CS222773B1 - Mexid crystallic catalyser for catalytic conversion of the hydrocarbons and method of making the same - Google Patents

Description

The present invention relates to a novel type of mixed crystalline catalysts effective for the catalytic conversion of hydrocarbons, or a mixture of hydrocarbons and a process for their preparation.

Catalytic conversion is understood to mean the conversion of hydrocarbons or a mixture of hydrocarbons taking place in the presence of a catalyst.

In many chemical processes, natural or synthetic aluminosilicates which are either amorphous or crystalline are used as catalysts. Crystalline aluminosilicates are in most cases more active than amorphous.

Synthetic mordenite or Y-zeolite aluminosilicates are among the most active catalysts in processes such as catalytic cracking, alkylations, dealkylations, disproporeionies, isomerizations and similar types of catalytic conversions occurring through the carbonium ion mechanism.

The present invention relates to a new type of mixed crystalline acid catalysts which are more active than raordenite or Y-zeolite catalysts.

The crystalline crystalline catalyst of the invention is a synthetic aluminosilicate, the crystalline structure of which comprises two perfectly mixed crystalline phases, a crystalline mordenite phase and a crystalline layered aluminosilicate phase. The structure of the layered aluminosilicate contains, in addition to silicon and aluminum, certain metals, the presence of which substantially increases the catalytic activity of the compound crystalline catalyst of the invention.

222 773

The mixed crystalline type catalysts of the present invention have a eummic emprioc formula of m SiO ₂ : n AlgO 3 ip QO: s DM, in which SiOg is silica,

Al ₂ ° 3 alumina,

QO oxide or metal oxides selected from the group consisting of copper, nickel, cobalt

D equivalent of anions selected from the group consisting of hydroxyl anion, fluoride anion, chloride anion, oxygen anion,

M equivalent of exchangeable cation or selected cations. ₍ from the group comprising cations of hydrogen, ammonium, alkali metals, alkaline earth metals, metals of the lanthanide group, with molar ratios

m my value from 2.71 to 64,81 n my value from 0.12 to 2.76 P my value from 0.01 to 3.29 8 my value from 0.23 to 1.82.

The catalysts of the invention are prepared by a hydrothermal synthesis of a mixture containing crystalline mordenite in an amount of from 0.74% by weight. % to 90.9 wt. and a reaction gel, the composition of which is represented by the formula a SiO ₂ : b Al 2 O 3: QO: d DM: e HgO, in which SiO _{2 is} silicon dioxide,

Al ₂ O ₃ alumina,

QO oxide or oxides of metal selected from the group consisting of copper, nickel, cobalt,

D equivalent of anion selected from the group consisting of hydroxy anion, fluoride anion, chloride anion, oxygen anion,

M equivalent of exchangeable cation, or cations selected from the group consisting of ammonium, alkali, alkaline earth,

HgO water and in molar ratios a has a value from 1.83 to 6.39 b has a value from 0.02 to 3.49 o has a value from 0.03 to 9.38

- 3 d has a value from 0.03 to 2.83 e has a value from 35 to 420. ^{222 773}

The hydrothermal synthesis is carried out in a pressure vessel, autoclave, at a temperature of from 160 ° C to 350 ° C at an autogenous pressure of water vapor for a period of from 3 to 200 hours. Effective mixing of said aqueous suspension is very advantageous and contributes to the reduction of the time required to form a synthetic mixture of crystalline aluminosilicate. After the synthesis is complete, the contents of the autoclave are cooled and the resulting crystalline product is separated from the mother liquor by filtration, sedimentation or centrifugation. The obtained synthetic crystalline aluminosilicate is preferably washed with distilled or demineralized water. It is preferable to subject the material synthesized in the presence of hydroxides or alkali metal salts or alkaline earths to ammonium hydroxide solutions or ammonium salt solutions such as nitrate, chloride, or ammonium acetate. Using other ammonium salts gives similar results. The crystalline material obtained before or after ionic ammonium salt solutions is also advantageously subjected to ion exchange with lanthanide group metal salt solutions, such as lanthanum nitrate, cerium, holmium, or a lanthanum metal nitrate solution. The ion-exchanged mixture of crystalline aluminosilicate according to the invention is dried and calcined at a temperature of from 250 ° C to 750 ° C. The calcined product in the H-form, decationized, or cationic decontaminated form is catalytically very effective in the conversion of hydrocarbons through a carbenium ion mechanism such as catalytic cracking, alkylation, disproporoionation, isomerization and the like.

The following examples illustrate the process of preparation, advantages and practical use of the catalysts of the invention, but without limiting the scope of the invention in any way. Example 1

To a flask containing 10 1, yield 640 g Si0 ₂ sol,

2000 ml of demineralized water and 253 g of aluminum chloride dissolved in a minimum of water. With vigorous stirring, a concentrated NH 4 OH solution was added until the pH of the mixture reached 10. The aluminum and silicon passed into a gel which was filtered and washed! demineralized water.

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The gel thus obtained was diluted with 1840 ml of demineralized water and 650 g of nickel acetate, 12% NaP solution and 30 g of NaOH dissolved in a minimum of water were added with stirring. The prepared reaction gel e1 was stirred for 3 hours and then 240 g of mordenite in the Na-form were added to it, the SiOg: AlgO4 molar ratio being 14. The thus prepared reaction mixture was further homogenized for 72 hours and then transferred to an autoclave where was subjected to a hydrothermal synthesis for 80 hours at 250 ° C and the autogenous water vapor pressure.

The hydrothermal synthesis product ea was filtered from the mother liquor and washed with 7000 ml of a 5% NH 4 OH solution, and then subjected to ion exchange solutions of ammonium acetate, and the product obtained was dried at 120 ° C. A portion of the dried product was calcined at 500 ° C for 8 hours. The calcined material ea thus obtained was designated as catalyst A.

The second part of the dried product ea was subjected to X-ray diffraction analysis and X-ray microanalysis. The results of these analyzes showed that it was a mixed material crystalline material comprising a mordenite phase and a layered aluminosilicate phase.

Example 2

In a 2 L container was added 120 g of the SiO? and an aluminum chloride solution containing 30.2 g of AlCl 2 · 6H 2 O. Under vigorous stirring, the resulting mixture was precipitated with a 14% NH 4 OH solution to pH 10. The resulting gel was filtered and washed with distilled water until a positive reaction to chloride ions disappeared in the filtrate.

The filtered gel was mixed with demineralized water to a volume of 1300 ml and a solution of 2.1 g NH 4 P, 11 ml concentrated NH 4 OH solution and 356 ml concentrated cobalt acetate solution was added with stirring. The resulting reaction gel was diluted with demineralized water and 87.6 g of synthetic mordenite in H-form was added with vigorous stirring and the molar ratio SiOg / AlgO2 was 20/1. The reaction mixture thus obtained was homogenized for 72 hours and then was subjected to hydrothermal synthesis in an autoclave at 280 ° C for 52 hours.

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The hydrothermal synthesis product was filtered from the mother liquor and dispersed in 3000 ml of demineralized water to which 180 g of NH4NO4 rats were added with vigorous stirring. at a concentration of 0.2 mol · L '\ ₀ p filtering, the crystalline material was dried at 110 ° C for 16 hours. The dried product was divided into two parts. The first portion was calcined at 485 ° C for 8 hours. The calcined material was designated as Catalyst B. The second portion of the dried product was subjected to X-ray. diffraction analysis, which showed it to be a mixed-structure crystalline aluminosilicate containing a mordenite phase and a layered aluminosilicate phase Example 3

A gel was obtained from the SiOg hydrosol and the aluminum chloride solution as in Example 1, to which 130 g of nickel acetate dissolved in 1300 ml of demineralized water was added,

8.3 g of NaOH dissolved in 50 ml of water and 10 g of NH4P. Finally, 64.2 g of copper acetate and 82 g of mordenite with a molar ratio of 33.2 SiOg / AlgOj were added under vigorous stirring. The reaction mixture thus prepared was homogenized for 5 days and then subjected to hydrothermal synthesis at 310 ° C for 38 hours.

The hydrothermal synthesis product was washed with distilled water and treated with ionic ammonium nitrate solutions, filtered and dried at 110 ° C. A portion of the dried product was calcined in air at 550 ° C for 10 hours. The calcined material was designated as Catalyst C.

Example 4

The catalytic activity of the catalysts of the invention was monitored using a conventional type flow apparatus on a toluene conversion model reaction, which is dealkylated to benzene in the reaction zone of the torus, disproportionated to benzene and xylenes, which is further isomerized. This model type of reaction provides data on dealkyfast-alkylation, disproportionation, and isomerization activity of the investigated catalysts, and is a well-established type of reaction for evaluating catalysts suitable for conversions through the carbenium ion mechanism.

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The reaction products were analyzed by gas chromatography. The toluene conversion was calculated according to the formula:

conversion of «100 -% unconverted toluene (% mol ·)

The results of the measurements of the catalytic activity of the catalysts according to the invention are summarized in Table 1 and also the catalytic activity of a cracking catalyst based on decationized zeolite Y and H-mordenite are compared.

Table 1

Catalyst Conversion (% mole)

Catalyst A 76.88 Catalyst B 82.31 Catalyst C 75.73 Y-zeolite 45,34 H-Mordenite 67.81

As shown experimentally in Table 1, the catalysts of the invention are highly active and 1 * 2 - 1.6 times outweigh the catalytic activity of the prior art catalysts.

Claims (2)

OBJECT OF THE INVENTION 222 773 1 · Zmesnekryštalický catalyst for the catalytic conversion of hydrocarbons extending mechanism of carbenium ions as catalytic cracking, alkylation, dealkylation, isomerization, disproportionation, characterized in that it is a crystalline synthetic aluminosilicate with mixed structure, the symmetry of the empirical formula is m _SiO2: n Algo ^ sp QO: with DM where it means SiOg silica AlgO ^ alumina, QO oxide or metal oxides selected from the group consisting of honey, nickel, cobalt, D equivalent of anion selected from the group consisting of hydroxyl anion, fluoride anion, chloride anion, oxygen anion, M equivalent of exchangeable cation, or cations selected from the group consisting of hydrogen, ammonium, alkali metals, alkaline earth metals, lanthanide group metals, and in molar ratios m has a value of 2.71 to 64.81 n having a value of 0.12 to 2 76 p has a value of 0.01 to 3.25 s having a value of 0.23 to 1.82, its mixed structure comprising a mordenite phase and a layered aluminosilicate phase. 2. A process for the preparation of a mixture of crystalline catalysts for the catalytic conversion of hydrocarbons according to claim 1, characterized in that the mixture contains crystalline mordenite in an amount of 0.74% to 90.9% by weight and a reaction gel of the formula a SiOg: AlgOj: c QO: d DM: e HgO 222 773 which means SiOg silica AlgOj aluminum oxide, QO oxide or metal oxides selected from the group consisting of honey, nickel, cobalt, D equivalent of anions selected from the group consisting of hydroxyl anion, fluoride anion, chloride anion, oxygen anion, M equivalent of exchangeable cation, or cations selected from the group consisting of ammonium, alkali, alkaline earth, HgO water, and in molar ratios a has a value from 1.63 to 6.35 b has a value from 0.02 to 3.45 c has a value from 0.03 to 5.38 d has a value from 0.03 to 2.83 e has a value of from 35 to 420, undergoes hydrothermal synthesis at a temperature of from 160 ° C to 350 ° C at an appropriate water vapor pressure for 3 to 200 hours, after which the material so prepared is subjected to ion exchange with ammonium hydroxide solutions or ammonium salt solutions and / or solutions containing metal cations of the lanthanide group and subsequent heat treatment by heating to a temperature in the range of from 250 ° C to 750 ° C, preferably from 350 ° C to 600 ° C.