%, alumina - of 35.5-37.5 wt.%, the boron oxide is 2.5 to 4.5 wt.% and the processing gas mixture is carried out with a feed rate of 1.0-200 h-1.

The preparation of the catalyst using, for example, as ammonium salts ammonium sulfate, ammonium chloride, as salts of zinc - acetic acid zinc.

Using the method of preparation of the catalyst as promotergene with boron oxide, together with treatment of the catalyst with a gas mixture, provide the complex extension of the period of stable activity of the catalyst, which, in turn, contributes to the efficiency of conversion of light hydrocarbon components in motor fuel.

The following examples illustrate the invention but do not restrict it.

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. Na2On the zeolite. In the prepared solution with stirring download 1245 g high zeolite in sodium form, the resulting suspension is heated to 50-60oC and maintained at this temperature for 2 hours, the Suspension of the zeolite is drained on a suction filter and after extraction of the mother liquor is washed in 12,45 l 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 0,5 suspension type suspension orthosilicate Nd (7Nd7ABOUT39SiO2), 10% solution of acetate of rhenium and a 15% solution of potassium acetate in amounts corresponding content in the catalyst of 0.2-0.5 % Re, 0.01 to 0.02 % and 0.1 Nd K. After that, the 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), Al2ABOUT3of 36.5 wt.% (757 g)2ABOUT33,5 wt. % (to 72.6 g). IN2ABOUT3enter to reduce the acidity of the binder. The procedure for preparation of the masses for the formation of: mixer load estimated number of cakes (1245 g), Al2ABOUT3757 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 are calcined in an electric furnace at a temperature of 500-550oWith 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 in wt.% - vysokogo the/SUB>ABOUT3= 39) 56,0; Al2ABOUT337,19;2ABOUT33,5; Zn 3,0; Re 0,2; Nd 0,01; 0,1.

Then spend processing catalyst gas mixture with a feed rate of its 200 h-1containing, wt.%: carbon monoxide 5; carbon dioxide 6; water vapor 15; 15 hydrogen; oxygen 5; nitrogen else if 500oC 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 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/cm in the quality of raw material used light hydrocarbons, C2-C5. The process is 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) 66,1 %, aliphatic hydrocarbons of 3.1 %, gas 28,0 % (including hydrogen - 2,5 %, methane - 4,0 %, WITH2- 7,5 %, WITH3+C4- 19 %), Cox - rest.

The catalyst prepared in this way preserves stable activity in the reaction of transformation of broad fraction of light hydrocarbons for 240 hours, and turned the with the method of the prototype, be 100 and 280 h, respectively. Evaluation of the stability of the catalyst was carried out on the yield of aromatic hydrocarbons. The decrease of the yield of aromatic hydrocarbons during long-term operation (30%) was estimated as a loss of stability and the continued operation impractical.

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 5; nitrogen else. A period of steady activity in the transformation of broad fraction of light hydrocarbons is 260 h, and straight-run gasoline 500 hours; feed rate of the gas mixture through the catalyst 70 h-1.

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 5; nitrogen else. A period of steady activity in the process of transformation of broad fraction of light hydrocarbons amounted to 220 h, and for gasoline 450 hours; feed rate (bandwidth) of the gas mixture through the catalyst 5 h-1.

A method of obtaining a zeolite-containing catalyst for conversion of hydrocarbons in the components of motor fuel comprising a mixture of a powder of zeolite-containing catalyst for conversion of hydrocarbons in the components of motor fuel comprising a mixture of a powder type zeolite ZMS-5 in the ammonium form with aqueous solutions of zinc salts and ammonium, promoting additives, filtering the mixture, washing the precipitate in water to remove anions, evaporation, formation of granules with a binder containing alumina Al2O3, drying, annealing step at 500-550oWith and subsequent processing at 450-550oWith a gas mixture of composition: carbon monoxide 4-5 wt. %, carbon dioxide 4-12 wt. % hydrogen 10-20 wt. %, oxygen 2-6 wt. % water vapor 5-15 wt. %, nitrogen else, characterized in that as promoting additives used orthosilicate neodymium 7Nd2O39SiO2in suspension and acetates of rhenium and potassium in the form of aqueous solutions, the formation of granules of zeolite Khujand is in 35.5 37.5 wt. %, boron oxide 2,5-4,5 wt. percent, and the processing gas mixture is carried out at a feed rate of the gas mixture of 1.0-200 h-1.

 

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