RU2579512C1 - Method for preparing catalyst and catalyst for alkylation of isobutane with isobutene - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: described is method for preparation of catalyst on the base of zeolite of NaNH₄Y type with residual content of sodium oxide not higher than 0.8 wt %, which includes soaking while mixing zeolite crystals with lanthanum nitrate water solution in quantity, which provides content of lanthanum in zeolite 3.0 wt %, mixing formed suspension with second suspension, obtained by peptisation of nitric acid water solution to pH 1-3 of aluminium hydroxide powder, granulation of mould mass, re-oxidising at room temperature for 18-24 h, drying with temperature increase of 2 degrees per minute and exposure at 110±10°C for not less than 5 h and tempering with temperature increase of 10 degrees per minute and exposure at 280±10°C for not less than 4 h and at 510±10°C for not less than 4 hours; powders of zeolite and aluminium hydroxide of pseudoboehmite modification have particle size not less than 40 mcm, with additional introduction into mould mass with mixing of powder of sulphated tetragonal zircon dioxide with content 5 wt % of (SO₄)₂ ^2- and with particles with size less than 40 mcm, as well as micro-needle wollastonite non-modified - natural calcium silicate CaSiO₃ with characteristic ratio l:d = (12-20):1 and length of microneedles 1<20 mcm, with the following weight ratio of components in mould mass, %: zoelite of NaNH₄Y type - (26.14-30.68), lanthanum nitrate (1.90-2.22), aluminium hydroxide (pseudoboehmite) - (14.88-19.40), sulphated zircon oxide - (9.90-14.61) and micro-needle wollastonite - natural calcium silicate CaSiO₃, nitric acid (0.44-0.57), water - to 100. Also described is catalyst, in which components are in weight ratio, %: zeolite of NaLaHY type - (49-55), aluminium oxide (22-30), sulphated zircon oxide (18-25), calcium silicate - (2-4).

EFFECT: increased mechanical strength of granules with preservation of high indices of process - conversion of isobutene and selectivity by trimethylpentanes with increase of their stability.

2 cl, 1 tbl, 8 ex

Description

The invention relates to the field of production of isobutane alkylation catalysts with isobutene and can be used in the production technology of isoalkanes alkylation catalysts with alkenes, as well as the production technology of isomerization catalysts.

The alkylation process and catalysts for its implementation are the subject of many research and development. This is due, on the one hand, to the enormous practical interest in the alkylation product, and, on the other hand, to the complexity of the process and the specific requirements for the catalyst. The alkylation product, gasoline-alkylate, is a high-octane component for producing high-quality gasolines. Taking into account the expected abandonment of the use of methyl tert-butyl ether as an octane enhancing additive, the development of catalysts for the production of 2,2,4-trimethylpentane (octane number 100), the product of isobutane alkylation with isobutene, is becoming increasingly urgent.

Modern industrial alkylation is based on the use of liquid acids, sulfuric and hydrofluoric. The main disadvantages of these catalysts are the high specific consumption, toxicity and corrosion activity, the need to separate the catalyst-product mixture with the subsequent disposal of spent acids. The progress of industrial alkylation is associated with the transition to the use of solid catalysts, which will avoid the above problems and get technological and economic advantages.

At present, a variety of solid systems have been proposed as catalysts for the liquid-phase alkylation of isobutane with alkenes: zeolites, heterogeneous liquid acids, aluminum chloride complexes, ion-exchange resins, heteropol and acids, chlorinated and sulfated metal oxides, etc. The main difficulty in the widespread industrial use of such alkylation catalysts it turned out to be their quick deactivation, which is associated with the blocking of active centers and the porous structure of side formations and of high-molecular hydrocarbons. Proposed solutions to this problem are the development of both catalysts with optimized chemical and phase compositions, acidity and a porous structure that reduce the likelihood of blocking, and the working conditions of solid alkylation catalysts, including their multiple regeneration. The latter circumstance puts forward additional stringent requirements for alkylation catalysts, namely the requirement of increased mechanical strength while maintaining high catalytic activity (conversion and selectivity).

The experience of studying isobutane alkylation with isobutene in the presence of solid catalysts showed the fundamental importance of the presence of both Lewis and Brønsted acid centers in the catalyst (LCC and BCC, respectively), as well as the positive effect of maintaining the catalyst in a suspended state, i.e. carrying out the process under conditions of mixing the catalyst granules or their movement in the reaction medium. The implementation of these process conditions ensures the achievement of the best results with respect to the activity, selectivity and duration of operation of solid alkylation catalysts.

Therefore, ensuring high operational performance of the catalyst: activity in the alkylation reaction (estimated degree of conversion of isobutene X, wt.% And selectivity Sel _TMP ,% - mass fraction of the target fraction - trimethylpentanes (TMP) in the reaction product) in combination with high crushing strength (on an end face - P _■, and forming MPa - P _○, MPa), and abrasion resistance (. P _and mass%) becomes possible only when targeted synthesis with the following: the mechanical strength and the catalytic activity largely determined by the chemical and phase composition, acidity and pore structure and the conditions of their creation, that is, are multifactorial and complex dependencies.

A known patent of the Russian Federation 2289477 [1], describing a method for producing an alkylation catalyst with increased strength (coefficient of resistance to cracking with a knife above 2.0 kg / mm diameter) and high rates of activity and selectivity. This is achieved by mixing a pentasil-type zeolite in which sodium cations are exchanged sequentially for ammonium, calcium or magnesium cations with a binder. As a binder, aluminum hydroxide of a pseudoboehmite structure with the addition of an inorganic acid to a pH of 2 ÷ 4 is used. The molded mass is characterized by the magnitude of the losses during calcination of the SPP = 35 ÷ 45 wt. %, and heat treatment is carried out in one to three steps.

However, the patent [1] relates to the preparation of catalysts for the alkylation of benzene with ethylene in order to obtain ethylbenzene. Reproduction of the catalyst preparation method and evaluation of the characteristics of the obtained solid catalyst during the alkylation of isobutane with isobutene showed its lack of activity and selectivity, respectively, X = 72% and Sel _TMP = 59%. Hereinafter, the indicated characteristics of the catalyst were evaluated by the results of the alkylation process under the following conditions: volume ratio of isobutane / isobutene - 19/1; pressure in the feed line - 6 bar; feed temperature - 20 ° C; volumetric feed rate - 3 h ^-1 ; reactor parameters: - reactor type - flow-through, volume of catalyst backfill fraction 1-2 mm - 15 cm ³ ; the temperature in the catalyst bed is 80 ° C, the pressure in the reactor is 6 ati; sampling frequency - 30 min, the duration of the feed is 4 hours. The activity was evaluated by the degree of conversion of isobutene:

и

, соответственно, начальная и конечная концентрации изобутена в реакционной смеси. Селективность Sel_ТМП - селективность по триметилпентанам (ТМП) рассчитывали по формуле:Where

and

, respectively, the initial and final concentration of isobutene in the reaction mixture. Sel selectivity _TMP - selectivity for trimethyl pentanes (TMP) was calculated by the formula:

where C _{TMP prod} - concentration of TMP in products; C _prod - concentration of products.

The indicators of the mechanical strength of the granules amounted to:

- Abrasion _{resistance, and} P = 65 wt. %, determined, hereinafter, according to GOST 16188 and calculated by the formula: P _and = 100 · (m _con / m _ref ), wt. %, where m _kon and m _ref are the mass of granules of the target fraction, respectively, after abrasion under the conditions of GOST and the original - before exposure.

- Crush strength along the end face P _■ = 5.2 MPa and along the generatrix P _○ = 2.4 MPa, determined hereinafter on the MP-2 device.

- P _■ - crushing along the end face of a cylindrical granule with equal diameter d and height h = d; the cylindrical granule is vertically located and the breaking load F _{i is} applied to the cross-sectional area of the granule equal to 0.785d ² and P _■ = F _i / 0.785d ² ;

- P _○ - crushing along the forming granules with equal diameter d and height h = d; while the cylindrical granule is horizontal and the breaking load is applied to the longitudinal sectional area of the granule equal to dh and P _○ = F _i / dh.

The average value for a sample of 26 granules is taken as the result of the determination.

The known method for producing a catalyst and a heterogeneous catalyst made in accordance with the patent [1] have the following disadvantages.

Firstly, insufficient activity and selectivity in the alkylation reaction of isobutane with isobutene.

Secondly, only a satisfactory strength of the granules along the end face P _■ and 2 times lower - along the generatrix P _○ ; abrasion resistance P _and - less than 70 wt. % accepted as satisfactory for the catalysts. A sharp difference in the values of the mechanical crushing strength in mutually perpendicular directions - along the end face P _■ and along the generatrix P _{○ of the} granule - is an indicator of the anisotropy of the solid and indicates the presence of significant attenuating internal stresses in its structure. They appear in the conditions of abrasive loads.

Known heterogeneous catalyst for producing gasoline alkylate, protected by RF patent No. 2384366 [2]. The invention relates to a solid heterogeneous superacid catalyst for producing gasoline alkylate by contacting a liquid mixture of isobutane and butenes with this catalyst, which is a porous composition from a template substrate consisting of particles of an "expanded" graphite, cerium (III) nitrate, intercalated with a mixture of acids and hexahydrate, possessing nanosized pores, and inorganic acid based on zirconium metallosilicates promoted with zinc or nickel sulfates deposited on particles of such graphite or mixtures thereof, having the general formula: (ZrO ₂ · 17SiO ₂ ) · 0.5MSO ₄ , where M = Zn ²⁺ and / or Ni ²⁺ . The invention also relates to a method for producing gasoline-alkylate by alkylating isobutane with a mixture of butenes in the presence of the above catalyst at a temperature of from 50 to 70 ° C, a pressure of from 1.7 to 3.0 MPa, a molar ratio of isobutane-butenes of 15: 1, a volumetric feed rate raw materials from 6.4 to 8.5 g / ml _cat · h, and subsequent possible regeneration of the specified catalyst. The invention allows to increase the service life of the catalysts and increase their activity and selectivity. Data on the mechanical strength of the catalyst in the invention are not given. Reproduction of the solid catalyst in accordance with Example 2 of the patent description [2] and evaluation of the characteristics of the obtained sample by the above methods showed rather high activity and selectivity, respectively, X = 88.3% and Sel _TMP = 81.9%, and the mechanical strength of the granules amounted to: crushing strength along the end face P _■ = 3.0 MPa, crushing along the generatrix P _○ = 1.9 MPa, abrasion resistance P _and = 54 wt. %

Known heterogeneous catalyst and described in the examples of the patent [2] the method of its preparation has the following disadvantages.

Firstly, low rates of mechanical strength of the catalyst. The reasons for the lack of strength are the nature of the proposed catalyst carrier, a “template substrate” made of particles of “expanded” intercalated porous graphite, which has a low density and internal stresses that weaken the frame of a solid porous body, and also the method used for tabletting the catalyst by dry pressing, which does not provide, taking into account the conditions of the final heat treatment, the formation of solid and resistant to liquid reaction medium crystallization-condensation contacts between particles graphite.

Secondly, the complexity of the technology for the preparation of “expanded” graphite, which requires special devices.

In the patent of the Russian Federation No. 2313391 [3], the authors of the invention relating to the processes for producing the high-octane gasoline component during the alkylation of isobutane with the butane-butylene fraction on heterogeneous catalysts proposed a solid heterogeneous catalyst, which is a solid porous superacid based on zirconium, hafnium metallosilicates or mixtures thereof, promoted salts of doubly or triply charged metal cations with doubly charged anions, and having the general formula (EO ₂ · aSiO ₂ ) · b (M _c X _d ), where E = Zr, Hf or their mixtures, a = 17-34, b = 0 5 when c = 1 and d = 1, M = Ni ^2+, Zn ²⁺ ZrO ^2+, X = SO ₄ ^2-, ZrF ₆ ^2-; b = 0.1666 with c = 2 and d = 3, M = Sc ³⁺ , Y ³⁺ Ga ³⁺ , X = SO ₄ ^2- , and the coefficients a and b may deviate up or down relative to the indicated values 20% for coefficient “a” and 5% for coefficient “b”. A method is also claimed for producing a high-octane component of gasoline-alkylate automobile fuel by alkylating isobutane with an industrial butane-butene fraction in the presence of said catalyst at a temperature of 75 to 102 ° C, a pressure of 1.7 to 2.5 MPa, and a molar ratio of isobutane butenes of 10 to 15 , with a volumetric feed rate of 6.4 to 8.5 g / cm ³ cat · h and subsequent possible regeneration of the specified catalyst. EFFECT: high rates of conversion, alkylate yield, productivity and catalyst life. However, the invention does not provide data on the mechanical strength of the catalyst. Reproduction of the solid catalyst in accordance with Example 2 of the invention [3] and evaluation of the characteristics of the obtained sample by the above methods showed its high activity and selectivity, respectively, X = 86.8% and Sel _TMP = 81.5%, and the mechanical strength of the granules was : crushing strength along the end face P _■ = 4.2 MPa and along the generatrix - P _○ = 3.4 MPa, abrasion resistance P _and = 66 wt. %

The known catalyst and the method for its preparation described in the examples have the following significant disadvantages.

Firstly, low strength characteristics both in terms of crushing resistance (P _■ , P _○ ) and abrasion resistance (P _and ). The reasons for the lack of strength are the nature of the porous structure of the catalyst, represented mainly by macropores (according to the authors, 80-300 and 100-1000 nm for samples K2 and K3), which are known to be concentrators of internal stresses that weaken a solid porous body.

Secondly, the used method of tabletting the catalyst is by dry pressing, which does not provide, taking into account the conditions of the final heat treatment, the formation of crystallization-condensation contacts between the particles of the catalyst components that are strong and resistant to the liquid reaction medium.

The closest catalyst and the method of its preparation to the claimed are a solid heterogeneous catalyst for the process of alkylation of isoparaffin hydrocarbons with olefins and the method of its production described in patent [4] of the Russian Federation No. 2505357, cl. IPC B01J 37/30, B01J 29/08, B01J 29/12, C07C 2/58, publ. 01/27/2014 (prototype).

In [4], a method for producing an isobutane alkylation catalyst with olefins based on a NaNH ₄ Y type zeolite with a residual content of sodium oxide of not more than 0.8 wt% was proposed, in which the zeolite is impregnated with an aqueous solution of lanthanum nitrate, taken in an amount providing the lanthanum content in the final catalyst, 0.5% -6.0% wt., a suspension is obtained; the boehmite structure aluminum hydroxide powder is peptized with an acid solution to a pH of 1-3 and another suspension is obtained. Then both suspensions are mixed, evaporated to formability and molded into granules. After which the obtained granules are dried at room temperature, dried at 50-120 ° C for at least 5 hours and calcined at 150-500 ° C for at least 4 hours. In the particular case, after calcination, palladium chloride is applied to the catalyst. A method for alkylating isobutane with olefins in the presence of said catalyst is also provided. EFFECT: simplification and cheapening of the process of producing a catalyst.

The catalyst obtained according to [4] contains, in accordance with the following examples: a zeolite of the NaNH ₄ Y type (with a residual content of sodium oxide of not more than 0.8% by weight) - (64.0-79.5) wt. %; lanthanum - (0.5-6.0) wt. % and alumina - (20-30) wt. %, in a particular case - palladium - 0.2 wt. %, and has, according to the authors, the following characteristics: butylene conversion - 99-100%, selectivity for TMP - 63.1-71.2%. Unfortunately, there are no data on the mechanical strength of the catalyst in the patent. The stability indicators of the conversion and selectivity indicators are not given depending on the duration of the catalyst.

Reproduction of the catalyst preparation method in accordance with Example 4 of the invention [4] and evaluation of the characteristics of the obtained catalyst according to the above methods showed its high activity and selectivity in the alkylation of isobutane with isobutene, respectively, X = 92.6% and Sel _TMP = 77.2%. Assessment of the stability of the characteristics of X and Sel _TMP showed their decrease over 4 hours by 11-15%. The mechanical strength indicators of the granules were: crushing - P _■ = 5.4 MPa and P _○ = 3.1 MPa, abrasion - P _and = 71 wt. %

Known / prototype / method for producing a catalyst and a catalyst described in the examples of the patent, have the following significant disadvantages.

Firstly, the catalyst obtained by the prototype method is characterized by a low mechanical strength of the granules both for crushing and abrasion; the reason for this is the use of boehmite modification (aluminum trihydroxide Al (OH) ₃ ) as Al ₂ O ₃ -binding - aluminum hydroxide, which is not sufficiently reactive with peptizing acids and, therefore, is low (for example, compared with pseudoboehmite aluminum hydroxide modifications - with aluminum monohydroxide AlOOH · nH ₂ O) plasticizing properties that would contribute to the optimal packing of zeolite particles during molding and the formation of granules after heat treatment as the maximum possible number of contacts per contact section unit, as well as the high strength of single contacts. Namely, these factors are one of the main that form the strength properties of granules.

Secondly, the crushing strengths of the catalyst granules P _■ and P _○ differ by almost 2 times, which indicates the anisotropy of the formed porous structure and the presence of significant internal stresses, and this can cause granule destruction during regeneration.

Thirdly, the presence of the catalyst obtained by the prototype method, a noticeable tendency to decrease over 4 hours of work initially high activity and selectivity in the process of alkylation of isobutane with isobutene under experimental conditions. The reason may be the deposition of by-products - high molecular weight olefin hydrocarbons, which deactivate active centers and screen the cavity of the zeolite.

The objective of the invention is the development of a method of preparing a catalyst and an isobutane alkylation catalyst with isobutene with increased mechanical strength of the granules while maintaining high process performance - isobutene conversion and selectivity for trimethylpentanes with an increase in their stability during mining in the alkylation process.

The solution of the technical problem and the achievement of the technical result - improving the operational properties of a heterogeneous catalyst, which is expressed both in increasing the mechanical strength of the catalyst while ensuring high rates of its catalytic activity (degree of conversion of isobutene and selectivity for trimethylpentanes), and in increasing their stability during mining in the process alkylation, that is, improving the properties of the catalyst compared to the prototype is due to: 1) education with peptis tion oxynitrate pseudoboehmite alumina with nitric acid, are effective and plasticizing binders, combined total mass of ingredient composition forming reinforcing beads; 2) optimizing the packing of particles of zeolite, pseudoboehmite and zirconium oxide when they are introduced into the molding mass in the form of powders with a particle size of less than 40 microns, in total the entire ingredient composition of the molding mass and calcined catalyst granules that strengthen them; 3) reducing the internal stresses in the pellets, when introduced into the composition of the molding material of the reinforcing additives - mikroigolchatogo wollastonite - natural calcium silicate CaSiO ₃ aspect ratio l: d = (12-20): 1, with the length of the microneedles l <20 m, the reinforcing effect as a provider on the mass during molding and on the texture of the calcined catalyst granules, and in the aggregate of the entire ingredient composition, increasing their mechanical strength; 4) optimization of the balance of acid centers of the catalyst when introducing into its composition in certain proportions both protonized and lanthanum-substituted zeolite type U, and aluminum oxide, sulfated zirconium oxide, calcium silicate, which, together with the entire ingredient composition of the catalyst, ensured high rates its catalytic activity - isobutene conversion and trimethylpentane selectivity, and also increased their stability during mining in the process of alkylation.

The task is achieved by a process for preparing the catalyst of alkylation of isobutane with isobutene based on zeolite type NaNH ₄ Y with a residual sodium oxide content of not more than 0.8 wt. %, including the impregnation with stirring of the crystals of zeolite with an aqueous solution of lanthanum nitrate in an amount providing a lanthanum content in the zeolite of 3.0 wt. %, mixing the resulting suspension with a second suspension obtained by peptization with an aqueous solution of nitric acid to a pH of 1-3 aluminum hydroxide powder, granulating the molding mass, drying at room temperature for 18-24 hours, drying with a temperature rise of 2 degrees per minute and holding at 110 ± 10 ° C for at least 5 hours and annealing with a temperature increase of 10 degrees per minute and holding at 280 ± 10 ° C for at least 4 hours and at 510 ± 10 ° C for at least 4 hours; powders of zeolite and aluminum hydroxide of pseudoboehmite modification have a particle size of less than 40 microns, and a powder of sulfated tetragonal zirconium dioxide with a content of 5 wt. % (SO ₄ ) ₂ ^{2 -} and with particles smaller than 40 microns, as well as non-modified microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio l: d = (12-20): 1 and microneedle length l <20 microns, at the following mass ratio of components in the molding material,%: zeolite type NaNH ₄ Y with a residual sodium content of not more than 0.8 wt. % - (26.14-30.68), lanthanum nitrate (1.90-2.22), aluminum hydroxide (pseudoboehmite) - (14.88-19.40), sulfated zirconium oxide - (9.90-14 , 61) and microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio l: d = (12-20): 1 with a microneedle length l <20 μm - (1.13-2.30), nitric acid - (0, 44-0.57), water - up to 100.

The problem is also solved by a catalyst with increased mechanical strength, high catalytic activity - the degree of conversion of isobutene, selectivity for trimethylpentanes during their stabilization during mining. The catalyst includes a zeolite of the NaLaHY type with a residual sodium oxide content of not more than 0.8 wt. % and modified 3.0 wt. % lanthanum, aluminum oxide, characterized in that it further comprises a sulfated tetragonal zirconium oxide containing 5 wt. % (SO ₄ ) ₂ ^2- , and microneedle wollastonite is a natural calcium silicate CaSiO ₃ with a characteristic ratio l: d = (12-20): 1 and microneedle length l <20 μm, and the catalyst components are in the following weight ratio,% : zeolite of the type NaLaHY - (49-55), alumina - (22-30), sulfated zirconium oxide (18-25), calcium silicate - (2-4).

A significant difference of the invention is the use in the preparation of the catalyst molding material containing from 26.14 to 30.68 wt. % zeolite crystals of the NaNH ₄ Y type (with a residual sodium content of up to 0.8 wt.%) impregnated with an aqueous solution of lanthanum nitrate from 1.90 to 2.22 wt. % of its content in mass, and from 14.88 to 19.40 wt. % aluminum hydroxide peptized with nitric acid to a pH of 1-3, additionally from 9.90 to 14.61 wt. % sulfated tetragonal zirconia with a content of 5 wt. % (SO ₄ ) ₂ ^{2 -} and with particles smaller than 40 microns, as well as from 1.13 to 2.30 wt. % non-modified microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio l: d = (12-20): 1 and microneedle length l <20 μm, aluminum hydroxide is introduced into the molding mass in the modification of pseudoboehmite, unlike the boehmite in the prototype, and the particle size of the zeolite and aluminum hydroxide powders is less than 40 microns; molding material contains from 0.44 to 0.57 wt. % nitric acid, water - up to 100. In the prior art, a similar combination of coating suspension ingredients with the indicated mass ratio (%) was not found and the preparation of a catalyst with increased strength and high catalytic activity and an increase in their stability during mining during alkylation is due to the following .

The formation during peptization of pseudoboehmite with nitric acid of aluminum oxynitrates, which are effective plasticizing and astringents, in the aggregate of the entire composition of the molding material, reinforcing granules.

Optimization of the packing of particles of zeolite, pseudoboehmite and zirconium oxide when they are introduced into the molding mass in the form of powders with a particle size of less than 40 μm, in total the entire ingredient composition of the molding mass and calcined catalyst granules, strengthens them.

Reduction of internal stresses in granules when micro-needle wollastonite is added to the molding composition — natural calcium silicate CaSiO ₃ with a characteristic ratio l: d = (12–20): 1 with a microneedle length l <20 μm, which has a reinforcing effect on the mass during molding , and the texture of the calcined catalyst granules, in the aggregate of the entire ingredient composition, increases their mechanical strength.

Optimization of the balance of the Brandsted and Lewis acid sites of the catalyst when both U protonated and lanthanum-substituted zeolite and aluminum oxide, sulfated zirconium oxide, calcium silicate are introduced in certain ratios, which, together with the entire ingredient composition of the catalyst, provided high rates its catalytic activity - isobutene conversion and trimethylpentane selectivity.

Introduction to the composition of the molding material of the additive - microneedle wollastonite with a characteristic ratio l: d = (12-20): 1 with a microneedle length l <20 μm (i.e., to the calcined catalyst - calcium silicate additive), which has, on the one hand reinforcing effect on the texture of calcined catalyst granules and promoting the formation of transport pores, which facilitates the removal of reaction products from the pores, and on the other hand, due to its basicity it neutralizes the strongest acid centers, which together increases the stability of indicators in the process of alkylation by reducing the likelihood of deposition of high molecular weight olefin hydrocarbons that deactivate active centers and screen the cavity of the zeolite.

A significant difference of the invention is the formation of a catalyst containing ingredients in the following weight ratio,%: zeolite of the NaLaHY type (with a residual sodium content of less than 0.8 wt.% And lanthanum - 3 wt.%) - (49-55), alumina - (22-30), sulfated tetragonal zirconium oxide containing (5) wt. % (SO ₄₎ ^2, - (18-25), calcium silicate - (2-4).

In the prior art, a similar combination of ingredients with the indicated mass ratio (%) was not found; obtaining a catalyst with high strength, high catalytic activity and an increase in their stability during mining during the alkylation process is due to the following.

The interaction during drying and calcination of the granules of the ingredients of their composition and the formation of strong crystallization-condensation contacts between particles of zeolite, alumina, sulfated zirconium oxide, having sizes less than 40 μm, and particles of micro needle wollastonite distributed between them, having a characteristic ratio l: d = (12 -20): 1 with a microneedle length l <20 μm, the formation, due to packing of the aggregate of these particles, the texture of the catalyst with transport pores, facilitating the supply of raw materials and removal of the product reaction, as well as optimizing the balance of the Brandsted and Lewis acid catalyst centers in the aggregate of the entire ingredient composition, which ensured high rates of its catalytic activity — isobutene conversion and trimethylpentane selectivity.

Thus, the claimed combination of features is essential and corresponds to an inventive step.

The following examples illustrate the proposed technical solution, but in no way limit it.

The following materials are used as starting materials.

The NaNH ₄ Y zeolite with a residual sodium content of not more than 0.8 wt% was obtained by the method described in [5], dried at 120 ° C to a constant weight, and dispersed to give a powder of the target fraction of less than 40 μm.

The aluminum hydroxide of the pseudoboehmite modification AlO (OH) · nH ₂ O, dried at 110 ° C, after which n = 1.05, is crushed by a ball mill and dispersed to give a powder of the target fraction of less than 40 microns.

Sulphated tetragonal zirconium oxide with a content of 5 wt. % sulfate ion was obtained by the method described in [6], crushed in a ball mill and dispersed with the release of the target fraction powder of less than 40 microns.

Lanthanum nitrate La (NO ₃ ) ₃ * 6H ₂ O.

Mikroigolchaty wollastonite unmodified - natural calcium silicate CaSiO ₃ aspect ratio l: d = (12-20): 1 and a length of microneedles l <20 microns.

Nitric acid HNO ₃ - in the form of an aqueous solution with a concentration of 50 wt. % (When peptization of aluminum hydroxide with nitric acid, its consumption is characterized by the so-called peptization equivalent of Pe equal to the number of mg equivalents of HNO ₃ per 1 g of aluminum hydroxide in terms of Al ₂ O ₃ ; in examples 1-8, the value of Pe = 0, 8 mEq HNO ₃ / g Al ₂ O ₃ formed from pseudoboehmite upon calcination of the granules).

Distilled water.

Example 1

4.48 g of La (NO ₃ ) ₃ * 6H ₂ O salt is dissolved in 30.0 cm ^{3 of} distilled water, 46.56 g of NaNH ₄ Y zeolite powder with a residual Na ₂ O content of less than 0.8 wt. %, at room temperature, with thorough stirring for 10 min, a suspension of 1 is obtained. 41.89 g of pseudoboehmite structure aluminum hydroxide powder is peptized with a nitric acid solution prepared by mixing 2.14 g of HNO _{3 at a} concentration of 50 wt.%, with 30.0 cm ³ of distilled water (slurry 2). Suspensions 1, 2 are mixed with 17.0 g of sulfated tetragonal zirconium oxide powder with a particle size of less than 40 μm and 4.0 g of unmodified microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio of l: d = (12-20): 1 and microneedle length l <20 μm, as well as with 8.1 cm ^{3 of} distilled water; thoroughly homogenize the resulting molding material to uniform color and plasticity; the ratio of the ingredients in it is as follows, wt. %: zeolite type NaNH ₄ Y - 25.58; lanthanum nitrate - 1.85; pseudoboehmite - 20.0; sulfated zirconium oxide - 9.34; wollastonite (calcium silicate) - 2.20; nitric acid - 0.60; water - 41.73. The mass is formed into granules by extrusion through a die with a diameter of the forming channel of 1.5 mm The granules are dried at room temperature for 18-24 hours, dried with a temperature increase of 2 degrees per minute and exposure at 110 ± 10 ° C for at least 5 hours and calcined with a temperature increase of 10 degrees per minute, exposure at 280 ± 10 ° C for at least 4 h and at 510 ± 10 ° C for at least 4 hours

Get the catalyst of mass composition,%: zeolite type NaLaHY (containing up to 0.8 wt.% Sodium and 3.0 wt.% Lanthanum) - 48.0; aluminum oxide - 31.0; sulfated zirconia - 17.0; calcium silicate - 4.0.

Example 2

4.58 g of La (NO ₃ ) ₃ * 6H ₂ O salt is dissolved in 30.0 cm ^{3 of} distilled water, 47.53 g of NaNH ₄ Y zeolite powder with a residual Na ₂ O content of less than 0.8 wt. %, at room temperature, with thorough stirring for 10 min, a suspension of 1 is obtained. 40.54 g of pseudoboehmite structure aluminum hydroxide powder is peptized with a nitric acid solution prepared by mixing 2.06 g of HNO _{3 at a} concentration of 50 wt. % with 30.0 cm ^{3 of} distilled water (suspension 2). Suspensions 1, 2 are mixed with 18.0 g of sulfated tetragonal zirconium oxide powder with a particle size of less than 40 μm and 3.0 g of unmodified microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio of l: d = (12-20): 1 and microneedle length l <20 μm, as well as with 8.3 g of distilled water; thoroughly homogenize the resulting molding material to uniform color and plasticity; the ratio of the ingredients in it is as follows, wt. %: zeolite type NaNH ₄ Y - 26.14; lanthanum nitrate - 1.90; pseudoboehmite - 19.4; sulfated zirconia - 9.90; wollastonite (calcium silicate) - 1.65; nitric acid - 0.57; water - 40.44. The mass is molded, dried, dried and calcined under the conditions described in example 1.

Get the catalyst composition, wt. %: zeolite type NaLaHY (containing up to 0.8 wt.% sodium and 3.0 wt.% lanthanum) - 49.0; alumina -30.0; sulfated zirconium oxide - 18.0; calcium silicate - 3.0.

Example 3

4.67 g of La (NO ₃ ) ₃ * 6H ₂ O salt is dissolved in 30.0 cm ^{3 of} distilled water, 48.50 g of NaNH ₄ Y zeolite powder with a residual Na ₂ O content of less than 0.8 wt. %, at room temperature, with thorough stirring for 10 minutes, a suspension of 1 is obtained. 31.08 g of pseudoboehmite structure aluminum hydroxide powder is peptized with a nitric acid solution prepared by mixing 1.58 g of HNO _{3 with a} concentration of 50 wt. % with 25.0 cm ^{3 of} distilled water (suspension 2). Suspensions 1, 2 are mixed with 25.0 g of sulfated tetragonal zirconium oxide powder with a particle size of less than 40 microns and 2.0 g of unmodified microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio of l: d = (12-20): 1 and microneedle length l <20 μm, as well as with 5.2 cm ^{3 of} distilled water; thoroughly homogenize the resulting molding material to uniform color and plasticity; the ratio of the ingredients in it is as follows, wt. %: zeolite type NaNH ₄ Y - 28.35; lanthanum nitrate - 2.05; pseudoboehmite - 15.81; sulfated zirconium oxide - 14.61; wollastonite (calcium silicate) - 1.17; nitric acid - 0.46; water - 37.55. The mass is molded, dried, dried, calcined under the conditions described in example 1.

Get the catalyst of mass composition,%: zeolite type NaLaHY (containing up to 0.8 wt.% Sodium and 3.0 wt.% Lanthanum) - 50.0; aluminum oxide - 23.0; sulfated zirconium oxide - 25.0; calcium silicate -2.0.

Example 4

4.86 g of La (NO ₃ ) ₃ * 6H ₂ O salt is dissolved in 30.0 cm ^{3 of} distilled water, 50.44 g of NaNH ₄ Y zeolite powder with a residual Na ₂ O content of less than 0.8 wt. %, at room temperature, with thorough stirring for 10 minutes, a suspension of 1 is obtained. 33.78 g of pseudoboehmite structure aluminum hydroxide powder is peptized with a nitric acid solution prepared by mixing 1.92 g of HNO _{3 with a} concentration of 50 wt. % with 30.0 cm ^{3 of} distilled water (suspension 2). Suspensions 1, 2 are mixed with 21.0 g of sulfated tetragonal zirconium oxide powder with a particle size of less than 40 μm and 2.0 g of unmodified microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio of l: d = (12-20): 1 and microneedle length l <20 μm, as well as with 5.8 cm ^{3 of} distilled water; thoroughly homogenize the resulting molding material to uniform color and plasticity; the ratio of the ingredients in it is as follows, wt. %: zeolite type NaNH ₄ Y - 28.42; lanthanum nitrate - 2.06; pseudoboehmite - 16.56; sulfated zirconium oxide - 11.83; wollastonite (calcium silicate) - 1.13; nitric acid - 0.48; water - 39.52. The mass is molded, dried, dried and calcined under the conditions described in example 1.

Get the catalyst composition, wt. %: zeolite type NaLaHY (containing up to 0.8 wt.% sodium and 3.0 wt.% lanthanum) - 52.0; aluminum oxide - 25.0; sulfated zirconium oxide - 21.0; calcium silicate - 2.0.

Example 5

4.86 g of La (NO ₃ ) ₃ * 6H ₂ O salt is dissolved in 32.0 cm ^{3 of} distilled water, 50.44 g of NaNH ₄ Y zeolite powder with a residual Na ₂ O content of less than 0.8 wt. %, at room temperature, with thorough stirring for 10 minutes, a suspension of 1 is obtained. 29.73 g of pseudoboehmite structure aluminum hydroxide powder is peptized with a nitric acid solution prepared by mixing 1.52 g of HNO _{3 with a} concentration of 50 wt.% from 25.0 cm ³ distilled water (suspension 2). Suspensions 1, 2 are mixed with 26.0 g of sulfated tetragonal zirconium oxide powder with a particle size of less than 40 microns (without the addition of microneedle wollastonite), as well as with 3.3 cm ^{3 of} distilled water; thoroughly homogenize the resulting molding material to uniform color and plasticity; the ratio of the ingredients in it is as follows, wt. %: Type zeolite NaNH ₄ Y - 29,51; lanthanum nitrate - 2.14; pseudoboehmite - 15.14; sulfated zirconium oxide - 15.21; wollastonite (calcium silicate) - 0; nitric acid - 0.44; water - 37.56. The mass is molded, dried, dried and calcined under the conditions described in example 1.

Get the catalyst of mass composition,%: zeolite type NaLaHY (containing up to 0.8 wt.% Sodium and 3.0 wt.% Lanthanum) - 52.0; aluminum oxide - 22.0; sulfated zirconium oxide - 26.0; calcium silicate - 0.

Example 6

5.14 g of La (NO ₃ ) ₃ * 6H ₂ O salt is dissolved in 35.0 cm ^{3 of} distilled water, 53.35 g of NaNH ₄ Y zeolite powder with a residual Na ₂ O content of less than 0.8 wt. %, at room temperature, with thorough stirring for 10 minutes, a suspension of 1 is obtained. 29.73 g of pseudoboehmite structure aluminum hydroxide powder is peptized with a solution of nitric acid prepared by mixing 1.52 g of HNO _{3 with a} concentration of 50 wt. % with 25.0 cm ^{3 of} distilled water (suspension 2). Suspensions 1, 2 are mixed with 19.0 g of sulfated tetragonal zirconium oxide powder with a particle size of less than 40 μm and 4.0 g of unmodified microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio of l: d = (12-20): 1 and microneedle length l <20 μm, as well as with 3.2 cm ^{3 of} distilled water; thoroughly homogenize the resulting molding material to uniform color and plasticity; the ratio of the ingredients in it is as follows, wt. %: zeolite type NaNH ₄ Y - 30.68; lanthanum nitrate - 2.22; pseudoboehmite - 14.88; sulfated zirconium oxide - 10.92; wollastonite (calcium silicate) - 2.30; nitric acid - 0.44; water - 38.56. The mass is molded, dried, dried and calcined under the conditions described in example 1.

Get the catalyst composition, wt. %: zeolite type NaLaHY (containing up to 0.8 wt.% sodium and 3.0 wt.% lanthanum) - 55.0; aluminum oxide - 22.0; sulfated zirconium oxide - 19.0; calcium silicate - 4.0.

Example 7

5.23 g of La (NO ₃ ) ₃ * 6H ₂ O salt is dissolved in 38.0 cm ^{3 of} distilled water, 54.32 g of NaNH ₄ Y zeolite powder with a residual Na ₂ O content of less than 0.8 wt. %, at room temperature, with thorough stirring for 10 minutes, a suspension of 1 is obtained. 28.38 g of pseudoboehmite structure aluminum hydroxide powder are peptized with a nitric acid solution prepared by mixing 1.44 g of HNO _{3 with a} concentration of 50 wt. % with 25.0 cm of distilled water (suspension 2). Suspensions 1, 2 are mixed with 18.0 g of sulfated tetragonal zirconium oxide powder with a particle size of less than 40 μm and 5.0 g of unmodified microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio of l: d = (12-20): 1 and microneedle length l <20 μm, as well as with 6.2 cm of distilled water; thoroughly homogenize the resulting molding material to uniform color and plasticity; the ratio of the ingredients in it is as follows, wt. %: zeolite type NaNH ₄ Y - 30.24; lanthanum nitrate - 2.19; pseudoboehmite - 13.75; sulfated zirconium oxide - 10.02; wollastonite (calcium silicate) - 2.78; nitric acid - 0.40; water 40.62. The mass is molded, dried, dried and calcined under the conditions described in example 1.

Get the catalyst of mass composition,%: zeolite type NaLaHY (containing up to wt. 0.8% sodium and 3.0 wt.% Lanthanum) - 56.0; aluminum oxide - 21.0; sulfated zirconium oxide - 18.0; calcium silicate - 5.0.

Example 8

5.23 g of La (NO ₃ ) ₃ * 6H ₂ O salt is dissolved in 40.0 cm ^{3 of} distilled water, 54.32 g of NaNH ₄ Y zeolite powder with a residual Na ₂ O content of less than 0.8 wt. %, at room temperature, with thorough stirring for 10 minutes, a suspension of 1 is obtained. 35.14 g of pseudoboehmite structure aluminum hydroxide powder are peptized with a nitric acid solution prepared by mixing 1.78 g of HNO _{3 with a} concentration of 50 wt. % with 30.0 cm ^{3 of} distilled water (suspension 2). Suspensions 1, 2 are mixed with 17.0 g of sulfated tetragonal zirconium oxide powder with a particle size of less than 40 μm and 1.0 g of unmodified microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio of l: d = (12-20): 1 and microneedle length l <20 μm, as well as with 1.9 cm ^{3 of} distilled water; thoroughly homogenize the resulting molding material to uniform color and plasticity; the ratio of the ingredients in it is as follows, wt. %: Type zeolite NaNH ₄ Y - 29,49; lanthanum nitrate - 2.13; pseudoboehmite - 16.60; sulfated zirconium oxide - 9.23; wollastonite (calcium silicate) - 0.54; nitric acid - 0.48; water - 41.12. The mass is molded, dried, dried and calcined under the conditions described in example 1.

Get the catalyst of mass composition,%: zeolite type NaLaHY (containing up to 0.8 wt.% Sodium and 3.0 wt.% Lanthanum) - 56.0; aluminum oxide - 26.0; sulfated zirconia - 17.0; calcium silicate - 1.0.

The obtained catalyst samples in examples 1-8 are tested according to the above methods and determine their strength properties (indicators of abrasion resistance P _and , wt.%, Crushing strength at the end face P _■ , MPa, and crushing strength along the generatrix P _○ , MPa) and catalytic activity in the alkylation reaction of isobutane with isobutene (indicators of the degree of conversion of isobutene X,%, and selectivity for TMP Sel _TMP ,%). The results are shown in table 1. The results of similar determinations for a catalyst sample reproducing the prototype are also presented there.

Examples 1-8 illustrate the effect on the strength properties of the catalyst granules and the parameters of its catalytic activity their preparation conditions: increasing the content of zeolite in the molding composition NaNH ₄ Y (having a sodium content less than 0.8 wt% and having a particle size less than 40 .mu.m.) Of 25 , 58 to 29.49 wt. % and lanthanum nitrate from 1.85 to 2.13 wt. % with the introduction of 13.75-20.0 wt. % aluminum hydroxide pseudoboehmite modification (with a particle size of less than 40 microns and peptized with nitric acid based on 0.8 mEq HNO ₃ / g Al ₂ O ₃ ), 9.23-15.21 wt. % sulfated tetragonal zirconium oxide (with a particle size of less than 40 microns and a sulfate ion content of 5 wt.%), as well as 0-2.78 wt. % non-modified microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio l: d = (12-20): 1 and microneedle length l <20 μm; the content of nitric acid in the molding composition was 0.44-0.60% by weight, and the water content was 37.55-41.73 wt. %

The indicated conditions for the preparation of catalyst samples correspond to an illustration of the effect of an increase in the content of zeolite NaLaHY in the composition of the finished catalyst (with a sodium content of less than 0.8 wt.% And lanthanum - 3 wt.%) From 48.0 to 56.0 wt. %, with a content of 21.0-31.0 wt. % alumina, 17.0-26.0 wt. % sulfated tetragonal zirconium oxide and 0-5.0 wt. % calcium silicate. Other things being equal, the preparation of the catalyst samples obtained in accordance with Examples 1-8 is characterized by strength and activity indicators that vary in the following ranges of values:

Abrasion resistance P _and , wt. % - from 75.1 to 90.1.

End crushing strength P _■ , MPa - from 6.5 to 8.7.

Crushing strength along the generatrix P _○ , MPa - from 5.9 to 7.5.

The degree of conversion of isobutene X, wt. % (after 0.5 h / after 4 h) - from 89.3 / 79.8 to 95.7 / 91.0.

Selectivity for TMP Sel _TMP , wt. % (after 0.5 h / after 4 h) - from 76.1 / 69.6 to 86.9 / 81.2.

The relevant indicators for the prototype sample are:

Abrasion resistance P _and , wt. % - from 71.0.

End crushing strength P _■ , MPa - from 5.4.

Crushing strength along the generatrix P _○ , MPa - from 3.1.

The degree of conversion of isobutene X, wt. % (after 0.5 h / after 4 h) - 92.6 / 83.4.

Selectivity for TMP Sel _TMP , wt. % (after 0.5 h / after 4 h) - 77.2 / 67.3.

The measurement results presented in the table showed that the samples of examples 2, 3, 4, 6, prepared by the claimed method and having the inventive ingredient composition of the catalyst exceed the prototype in terms of strength and catalytic activity and their stability during the alkylation of isobutane with isobutene under test conditions. Going beyond the claimed limits of the method of preparation of the catalyst and the ingredient composition of the catalyst (examples 1, 5, 7 and 8) lead to the deterioration of one or more indicators of achievement of the claimed technical result.

Thus, the inventive method can significantly increase the mechanical strength of the catalyst at high catalytic activity, characterized by the conversion of isobutene and selectivity for trimethylpentenes, and to increase the stability of these indicators when working out the catalyst during the alkylation process by using a molding composition of a certain composition, additionally containing sulfated tetragonal zirconia and microneedle wollastonite unmodified with a characteristic ratio l: d = (12-20 ): 1 and a microneedle length l <20 μm, also due to the use of zeolite, sulfated zirconia, aluminum hydroxide powders with a particle size of less than 40 μm, and aluminum hydroxide - pseudoboehmite modification, resulting in a mechanically strong catalyst of a certain composition, additionally containing sulfated tetragonal zirconia and calcium silicate, which is highly effective and stable in the process of alkylation of isopentane with isopentenes.

Information sources

1. RF patent No. 2289477.

2. RF patent No. 2384366.

3. RF patent No. 2313391.

4. RF patent No. 2505357.

5. P.P. Shiriazdanov, U.S. Rysaev, S.A. Akhmetov, A.P. Turanov, Yu.V. Morozov, E.A. Nikolaev "Petrochemistry", 2009, t. 49, No. 1, p. 90-93.

6. A.V. Lavrenov. Alkylation of isobutane with butenes on zirconium sulfate catalysts. Diss. for a job. student Ph.D. Tomsk, 2004

Claims (2)

1. A method of producing an isobutane alkylation catalyst with isobutene based on a NaNH ₄ Y type zeolite with a residual sodium oxide content of not more than 0.8 wt.%, Comprising impregnating zeolite crystals with an aqueous solution of lanthanum nitrate in an amount providing a zeolite content of 3.0 wt.% lanthanum, mixing the resulting suspension with a second suspension obtained by peptization with an aqueous solution of nitric acid to a pH of 1-3 aluminum hydroxide powder, granulation of the molding material, drying at room temperature for 18-24 hours, drying with a temperature rise of 2 degrees per minute and exposure at 110 ± 10 ° C for at least 5 hours and calcination with a temperature rise of 10 degrees per minute, exposure at 280 ± 10 ° C for at least 4 hours and at 510 ± 10 ° C at least 4 hours, characterized in that the pseudoboehmite modification zeolite and aluminum hydroxide powders have a particle size of less than 40 microns, and sulfated tetragonal zirconia powder with a content of 5 wt.% Is additionally added to the molding mass with stirring $${\left(S{O}_{\mathrm{four}}\right)}_2^{2-}$$

and with particles smaller than 40 microns, as well as unmodified microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio l: d = (12-20): 1 and microneedle length l <20 microns, with the following mass ratio of components in the molding mass, %: zeolite of the type NaNH ₄ Y (26.14-30.68), lanthanum nitrate (1.90-2.22), aluminum hydroxide (pseudoboehmite) (14.88-19.40), sulfated zirconia (9, 90-14.61) and microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio l: d = (12-20): 1 with a microneedle length l <20 μm (1.13-2.30), nitric acid (0 , 44-0.57), water up to 100. 2. The catalyst prepared according to claim 1, comprising a zeolite of the NaLaHY type with a residual content of sodium oxide of not more than 0.8 wt.% And a modified 3.0 wt.% Of lanthanum, alumina, characterized in that it further comprises sulfated tetragonal zirconia containing 5 wt.% sulfate ion, and microneedle wollastonite - natural calcium silicate CaSiO ₃ with a characteristic ratio l: d = (12-20): 1 and a microneedle length l <20 μm, and the catalyst components are in the following weight ratio, %: zeolite type NaLaHY (49-55), alumina (22-30), sul fattened zirconium oxide (18-25), calcium silicate (2-4).