The method of producing cracking catalyst

 

(57) Abstract:

Usage: oil refining, in particular the production of catalysts cracking. The inventive catalyst is obtained by mixing zeolite Y, clay, water and a binder, followed by molding, drying and calcining. As a binder used alumina trihydrate, calcined at 800 - 1100oC for from 0.5 to 2.0 and treated with nitric acid from the calculation of 0.10 - 0.20 mol NHO31 mol Al2O3at 150 - 180oWith over 4 to 18 hours a Binder is mixed with the zeolite and the clay mass ratio of binder: zeolite: clay= 1:(2 - 10):(15oC44). Zeolite Y is used in rare earth, ammonium, hydrogen or a mixed ion-exchange form. table 1.

The invention relates to methods for heterogeneous catalysts, in particular catalysts cracking.

There is a method of preparation of the catalyst, which consists in the fact that the mixed suspension consisting of sodium silicate and clay with a solution of aluminum sulfate obtained gel-like suspension is maintained at a pH of 9.0 to 9.6, then add the sodium aluminate solution and subjecting the resulting suspension aluminosilicate gel ageing necessary to do Puja of the pH value by addition of an aqueous suspension of hydroxides of Mg or Ca and / or oxides of these metals in amounts < 3% wt. in the matrix of the final catalyst.

The resulting matrix contains the silicate in the amount of 55 to 80 wt. (when the content in alumosilicate 15 of 35% primarily 22 -28 wt. aluminium oxide).

In the matrix type zeolite NaY or pre-modified with cations and thermally stable, for example, the calcined RSU. Then the catalyst is filtered off, Rasulova and dried in the spray dryer to obtain a microspherical catalyst for a process fluid, or after filtration is dried, crushed and molded in the form of pellets, tablets, granules having a size of 1/8 to 1/4 inch for use in processes with a fixed or moving bed of catalyst.

After molding to particles of the desired size and shape of the catalyst is washed with 2 10% solution of ammonium sulfate, then either acidified to pH 4 to 5, or padmalochan to pH 8 to 9 with water at 65 80oWith the removal of soluble impurities (up to the content of Na+< 1 wt. preferably < 0.5. (calculated as Na2O) content SO24-< 0.5 wt.% preferably 0.1 to 0.3 wt. )

The pH value of washing solutions depends on the nature of the zeolite component in the catalyst is obtained by adding to the water will eraut ion exchange with suitable cations, for example, solutions containing AG3+.

The content of zeolite in the catalyst 5 25% mainly 10 to 20 wt. the clay content of 0 to 40%, mostly 25 to 35 wt. (1).

The known method according to which the clay is predominantly kaolinitic, thoroughly mixed with sodium silicate, zeolite Y (Na+Mor RA3+or NH+4or mixed ion-exchange forms) and water to obtain a homogeneous suspension.

The resulting mixture is dried (if for the formation of microspheres in the spray dryer to a moisture content of 10 to 20% then mixed with the buffer solution of ammonium salt, for example ammonium sulfate, and incubated at pH 4 to 7, adjusting the pH by adding acid to gel formation SiO2.

If the original zeolite is used in the Na-form, or the degree of ion exchange in the original zeolite is not high enough, spend additional ion exchange ions AG3+, NH+4or their mixture to the Na content in the catalyst of 0.7 wt. (Na2O) or less.

The catalyst is filtered off and thoroughly washed prior to the absence SO24-reaction with BaCl2.

The content of zeolite and clay in the catalyst (dry matter) 10-30. the zeolite per 1 part of weight of SiO2(on dry substance of catalyst) /2/.

A known method of producing cracking catalyst, whereby the NaY zeolite with a molar ratio of 4.8 and a content of Na2O 13,8% mixed with sodium aluminate solution at pH 13, and then sulfuric acid was adjusted to a pH of 5.7 for the deposition of the gel aluminium hydroxide. The resulting aqueous suspension is subjected to ion exchange with ammonium sulfate at pH 5.0 to 6.0, maintaining the pH by adding sulfuric acid to the content of Na2O 2.5% (on dry substance). The mixture is filtered, washed to the absence of SO24-and dried at 100oC.

The mixture of zeolite-Almagell is dispersed in water with kaolin clay and pseudoboehmite (pseudoboehmite pre peptizer formic acid, for example in the ratio 0,095 ml. of 90% formic to you on 1 g of Al2O3), then add the ammonium polysilicate. The resulting suspension is dried in the spray dryer. After spray drying the zeolite in the catalyst composition can be further exchanged for cations NH+4and(or) RA3+to reduce the content of Na2O to <1 wt.

The ratio of the components in the catalyst (3):

zeolite is 5 to 50 wt.

alumohydrogen 2 to 30 wt. (Al.

There is a method in which the binder is aluminum monohydrate, obtained by hydrolysis of aluminum alkoxide, peptizer aqueous solution of formic acid, then add clay. After intensive stirring to a suspension type zeolite Y in the AG-form, then the ammonium polysilicate and 0.2 to 2.5 wt. Al2(OH)5NO3(calculated on dry substance of the catalyst).

The ratio of the components (4)

binder 7 mos.

clay 60 70%

SiO21 7%

zeolite 10 -35%

All known methods of preparation of the catalyst require a lot of reagents, technologically sophisticated and are accompanied by a number of sinks. So, for the synthesis of catalysts required sodium silicate, aluminum sulfate, sodium aluminate, hydroxides or oxides of alkaline-earth metals, ammonium sulphate, hydrochloric acid, ammonia (1); sodium silicate, ammonium sulfate and sulfuric acid (2); sodium aluminate, sulfuric acid, formic acid, ammonium polysilicate, pseudoboehmite (3), a typical way to obtain which pereosazhdeniya, also requires a large number of acids and bases, stages and is accompanied by numerous drains (5).

For the synthesis of the catalyst by the method used in (4), the MINIA receive in turn a reaction triethylamine and ethylene with subsequent oxidation of aluminiumraw (5).

These methods of obtaining catalysts have many stages, including such time-consuming and laborious, as the filtering and washing, and a large amount of wastewater containing toxic chemicals.

The closest known solution of an analogous problem to the technical essence is a method of producing a catalyst, which consists in the fact that the zeolite Y in rare earth, ammonium, hydrogen or a mixed ion-exchange form with the content of oxides of alkali metals > 1% (by weight) is mixed with chlorhydrate aluminum, water and clay, preferably kaolin, in a ratio of 5 to 25 wt. chlorhydrate aluminum (Al2O3), 1 to 60 wt. zeolite, 0 to 90% clay, to obtain a mixture of plastic or liquid consistency. The mixture is formed into particles of desired shape and size (microsphere, granules, beads), dried and calcined at 300 700oWith (6).

In this way the preparation of the catalyst as a binder using an aluminium oxychloride (7,8), we get sufficiently complex technology, requiring the use of aluminum metal and (or) aluminum chloride.

The most frequently used method to obtain axiala is the dissolution of metal al is m hydrogen.

The main objective of the proposed solution is the development of waste-free, closed and relatively simple technology of preparation of the catalyst cracking.

This problem is solved by the claimed method of producing cracking catalyst comprising a mixture of zeolite Y, clay, water and a binder, forming, drying and calcining, in which the binder used alumina trihydrate, calcined at 800 -1100oC for 0,5 2,0, treated with nitric acid from the calculation of 0.10 to 0.20 moles of HNO31 mol Al2O3at 150 180oWith over 4 to 18 h and mixed with the zeolite and the clay mass ratio of binder:zeolite:clay 1:(2 - 10):(15:44)

Zeolite Y is used in rare earth, ammonium, hydrogen or a mixed ion-exchange form.

Comparative analysis of the proposed solutions with the prototype shows that the inventive method differs from the known fact that the use as a binder alumina trihydrate, calcined at 800 -1100oC for 0.5 to 2.0 sec, the resulting product is treated with nitric acid based 0,20 0,10 mol HNO3on mol Al2O3at 150 180oWith over 4 to 18 h and mixed with the zeolite and clay in mass criterion of "novelty."

Example 1. 100 g of a technical three-hydrate of alumina-gibbsite (calculation on Al2O3) calcined at a temperature of 800oWith over 2.0 with, mixed with 12.5 ml 56% nitric acid and 300 ml of water and the mixture is stirred at 150oWith over 18 PM

3 g of the product (hereinafter, calculation of the score. dry matter) are thoroughly mixed with 51 g of kaolin clay and water, then add 6 g of zeolite Y in WA Na-form (the content of Na2O 1.5% of the content of RSO -18,1%). The mixture of plastic consistency with a water content of 55% is formed into pellets with a diameter of 5 mm, the Catalyst was dried at 120 140oC for 6 h and calcined at 500 -750oC for 2 h with a gradual temperature increase, then at 750oC for 4 h (sample A).

Example 2. The catalyst prepared according to example 1, except that the alumina trihydrate calcined at 1100oC for 0.5 s, add an 8.4 ml of nitric acid, treated with acid at 180oC for 4 h and the catalyst was injected 12 g of zeolite and 45 g of kaolin clay (sample B).

Example 3. The catalyst prepared according to example 1, except that the alumina trihydrate calcined at 950oWith over 1,2, type of 16.7 ml of nitric acid, treated with acid is In).

Example 4. The catalyst prepared according to example 3 except that the catalyst is injected 12 g of zeolite Y in HNa-form (the content of Na2O 2.3% of RSA 10,8%) and 46.8 g of kaolin clay (sample G).

Example 5 (the prototype).

The catalyst prepared according to example 2, only as a binder used aluminium oxychloride Al2Cl(OH)5in the amount of 6 g and the composition is administered to 42 g of kaolin clay (sample D).

Example 6. Samples a,B,C,D and e for 6 h and treated with 100% water.steam at 750oWith, and then determine their bulk density, crushing strength, wear in the airlift and indicators of catalytic activity in the cracking of kerosene-gas oil fraction according to the OST 38.01176-79: t 460oWith ASHI 1.44 x-1.

The figures given in the table.

The comparison of the obtained data shows that the samples prepared in accordance with the proposed solution, in terms of bulk density, strength and catalytic activity are at the level of the sample prepared according to the prototype, and more selective output of gasoline and coke.

The proposed solution allows to use a much smaller amount of the binder is 2 to 5% than at a known solution analogichnogo decomposition of the binder), at which cracking occurs selectivity (2).

The proposed technology is malariacontrol, waste, drainage and quite simple. The raw materials and reagents are not a deficiency.

The method of producing cracking catalyst comprising a mixture of zeolite, clay, water and a binder, forming, drying and calcining, characterized in that the binder used alumina trihydrate, calcined at 800 1100oC for 0,5 2,0, treated with nitric acid at a rate of 0.1 to 0.2 mol of acid per 1 mol of aluminum oxide at 150 180oWith over 4 to 18 h and mixed with the zeolite and The clay mass ratio of binder: zeolite: clay 1 (2 10) (15 44).

 

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