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%
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 PM3 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).
FIELD: petroleum processing and petrochemical processes.
SUBSTANCE: invention relates to some catalyst compositions and processes capable of lowering level of sulfur compounds commonly present as parts of gasoline fraction streams in fluidized-bed catalytic cracking processes. Equilibrium cracking catalyst composition is used comprising at least one Y-type zeolite having kinetic activity in feedstock conversion equal to about 3 combined with alumina-based composite, which contains Lewis acid in amount of at least 50% by weight based on the total catalyst composition.
EFFECT: achieved kinetic activity of equilibrium catalyst during feedstock conversion equal to about 2.
27 cl, 2 dwg, 3 tbl, 3 ex
FIELD: petroleum processing.
SUBSTANCE: catalyst represents a mixture comprising: particulate catalyst prepared by homogenously dispersing crystalline aluminosilicate zeolite in inorganic oxide matrix and particulate additive-type catalyst deactivating metals impairing catalyst and contained in oil feedstock, un which catalyst calcium carbonate with average particle diameter 0.001 to 30 μm is dispersed in inorganic matrix through which amount of said calcium carbonate achieved 30 to 70% based on dry material. Ratio of catalyst to additive-type catalyst ranges between 99.9:1 and 50:50. Catalyst shows excellent cracking power and is able to process petroleum distillation residues.
EFFECT: increased catalytic activity and prolonged lifetime.
3 cl, 8 dwg, 11 tbl, 14 ex
FIELD: petroleum processing and catalysts.
SUBSTANCE: method consists in performing ion exchanges by rare-earth and ammonium cations on zeolite NaY, two-step ultrastabilization of zeolite in water steam medium, mixing zeolite with matrix components to form composition, and spray drying of resulting composition followed by calcination and preparation of catalyst. In the first stage, ultrastabilization of zeolite is conducted at 550-650°C and partial water steam pressure within a range 0.1 to 1.0 atm. In the second stage, ultrastabilization is performed after spray drying by calcination of composition at 650-750°C and partial water steam pressure within a range 0.05 to 0.3 atm.
EFFECT: increased lattice module of zeolite and relative crystallinity resulting in increased catalytic activity.
6 cl, 1 tbl, 9 ex
FIELD: petroleum processing.
SUBSTANCE: catalyst is characterized by that content of rare-earth elements in crystalline lattice of Y-zeolite, based on RE2O3, is 4 to 15 wt %, initial size of elementary cell is 2.450 to 2.458 nm, and size of equilibrium structure of elementary cell after its treatment with 100% steam at 800°C for 17 h exceeds 2.430 nm. Also described is a method for preparation of above catalyst for hydrocarbon cracking comprising (1) drying Y-zeolite with rare-earth element ions to water level below 10%, then, at a weight ratio SiCl4/Y-zeolite, interacting zeolite with gaseous SiCl4 supplied with dry air at 150-600°C for a period of time from 5 min to 2 h after reaction followed by removing residual soluble by-products in zeolite by washing with decationized water; (2) mixing and suspending 10-50% Y-zeolite with rare-earth element ions prepared in step (1), 10-60% binder, and 2-75% clay followed by forming catalyst by spray drying and using it.
EFFECT: increased catalytic activity, hydrothermal stability, degree of heavy oil conversion, and selectivity with respect to gasoline, dry gas, and coke, and considerably reduced content of olefin in produced gasoline.
33 cl, 3 dwg, 17 tbl, 36 ex
SUBSTANCE: description is given of a method of alkylation of hydrocarbon compounds, including obtaining of a catalyst, containing ion-exchanged zeolite Y, containing ions of an alkaline metal, ions of an alkaline-earth metal or their mixture with crystal size of not more than 100 nm, and reaction of the alkylable hydrocarbon with the alkylating agent in the presence of a catalyst under alkylation reaction conditions.
EFFECT: obtaining of a petrol product with a higher octane number.
24 cl, 1 tbl, 5 ex
SUBSTANCE: description is given of a catalytic composition for hydrocracking, which consists of a carrier, containing zeolite with a faujasite structure with cell dimension ranging from 24.10 to 24.40 Å , volume ratio of silicon oxide:aluminium oxide (SAR) of approximately 12, and surface area of at least 850 m2/g, according to the BET and ASTM D 4365-95 measurement method on adsorption of nitrogen with p/po 0.03 value, and volume of micropores of at least 0.28 ml/g, hydrogenating component - at least one metal, chosen from group VIB and VIII metals, and optionally a binding substance. The catalytic composition is obtained using a method which involves a) preparation of the initial zeolite with faujasite structure with ratio of silicon oxide to aluminium oxide ranging from 4.5 to 6.5 and content of alkali less than 1.5 wt %; b) hydrothermal treatment of the above mentioned zeolite at temperature of 600-850°C and partial pressure, coming from an external source, in the range of 0.2-1 atm for a period of time, sufficient for obtaining intermediate zeolite with cell dimension of 24.30-24.45 Å ; c) contacting intermediate zeolite with an acidifying solution, containing an acid and optionally an ammonium salt, under conditions conducive for obtaining zeolite with large surface area of faujasite structure with cell dimension in the range 24.10-24.40 Å , volume ratio of silicon oxide:aluminium oxide greater than 12 and surface area of at least 850 m2/g, according to the BET and ASTM D 4365-95 measuring method, on adsorption of nitrogen with p/po 0.03 value, and volume of micropores of at least 0.28 ml/g and d) optional mixing of the above mentioned zeolite with a binding substance and/or a second cracking component, extrusion and baking; and e) adding at least one hydrogenating component to zeolite from stage (c) or to a catalyst at stage (d) or after it. Description is also given of a method of converting hydrocarbon raw material to low-boiling point materials, by contacting the raw material with hydrogen at high temperature and pressure in the presence of the above mentioned catalyst.
EFFECT: obtaining a catalytic composition with high selectiveness on average disciplines.
10 cl, 5 tbl, 3 ex
SUBSTANCE: invention relates to field of oil-processing and oil-chemical industry, namely to preparation of catalysts of deep catalytic cracking of oil fractions for C2-C4 olefin and high-octane petroleum production. Claimed catalyst for deep oil fraction cracking contains ultrastable zeolite Y in cation-decationated form, zeolite HZSM-5, and as matrix components bentonite clay, aluminium hydroxide and amorphous alumosilicate are used with the following component content, wt %: zeolite Y 10-30; zeolite HZSM-5 - 10-30; bentonite clay - 15-40; aluminium hydroxide - 0-20; amorphous alumosilicate - 20-40. Claimed method of preparing catalysts for deep oil fraction cracking includes passing ionic exchanges of Na cations, contained in zeolite Y onto cations of rare earth metals and ammonium, ultrastabilisation of zeolite in water steam medium, mixing of zeolite Y with suspension of zeolite HZSM-5 and matrix components, dispersion drying of obtained composition with further burning and obtaining catalyst, as matrix components bentonite clay and amorphous alumosilicate or bentonite clay, aluminium hydroxide and amorphous alumosilicate being used.
EFFECT: obtaining catalyst ensuring high output of both C2-C4 olefins and petroleum.
2 cl, 2 tbl, 14 ex
SUBSTANCE: mould catalyst for hydrocracking contains at least zeolite Y and inorganic high-melting oxide with monomodal pores distribution (by mercury porosimetre) whereat at least 50% of total volume is represented with pores having diametre in the range from 4 to 50 nm and the volume at least 0.4 ml/g. The method for carrier preparation and the carrier obtained with this method are described; the said method includes moulding of the mixture containing at least zeolite Y and high-melting oxide with calcinations losses in the range (LIR) from 55 to 75%. The catalytical composition for hydrocracking includes said carrier, at least one component of hydrogenating metal selected from the metal of groups V1B and group V111 and optionally at least one promoting element selected from silicon boron in the case when carrier virtually does not contain the alumosilicate zeolite. The method for catalytical composition preparation and composition obtained with this method are described; the said method includes optional calcinations of the said carrier, precipitation of the at least one hydrogenating metal selected from described above ones in the corresponding amount; the said precipitation is carried out by impregnation with solution containing organic compound having at least two functional groups selected from carboxyl, carbonyl and hydroxyl groups. The hydrocracking method with application of the aforementioned catalytical composition is described.
EFFECT: enhancing of the catalytical composition activity, selectivity and hydrogenation ability.
18 cl, 5 tbl