RU2482917C1 - Method of producing heterogeneous catalyst for producing valuable and energy-saturated gasoline components - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: production of a heterogeneous catalyst for producing valuable and energy-saturated gasoline components by alkylating isobutane with olefins based on a NaNHY zeolite with residual content of sodium oxide of not more than 0.8 wt %, involving treating the zeolite with aqueous solution of a lanthanum salt, extrusion moulding, drying and calcining the obtained catalyst, wherein the zeolite is treated with aqueous lanthanum nitrate solution taken in an amount which ensures content of lanthanum in the end catalyst of 0.5-3.5 wt %; said treatment is carried out at 90-135°C and saturated vapour pressure; after treating with aqueous lanthanum nitrate solution, the zeolite is further treated with aqueous ammonium nitrate solution and a wet cake is obtained; said cake is mixed with another wet cake obtained from binder - aluminium hydroxide with a boehmite structure, which is peptised at pH 1-4 with a solution of a mineral or organic acid; the obtained mixture is evaporated; after moulding, the extruded articles are cured; drying is carried out at 120°C for 5 hours; calcination is carried out first at 300°C for 1.5 hours and then at 500°C for 2.5 hours; after calcination, palladium chloride is deposited on the catalyst, said palladium chloride being dissolved while heating in 25% ammonia solution and taken in an amount which ensures content of palladium in the finished catalyst of 0.05-0.3 wt %, and the catalyst is cured again at room temperature, dried at 120°C and cured at 500°C for 3 hours.EFFECT: cheap method of producing the catalyst is disclosed.2 cl, 1 tbl, 8 ex

Description

The invention relates to a technology for the production of catalysts and can be used for the alkylation of isoparaffin hydrocarbons with olefins in the oil refining and petrochemical industries in order to obtain alkylbenzene.

Alkylbenzene is a mixture of energetically saturated hydrocarbons (mainly trimethylpentanes and dimethylhexanes) with an octane rating of at least 93 by the motor method. They are used to increase the detonation resistance of gasolines. Isoparaffins (alkylbenzene, alkylate) obtained in the process of isobutane alkylation with olefins are characterized by the following main indicators:

- high octane numbers - 93 ÷ 94 by the motor method, 96 ÷ 99 by the research method;

- do not contain aromatic and unsaturated hydrocarbons, sulfur and oxygen compounds;

- have an even octane characteristic in terms of boiling points in the range of 40 ÷ 200 ° C.

Such indicators make it possible to consider alkylbenzene the most valuable component of automotive fuel, given the global trend of a decrease in the content of aromatic hydrocarbons in gasoline.

At present, both in Russia and in the world there is no production of alkylbenzene on heterogeneous catalysts. As catalysts for this process, liquid sulfuric or hydrofluoric acid is used in industry, which is associated with operational and environmental problems. Therefore, the task of developing an effective heterogeneous catalyst for the process of alkylation of isoparaffin hydrocarbons with olefins is very urgent.

A known method of producing a catalyst for the alkylation of isoparaffin hydrocarbons with olefins by ion exchange of zeolite granules of the type of faujasite, molded with 30% aluminum oxide to calcium cations, rare earth elements, ammonium. The degree of exchange for the rare-earth elements of the obtained sample is 47-50%, for the ammonium group - 14% [USSR Author's Certificate No. 507350, cl. B01J 21/16, 1972].

The disadvantage of this method of preparation of the catalyst is the preparation of a catalyst with low activity and selectivity in the alkylation reaction of isoparaffin hydrocarbons with butylenes and propylene. The yield of alkylate does not exceed 60-70 wt.% Of the missed butylenes, and the content of saturated hydrocarbons in the alkylate is 75-80%.

A known method of producing a catalyst for the alkylation of isoparaffin hydrocarbons with olefins by ion exchange of a faujasite type zeolite with aqueous solutions of calcium salts, rare earth elements, ammonium at a temperature of 150-220 ° C and saturated vapor pressure. The yield of alkylate in the presence of such a catalyst increases to 85%, with the conversion of olefins 88-93% [USSR author's certificate No. 936991, cl. B01J 37/30, B01J 29/08, 1982].

The disadvantage of this method is the high consumption of rare earth elements for ion exchange of the initial sodium form of faujasite.

A known method of producing a catalyst for producing valuable and energy-rich components of gasolines by alkylating isobutane with olefins, which is zeolite Y with a molar ratio of SiO ₂ / Al ₂ O ₃ = 4.5-5, in which sodium cations are replaced by NH ₄ ⁺ cations to the extent exchange of 95% and ions of rare earth elements up to 60% of the exchange capacity, including contact of the zeolite with aqueous solutions of salts of polyvalent metals, drying, molding with the addition of a binder [US Patent No. 3549557, class. 252-455, publ. 1970]. Alkylation of isobutane with butene-1 with a ratio of 20: 1 in the reaction mixture was carried out at an olefin feed rate of 0.05 h ^-1 , a temperature of 38 ° C and a pressure of 34 atm. After 6 hours of operation, an alkylate is obtained with a relatively high yield of 185%, counting on butene-1. The content of the C ₈ fraction in the alkylate is about 70%, and the content of trimethyl pentanes in it is about 80%.

The disadvantage of this method is the relatively high consumption of rare-earth elements for carrying out ion exchange of zeolite, as well as unacceptably low load on olefins and at the same time low stability of its operation: after 5-6 hours of operation, the content of unsaturated compounds in alkylate is 10-20%.

A known method of producing a catalyst described in [US Patent No. 3549557, class. 252-455, publ. 1970], according to which the initial HNaY zeolite with a molar ratio of Na ₂ O / Al ₂ O ₃ = 0.31 and SiO ₂ / Al ₂ O ₃ = 5.5 in order to remove residual sodium is initially subjected to ion exchange for ammonium cations from 2M solution of ammonium nitrate at a temperature of 100 ° C for 2 hours. Then a 3-fold ion exchange is carried out for lanthanum cations, each time using a fresh solution of lanthanum nitrate, at a temperature of 100 ° C for 2 hours, the result is a zeolite with the formula: H _26.4 La _8.4 Na _0.95 Al _{52, 6} Si _139.4 O ₃₈₄ , for which the physicochemical properties are studied and tested in the alkylation reaction of isobutane with butylenes.

The disadvantage of this method of producing a catalyst is the large number of operations to obtain a catalyst of the required composition, as well as the high consumption of lanthanum (fresh solution is used each time) during ion exchange of zeolite.

There is also known a method of producing a catalyst in which a polycation-decationized form of zeolite Y, modified with metals of group VIII of the elements, is obtained by ion exchange of a NaY zeolite with a molar ratio of SiO ₂ / Al ₂ O ₃ = 4.0 to ammonium cations to a residual Na ₂ O content of less than 2 , 0 wt.% [PP Shiryazdanov, U.S. Sh. Rysaev, S. A. Akhmetov, A. P. Turanov, Yu. V. Morozov, E. A. Nikolayev "Petrochemistry", 2009, vol. 49 No. 1 , p.90-93]. The obtained ultra-stable form of zeolite Y is subjected to ion exchange for calcium cations, then ion exchange for rare-earth cations, then modified in a solution of nickel or cobalt salts. The thus obtained zeolite was tested in the reaction of alkylation of isobutane with butenes at a temperature of 50-90 ° C, pressure 1.3-2.0 MPa, against paraffin / olefin = 1.10, the volume hourly space velocity of 0.8-1.2 h ^{- 1} . Moreover, the selectivity for hydrocarbons C ₈ reached 83 wt.%.

The disadvantage of the catalyst and the method of carrying out the alkylation reaction using it is the low volumetric feed rate: with a paraffin / olefin ratio of 10/1 and a feed volumetric rate of 0.8-1.2 h ^-1, the feed rate of olefins will be no more than 0, 09 h ^-1 , which from a practical point of view is uneconomical, since it will require the use of reactors with a very large catalyst load.

1. The closest in technical essence and the achieved result is a method of producing a catalyst for producing valuable and energy-rich components of gasolines by alkylating isobutane with C ₂ ÷ C ₄ olefins based on a faujasite type zeolite described in [SU 1309383, B01J 29/12, C07B 37 / 00, 10.20.1996]. According to a known technical solution, the catalyst has the following composition, wt.%: Sodium oxide 0.26-0.8; rare earth oxide 12.0-20.0; calcium oxide 0.8-4.2; platinum or palladium oxide 0.02-1.2; aluminum oxide and silicon dioxide - the rest. The method includes treating zeolite with an aqueous solution of an industrial mixture of rare earth elements, including lanthanum salts, molding, treating with aqueous solutions of ammonium nitrate and palladium salts, drying and calcining. Testing of the catalyst during the alkylation of isobutane with ethylene at 90 ° C, a feed rate of 1.3 h ^-1 and a duration of 7 h shows an alkylate yield of 190 ÷ 210 wt.%.

The disadvantage of the proposed method is the low selectivity of the catalyst for the target product Σiso-C ₈ (total isooctanes) - 67.4 wt.% During the alkylation of isobutane with olefins, in particular butenes.

A common disadvantage of obtaining heterogeneous catalysts according to the methods described above is the complexity and high cost of the described methods associated with:

- the use of significant amounts of lanthanum, a rare-earth element (up to 10-15% per catalyst), the cost of which has recently grown sharply (by an order of magnitude);

- the need to use high temperatures in ion exchange - up to 220 ° C;

- the presence of a large number of operations with solutions.

The objective of the present invention is to develop a cost-effective and simple in comparison with the prototype method of producing a catalyst with activity, selectivity for hydrocarbons iso-C ₈ and the stability of the work is not inferior, and in some cases exceeding the corresponding figures for the prototype.

The problem is solved in that a method for producing a heterogeneous catalyst for producing valuable and energetically saturated gasoline components by alkylating isobutane with olefins based on a NaNH ₄ Y type zeolite with a residual sodium oxide content of not more than 0.8 wt.%, Including treating the zeolite with an aqueous salt solution, is proposed. lanthanum, drying and calcining the obtained catalyst, in which the zeolite is first treated with an aqueous solution of lanthanum nitrate, taken in an amount that provides the content of lanthanum oxide in the final . Atalizatore 0.5% -3.5% by weight, said treatment is carried out at 90-135 ° C and a saturated vapor pressure, and treated with an ammonium nitrate solution - obtained wet cake; the boehmite structure aluminum hydroxide powder is peptized with a solution of mineral or organic acid to pH 1-4 and another wet cake is obtained, then both wet cake are mixed, evaporated, if necessary, to formability and formed by extrusion into granules, after which the obtained granules are dried at room temperature temperature, dried at 120 ° C for 5 hours and first calcined at a temperature of 300 ° C for 1.5 hours, and then at 500 ° C for 2.5 hours, after calcination, palladium chloride is applied to the catalyst, a solution when heated in a 25% ammonia solution and taken in an amount providing a palladium content in the finished catalyst of 0.05-0.3 wt.% and the catalyst is again dried at room temperature, dried at 120 ° C and calcined at 500 ° C for 3 hours.

As a mineral or organic acid, nitric acid or oxalic acid or acetic acid is used.

The technical result consists in simplifying and reducing the cost of the method of producing the catalyst with its high activity and selectivity for hydrocarbons iso-C ₈ :

- reduced lanthanum content (about 8 times);

- excluded the stage of ion exchange with a solution of calcium nitrate;

- reduced the number of ion exchanges.

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

Example 1

200 g (in terms of the substance calcined at 600 ° C) pellets of ultra-stable type Y zeolite in ammonium form, the production method of which is described, for example, in [PP Shiryazdanov, U.S. Sh. Rysaev, S. A. Akhmetov, A. P. Turanov, Yu.V. Morozov, E. A. Nikolaev “Neftekhimiya”, 2009, vol. 49 No. 1, pp. 90-93] with a residual sodium oxide content of not more than 0.8 wt.%, Loaded into the apparatus a stirrer, is poured lanthanum nitrate solution (concentration 7.5 g / dm ^3, the amount of solution 1 dm ^3), preheated to 130 ° C, allowed to stand 3 hours at constant stirring, cooled, discharged and filter yvayut from the mother liquor substantially free of lanthanum. Processing with lanthanum nitrate is carried out at a saturated vapor pressure.

Then, the obtained zeolite is washed with demineralized water (water vapor condensate).

Thus washed zeolite is again loaded into the apparatus with a stirrer, filled with a solution of ammonium nitrate with a concentration of NH ₄ NO _{3 of} 50 g / dm ³ and washing is carried out with demineralized water (condensate) to remove loosely bound lanthanum from the zeolite that is not fixed in the cation exchange positions of the zeolite. After washing with ammonium nitrate, the zeolite is squeezed from the mother liquor, washed with demineralized water (condensate) and the zeolite is obtained in the form of a wet cake (cake 1).

66.67 g (in terms of the substance calcined at 850 ° C) of the boehmite structure aluminum hydroxide powder with a solution of oxalic acid are peptized to pH = 2 (cake 2).

Thoroughly mix cakes 1 and 2, evaporate to formability and form into granules. The granules are dried at room temperature, dried at 120 ° C for 5 hours and calcined at 300 ° C for 1.5 hours and at 500 ° C for 2.5 hours.

0.27 dm ^{3 of a} solution containing 0.9 g of palladium chloride dissolved by heating in a 25% ammonia solution is applied to the calcined catalyst base by the method of residual moisture absorption, the catalyst is dried at room temperature, dried at 120 ° C, calcined at 500 ° C for 3 hours.

A catalyst is obtained with a content of 1.1% lanthanum oxide and 0.2% Pd.

The obtained catalyst sample was tested in the alkylation reaction of isobutane with olefins in a laboratory micropilot plant, at a temperature of 80 ° C, a pressure of 12.3 MPa, the ratio of isobutane: olefins in the feedstock 10: 1, the volumetric feed rate of the feedstock for olefins 0.15 h ^-1 , duration feedstock 8 hours. A mixture of butylenes is used as olefins. The test results are presented in table 1.

Example 2

200 g (in terms of the substance calcined at 600 ° C) pellets of ultra-stable type Y zeolite in the ammonium form described in [5] with a residual content of sodium oxide of not more than 0.8 wt.%, Loaded into the apparatus with a stirrer, filled with a solution lanthanum nitrate (concentration 3.4 g / dm ³ , the amount of solution 1 dm ³ ), heated to 90 ° C, kept for 6 hours with constant stirring, cooled, discharged and filtered from the mother liquor, practically free of lanthanum. Processing with lanthanum nitrate is carried out at a saturated vapor pressure.

Then, the obtained zeolite is washed with demineralized water (water vapor condensate).

Thus washed zeolite is again loaded into the apparatus with a stirrer, it is filled with a solution of ammonium nitrate with a concentration of NH ₄ NO _{3 of} 50 g / dm ³ and washing is performed to remove loosely bound lanthanum from the zeolite that is not fixed in the cation exchange positions of the zeolite. After washing with ammonium nitrate, the zeolite is squeezed from the mother liquor, washed with demineralized water (condensate) and the zeolite is obtained in the form of a wet cake (cake 1).

66.67 g (in terms of the substance calcined at 850 ° C) of the boehmite structure aluminum hydroxide powder with a solution of acetic acid were peptized to pH = 3 (cake 2).

Thoroughly mix cakes 1 and 2, evaporate to formability and form into granules. The granules are dried at room temperature, dried at 120 ° C for 5 hours and calcined at 300 ° C for 1.5 hours and at 500 ° C for 2.5 hours.

0.27 dm ^{3 of a} solution containing 1.13 g of palladium chloride dissolved by heating in a 25% ammonia solution is applied to the calcined catalyst base by the method of residual moisture absorption, the catalyst is dried at room temperature, dried at 120 ° C, calcined at 500 ° C for 3 hours.

A catalyst is obtained with a content of 0.5% lanthanum oxide and 0.25% Pd.

The obtained catalyst sample was tested in the alkylation reaction of isobutane with olefins in a laboratory micropilot plant, at a temperature of 80 ° C, a pressure of 12.3 MPa, the ratio of isobutane: olefins in the feedstock 10: 1, the volumetric feed rate of the feedstock for olefins 0.15 h ^-1 , duration feedstock 8 hours. A mixture of butylenes is used as olefins.

The test results are presented in table 1.

Example 3

200 g (in terms of the substance calcined at 600 ° C) pellets of ultra-stable type Y zeolite in the ammonium form described in [5] with a residual content of sodium oxide of not more than 0.8 wt.%, Loaded into the apparatus with a stirrer, filled with a solution lanthanum nitrate (concentration of 12.3 g / dm ³ , the amount of solution is 1 dm ³ ), heated to 120 ° C, incubated for 4 hours with constant stirring, cooled, discharged and filtered from the mother liquor, practically free of lanthanum. Processing with lanthanum nitrate is carried out at a saturated vapor pressure.

Then, the obtained zeolite is washed with demineralized water (water vapor condensate).

The zeolite thus washed is again loaded into the apparatus with a stirrer, filled with a solution of ammonium nitrate with a concentration of NH ₄ NO _{3 of} 50 g / dm ³ to remove loosely bound lanthanum from the zeolite that is not fixed in the cation exchange positions of the zeolite. After washing with ammonium nitrate, the zeolite is squeezed from the mother liquor, washed with demineralized water (condensate) and the zeolite is obtained in the form of a wet cake (cake 1).

66.67 g (in terms of the substance calcined at 850 ° C) of the boehmite structure aluminum hydroxide powder with a solution of nitric acid were peptized to pH = 2 (cake 2).

Thoroughly mix cakes 1 and 2, evaporate to formability and form into granules. The granules are dried at room temperature, dried at 120 ° C for 5 hours and calcined at 300 ° C for 1.5 hours and at 500 ° C for 2.5 hours.

0.27 dm ^{3 of a} solution containing 1.35 g of palladium chloride dissolved by heating in a 25% ammonia solution is applied to the calcined catalyst base by the method of residual moisture absorption, the catalyst is dried at room temperature, dried at 120 ° C, calcined at 500 ° C for 3 hours.

A catalyst is obtained with a content of 1.8% lanthanum oxide and 0.3% Pd.

The obtained catalyst sample was tested in the alkylation reaction of isobutane with olefins in a laboratory micropilot plant, at a temperature of 80 ° C, a pressure of 12.3 MPa, the ratio of isobutane: olefins in the feedstock 10: 1, the volumetric feed rate of the feedstock for olefins 0.15 h ^-1 , duration feedstock 8 hours. A mixture of butylenes is used as olefins.

The test results are presented in table 1.

Example 4

200 g (in terms of the substance calcined at 600 ° C) pellets of ultra-stable type Y zeolite in the ammonium form described in [5] with a residual content of sodium oxide of not more than 0.8 wt.%, Loaded into the apparatus with a stirrer, filled with a solution lanthanum nitrate (concentration 4.8 g / dm ³ , the amount of solution 1 dm ³ ), heated to 135 ° C, kept for 3 hours with constant stirring, cooled, discharged and filtered from the mother liquor, practically free of lanthanum. Processing with lanthanum nitrate is carried out at a saturated vapor pressure.

Then, the obtained zeolite is washed with demineralized water (water vapor condensate).

The zeolite thus washed is again loaded into the apparatus with a stirrer, filled with a solution of ammonium nitrate with a concentration of NH ₄ NO _{3 of} 50 g / dm ³ to remove loosely bound lanthanum from the zeolite that is not fixed in the cation exchange positions of the zeolite. After washing with ammonium nitrate, the zeolite is squeezed from the mother liquor, washed with demineralized water (condensate) and the zeolite is obtained in the form of a wet cake (cake 1).

66.67 g (in terms of the substance calcined at 850 ° C) of the boehmite structure aluminum hydroxide powder with a solution of nitric acid were peptized to pH = 3 (cake 2).

Thoroughly mix cakes 1 and 2, evaporate to formability and form into granules. The granules are dried at room temperature, dried at 120 ° C for 5 hours and calcined at 300 ° C for 1.5 hours and at 500 ° C for 2.5 hours.

0.27 dm ^{3 of a} solution containing 0.45 g of palladium chloride dissolved by heating in a 25% ammonia solution is applied to the calcined catalyst base by the method of residual moisture absorption, the catalyst is dried at room temperature, dried at 120 ° C, calcined at 500 ° C for 3 hours.

A catalyst is obtained with a content of 0.7% lanthanum and 0.1% Pd.

The obtained catalyst sample was tested in the alkylation reaction of isobutane with olefins in a laboratory micropilot plant, at a temperature of 80 ° C, a pressure of 12.3 MPa, the ratio of isobutane: olefins in the feedstock 10: 1, the volumetric feed rate of the feedstock for olefins 0.15 h ^-1 , duration feedstock 8 hours. A mixture of butylenes is used as olefins.

The test results are presented in table 1.

Example 5

200 g (in terms of the substance calcined at 600 ° C) pellets of ultra-stable type Y zeolite in the ammonium form described in [5] with a residual content of sodium oxide of not more than 0.8 wt.%, Loaded into the apparatus with a stirrer, filled with a solution lanthanum nitrate (concentration of 13.6 g / dm ³ , the amount of solution is 1 dm ³ ), heated to 100 ° C, kept for 6 hours with constant stirring, cooled, discharged and filtered from the mother liquor, practically free of lanthanum. Processing with lanthanum nitrate is carried out at a saturated vapor pressure.

Then, the obtained zeolite is washed with demineralized water (water vapor condensate).

The zeolite thus washed is again loaded into the apparatus with a stirrer, filled with a solution of ammonium nitrate with a concentration of NH ₄ NO _{3 of} 50 g / dm ³ to remove loosely bound lanthanum from the zeolite that is not fixed in the cation exchange positions of the zeolite. After washing with ammonium nitrate, the zeolite is squeezed from the mother liquor, washed with demineralized water (condensate) and the zeolite is obtained in the form of a wet cake (cake 1).

66.67 g (in terms of the substance calcined at 850 ° C) of the boehmite structure aluminum hydroxide powder with a solution of nitric acid were peptized to pH = 1 (cake 2).

Thoroughly mix cakes 1 and 2, evaporate to formability and form into granules. The granules are dried at room temperature, dried at 120 ° C for 5 hours and calcined at 300 ° C for 1.5 hours and at 500 ° C for 2.5 hours.

0.27 dm ^{3 of a} solution containing 0.23 g of palladium chloride dissolved by heating in a 25% ammonia solution is applied to the calcined catalyst base by the method of residual moisture absorption, the catalyst is dried at room temperature, dried at 120 ° C, calcined at 500 ° C for 3 hours.

A catalyst is obtained with a content of 2.0% lanthanum and 0.05% Pd.

The obtained catalyst sample was tested in the alkylation reaction of isobutane with olefins in a laboratory micropilot plant, at a temperature of 80 ° C, a pressure of 12.3 MPa, the ratio of isobutane: olefins in the feedstock 10: 1, the volumetric feed rate of the feedstock for olefins 0.15 h ^-1 , duration feedstock 8 hours. A mixture of butylenes is used as olefins.

The test results are presented in table 1.

Example 6

200 g (in terms of the substance calcined at 600 ° C) pellets of ultra-stable type Y zeolite in the ammonium form described in [5] with a residual content of sodium oxide of not more than 0.8 wt.%, Loaded into the apparatus with a stirrer, filled with a solution lanthanum nitrate (concentration of 17.9 g / dm ³ , the amount of solution is 1 dm ³ ), heated to 110 ° C, incubated for 5 hours with constant stirring, cooled, discharged and filtered from the mother liquor, practically free of lanthanum. Processing with lanthanum nitrate is carried out at a saturated vapor pressure.

Then, the obtained zeolite is washed with demineralized water (water vapor condensate).

Thus washed zeolite is again loaded into the apparatus with a stirrer, it is filled with a solution of ammonium nitrate with a concentration of NH ₄ NO _{3 of} 50 g / dm ³ and washing is performed to remove loosely bound lanthanum from the zeolite that is not fixed in the cation exchange positions of the zeolite. After washing with ammonium nitrate, the zeolite is squeezed from the mother liquor, washed with demineralized water (condensate) and the zeolite is obtained in the form of a wet cake (cake 1).

66.67 g (in terms of the substance calcined at 850 ° C) of the boehmite structure aluminum hydroxide powder with a solution of nitric acid were peptized to pH = 3 (cake 2).

Thoroughly mix cakes 1 and 2, evaporate to formability and form into granules. The granules are dried at room temperature, dried at 120 ° C for 5 hours and calcined at 300 ° C for 1.5 hours and at 500 ° C for 2.5 hours.

0.27 dm ^{3 of a} solution containing 0.68 g of palladium chloride dissolved by heating in a 25% ammonia solution is applied to the calcined catalyst base by the method of residual moisture absorption, the catalyst is dried at room temperature, dried at 120 ° C, calcined at 500 ° C for 3 hours.

A catalyst is obtained with a content of 2.6% lanthanum oxide and 0.15% Pd.

The obtained catalyst sample was tested in the alkylation reaction of isobutane with olefins in a laboratory micropilot plant, at a temperature of 80 ° C, a pressure of 12.3 MPa, the ratio of isobutane: olefins in the feedstock 10: 1, the volumetric feed rate of the feedstock for olefins 0.15 h ^-1 , duration feedstock 8 hours. A mixture of butylenes is used as olefins.

The test results are presented in table 1.

Example 7

200 g (in terms of the substance calcined at 600 ° С) pellets of ultra-stable type Y zeolite in the ammonium form described in [5] with a residual content of sodium oxide of not more than 0.8 wt.%, Loaded into the apparatus with a stirrer, filled with a solution lanthanum nitrate (concentration of 20.6 g / dm ³ , the amount of solution is 1 dm ³ ), heated to 135 ° C, incubated for 3 hours with constant stirring, cooled, discharged and filtered from the mother liquor, practically free of lanthanum. Processing with lanthanum nitrate is carried out at a saturated vapor pressure.

Then, the obtained zeolite is washed with demineralized water (water vapor condensate).

The zeolite thus washed is again loaded into the apparatus with a stirrer, filled with a solution of ammonium nitrate with a concentration of NH ₄ NO _{3 of} 50 g / dm ³ to remove loosely bound lanthanum from the zeolite that is not fixed in the cation exchange positions of the zeolite. After washing with ammonium nitrate, the zeolite is squeezed from the mother liquor, washed with demineralized water (condensate) and the zeolite is obtained in the form of a wet cake (cake 1).

66.67 g (in terms of the substance calcined at 850 ° C) of the boehmite structure aluminum hydroxide powder with a solution of nitric acid were peptized to pH = 3 (cake 2).

Thoroughly mix cakes 1 and 2, evaporate to formability and form into granules. The granules are dried at room temperature, dried at 120 ° C for 5 hours and calcined at 300 ° C for 1.5 hours and at 500 ° C for 2.5 hours.

0.27 dm ^{3 of a} solution containing 0.45 g of palladium chloride dissolved by heating in a 25% ammonia solution is applied to the calcined catalyst base by the method of residual moisture absorption, the catalyst is dried at room temperature, dried at 120 ° C, calcined at 500 ° C for 3 hours.

A catalyst is obtained with a content of 3.0% lanthanum and 0.1% Pd.

The obtained catalyst sample was tested in the alkylation reaction of isobutane with olefins in a laboratory micropilot plant, at a temperature of 80 ° C, a pressure of 12.3 MPa, the ratio of isobutane: olefins in the feedstock 10: 1, the volumetric feed rate of the feedstock for olefins 0.15 h ^-1 , duration feedstock 8 hours. A mixture of butylenes is used as olefins.

The test results are presented in table 1.

Example 8

200 g (in terms of the substance calcined at 600 ° C) pellets of ultra-stable type Y zeolite in the ammonium form described in [5] with a residual content of sodium oxide of not more than 0.8 wt.%, Loaded into the apparatus with a stirrer, filled with a solution lanthanum nitrate (concentration of 24.1 g / dm ³ , the amount of solution is 1 dm ³ ), heated to 135 ° C, incubated for 3 hours with constant stirring, cooled, discharged and filtered from the mother liquor, practically free of lanthanum. Processing with lanthanum nitrate is carried out at a saturated vapor pressure.

Then, the obtained zeolite is washed with demineralized water (water vapor condensate).

The zeolite thus washed is again loaded into the apparatus with a stirrer, filled with a solution of ammonium nitrate with a concentration of NH ₄ NO _{3 of} 50 g / dm ³ to remove loosely bound lanthanum from the zeolite that is not fixed in the cation exchange positions of the zeolite. After washing with ammonium nitrate, the zeolite is squeezed from the mother liquor, washed with demineralized water (condensate) and the zeolite is obtained in the form of a wet cake (cake 1).

66.67 g (in terms of the substance calcined at 850 ° C) of the boehmite structure aluminum hydroxide powder with a solution of nitric acid were peptized to pH = 3 (cake 2).

Thoroughly mix cakes 1 and 2, evaporate to formability and form into granules. The granules are dried at room temperature, dried at 120 ° C for 5 hours and calcined at 300 ° C for 1.5 hours and at 500 ° C for 2.5 hours.

0.27 dm ^{3 of a} solution containing 0.45 g of palladium chloride dissolved by heating in a 25% ammonia solution is applied to the calcined catalyst base by the method of residual moisture absorption, the catalyst is dried at room temperature, dried at 120 ° C, calcined at 500 ° C for 3 hours.

A catalyst is obtained with a content of 3.5% lanthanum and 0.1% Pd.

The obtained catalyst sample was tested in the alkylation reaction of isobutane with olefins in a laboratory micropilot plant, at a temperature of 80 ° C, a pressure of 12.3 MPa, the ratio of isobutane: olefins in the feedstock 10: 1, the volumetric feed rate of the feedstock for olefins 0.15 h ^-1 , duration feedstock 8 hours. A mixture of butylenes is used as olefins.

The test results are presented in table 1.

From the test results of the catalysts prepared according to examples 1-4, shown in table 1, it is obvious that in the main parameters: conversion, alkylate yield, iso-C ₈ hydrocarbon selectivity, the obtained catalysts are not inferior, and in some cases, exceed the corresponding parameters for the prototype.

Table 1 The test results of catalyst samples in the alkylation reaction of isobutane with olefins Example for example Butylene conversion, wt.% The yield of alkylate, wt.% ΣC ₅ -C ₇ , wt.% Σiso-C ₈ , wt.% ΣС ₉ , wt.% ΣТMP * ΣDMG ** ΣC ₈ non / id one one hundred 206 12,2 83.1 4.7 75.1 6.0 2 2 99 188 13.6 80.1 6.3 71.9 6.7 1,5 3 one hundred 198 11.6 83,2 5.2 74.7 6.4 2.1 four 99 196 13.6 80.3 6.1 72.9 6.5 0.9 5 one hundred 196 11.5 83.0 5.5 74,2 7.7 1,1 6 one hundred 196 12.3 81.9 5.8 72.7 7.8 1.4 7 one hundred 195 13.1 81.0 5.9 71.9 7.5 1,6 8 one hundred 192 13.9 80.0 5.5 70.8 7.6 1,6 prototype one hundred 182 13.7 80.0 6.3 70.8 6.6 6.2 TMP * - trimethylpentanes DMG ** - dimethylhexanes

Claims (2)

1. A method of producing a heterogeneous catalyst for producing valuable and energy-rich components of gasolines by alkylating isobutane with olefins based on a NaNH ₄ Y type zeolite with a residual sodium oxide content of not more than 0.8 wt.%, Comprising treating the zeolite with an aqueous lanthanum salt solution, extrusion molding , drying and calcining the obtained catalyst, characterized in that for the processing of zeolite using an aqueous solution of lanthanum nitrate, taken in an amount that ensures the content of lanthanum in the final catalysis ore 0.5-3.5 wt.%, the specified processing is carried out at 90-135 ° C and saturated vapor pressure, after treatment with an aqueous solution of lanthanum nitrate, the zeolite is further treated with an aqueous solution of ammonium nitrate and a wet cake is obtained, said cake is mixed with another wet a cake obtained from a binder - aluminum hydroxide of boehmite structure, peptized at a pH of 1 ÷ 4 with a solution of mineral or organic acid, the resulting mixture is evaporated, after molding the extrudates are dried, and drying is carried out at 120 ° C for 5 hours, and calcination, first at a temperature of 300 ° C for 1.5 hours, and then at 500 ° C for 2.5 hours, after calcination, palladium chloride dissolved in 25 % ammonia solution and taken in an amount providing a palladium content in the finished catalyst of 0.05-0.3 wt.% and the catalyst is again dried at room temperature, dried at 120 ° C and calcined at 500 ° C for 3 hours 2. The method according to claim 1, characterized in that as a mineral or organic acid using nitric acid or oxalic acid, or acetic acid.