CS219665B1 - Multicomplex catalyst for catalytic hydroconversion of hydrocarbons and its production processes - Google Patents

Abstract

The invention relates to a catalyst suitable for catalytic hydroconversion of hydrocarbons and a method of producing the same. The catalyst comprises three aluminosilicate components and a metal component. One aluminosilicate component is synthetic mordenite with a different molar ratio of SiO2 : Al2O3, the second is synthetic aluminosilicate containing metals increasing its catalytic activity and the third component is a material selected from the group comprising various types of natural and synthetic aluminosilicates. The metal component is selected from metals of the 6th and 8th groups of the periodic table. The method of producing the catalyst comprises homogenizing aluminosilicate components containing the metal component and heat treating them under specified conditions. The catalyst can be used in hydroconversions of hydrocarbons or mixtures of hydrocarbons such as hydrocracking, disproportionation, hydroisomerization, hydrodearomatization, dealkylation, transalkylation and the like.

Description

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BACKGROUND OF THE INVENTION The present invention relates to a novel type of multi-component difunctional catalysts effective for the catalytic hydroconversion of hydrocarbons or mixtures of hydrocarbons and the process for their preparation.

Hydroconversion means the conversion of hydrocarbons or mixtures of hydrocarbons occurring in the presence of hydrogen or hydrogen-containing gas. Hydroconversion of hydrocarbons contemplated by the invention relates to hydrocracking, disproportionation, hydrodearomatization, hydroisomerization, disalkylation, catalytic reforming, transalkylation, and similar processes of overfunctional catalysts.

More specifically, under the hydrocarbon hydrocarbon or hydrocarbon blend catalysts, hydroprocessing of petroleum distillates or hydrocarbon distillates obtained from coal processing is understood; hydroisomerization of alkanes, cycloalkanes, alkylated aromatic hydrocarbons, alkenes and / or mixtures thereof, hydrotreating of motor and jet fuels; disproportionation of alkenes, cycloalkenes and alkyl-substituted aromatic hydrocarbons, disalkylation of alkylaromatic hydrocarbons, transalkylation of aromatic hydrocarbon mixtures with various numbers of alkyl substituents, and catalytic reforming of hydrocarbon distillates boiling in the gasoline distillation range. The hydrocarbons or mixtures of hydrocarbons contemplated, but which do not contain sulfur and / or buffered compounds, may be included as additives. In many chemical processes, natural or synthetic aluminosilicates which are either amorphous or crystalline are used as catalysts. These aluminosilicates together with metals. to8. periodic groups (e.g., Mo, Re, Pt, Pd, Ni, Co, Ir, etc.) in the form of difunctional catalysts on a large scale are used in hydroprocessing such as hydrocracking, hydroisomerization, disproportionation, transalkylation, and the like.

Thus, the difunctional catalysts contain two active components; aluminosilicate (acidic component) and metal, respectively. its compound (hydrogenation / dehydrogenation component). Difunctional catalysts containing crystalline zeolite as the acidic component are more active and selectively more active than catalysts containing amorphous aluminosilicates. The most active difunctional catalysts include those containing the H-formusynthetic mordenite.

The present invention relates to a new type of difunctional catalysts which are more active and more selective and more deficient catalysts, comprising as an acidic component the H-form of the synthetic mordenite. According to the invention, the described difunctional catalysts can be referred to as multi-component disintegrating catalysts in view of the phase composition of the acid component of these catalysts.

The multi-component difunctional catalysts of the invention suitable for catalytic hydroconversion hydrocarbons or hydrocarbon mixtures are prepared by 219665 by mixing together the individual aluminocrystalline components A, B and C, wherein under component A the synthetic layered aluminosilicate having the empirical formula; m SiO2: n A12O3: p QO: with DM: t H? Ov where SiO2 is silicon dioxide A12O3 alumina QO metal oxide or oxides selected from the group consisting of copper, beryllium, magnesium, zinc, nickel, cobalt, D anions selected from the group consisting of a hydroxyl anion, a fluoride anion, a chloride anion, an anion of oxygen, an M equivalent of a replaceable cation or cations selected from the group consisting of hydrogen, ammonium, alkali metal, alkaline earth metal, H 2 O water, wherein the molar ratio is from 2.01 to 3.97 n has a value of 0.02 to 2.96 p having a value of 0.03 to 3.50 s having a value of 0.03 to 1.00 t having a value of 3.50 to 5.10 at 60% relative humidity.

Component B is understood to mean a material selected from the group consisting of alumina. 1 silicagel and / or crystalline aluminosilicate such as type X zeolites, Y type zeolites, halloyzite, natural or synthetic montmorillonite, kaolinite, natural mordenite, natural butbosynthetic clinoptilolite, mixtures thereof, natural or non-natural or natural mixed structures.

Component C within the meaning of the invention is understood to be a synthetic mordenite having a SiO 2: Al 2 O 3 molar ratio of from 9: 1 to 80: 1. The preparation of the catalyst according to the invention comprises homogenizing the mixture of said components A, B and C with a dry process (e.g. in a mill mill) or wet forming a homogenized mixtures in order to obtain a catalyst in the form of desired dimensions and shapes such as sapphires, extrudates, tablets and the like. The catalysts thus prepared according to the invention are further dried at a temperature of 80 ° C-150 ° C and calcined at a temperature of 150 ° C to 750 ° C. In order to obtain difunctional catalysts, it is necessary, prior to mixing the aluminosilicate constituents A, B and C, to introduce into these constituents the hydrogenation metals of the 6th and 8th periodic groups, such as platinum, palladium, nickel, cobalt, iridium, rhenium, molybdenum and the like. , or mixtures thereof with known processes, such as, for example, anionic impregnation. These hydrogenation metals can also be introduced after mixing components A, B and C, i.e., the mixture of components A, B and C. By both processes, the catalysts are characterized by high activity and selectivity.

The final step in the preparation of the catalysts according to the invention is the reduction of the calcined catalyst in a hydrogen stream or hydrogen-containing gas to convert the metals of the 7th and 8th periodic groups to an atomic state which is carried out directly in the reactor.

The multi-component difunctional catalysts according to the invention comprise the aluminosilicate components A, B and C, wherein the catalyst mixture comprises from 10% to 90% by weight. % of component A, from 1% to 80% by weight; % of component B, from 1% to 80% by weight. the components C and the metal or mixture of metals 6 to 8 of the group of the periodic system, wherein in the case of the metals of the 7th and 8th periodic groups their content in the catalyst is from 0.01% to 6.5% by weight. and in the case of metals of the 6th periodic group, from 0.5 to 25% by weight. the total weight of the catalyst. Subsequently, the examples illustrate the method of preparation, the advantages and the practical use of the catalyst according to the invention, without, however, limiting the subject matter of the invention in any way. Example 1

Synthetic mordenite dealuminated with hydrochloric acid solution to 17.8 SiO / AlO; was subjected to an ionic solution of [Pd (NH 3) 4] (NO 3) 2 so that after drying at 120 ° C it contained 0.6% palladium. Natural halloyite in which alkali metal cations have been removed by an ionic solution of acetonitrile is impregnated with a PdCT solution to contain 0.5% Pd, Component A with a bound zinc, containing about 0.5% by weight of PdCT. The Pd was dry blended and subsequently homogenized with the above-described synthetic mordenite and halloyite in a ball mill for 2 hours and then wet for 6 hours. By extrusion of this homogenized mixture, a catalyst labeled A was prepared which after drying and calcining for 480 hours. ° C contained 20% by weight of synthetic mordenite, 30% of halloyite and 50% of component A. Example Z.

The synthetic H-mordenite was treated with the ionic nickel nitrate solution so that it contained 2.2 wt. nickel. A homogeneous mixture was prepared from the modified mordenite, component A containing magnesium and nickel, and hydrochloric acid-activated clinoptilolite, which was impregnated with a solution of H 2 PtCl 6 and calcined in a muffle furnace at 500 ° C for 6 hours. By tableting the calcined mixture, Catalyst B was prepared which contained 30% of component A, 60% of clinoptilolite and 10% of H-mordite. Example 3.

The mixture of NH4-form zeolite Y, synthetic homordenite and component A with structurally bonded cobalt was impregnated with PdCl2 solution so that the dried catalyst C contained 50% mordenite, 35% NH4-Y zeolite and 15% component A. Palladium catalyst content was calcined at 480 ° C, 0.72 wt. Example 4. 219665

The synthetic mordenite in the H-form containing the palladium (0.3% by weight) ion-exchange process with a molar ratio of 24.8 SiO 2: Al 2 O 3 was mixed with the nickel-containing component A and the natural mordenite which had been treated with hydrochloric acid activation. The resulting mixture was homogenized under dry conditions and then wet, then impregnated with a solution of H2PtCl6, such that it contained a total of 0.4% by weight. platinum. By extrusion of the homogenized mixture, a catalyst D was prepared which, after calcination at 500 ° C, contained 60% of component A, 15% of synthetic and 25% of wt. natural mordenite. Example 5.

The catalytic activity of the difunctional catalysts of the invention in the hydrotreating process was monitored on a flow-through microarray-type at a pressure of 0.25 MPa on a hydrocracking model reaction of n-hexane.

H-form syntheticordenite with a 17.6 SiO 2 / Al 2 O 3 molar ratio of 0.8 wt. Spatial volume velocity of injected Hexane was 1.0 h ”1. The reaction products were analyzed by gas chromatography. As shown experimentally by the results (Table 1), the high activity catalysts of the invention, the same n-hexane conversion with the catalysts of the present invention reaches a lower temperature.

Table 1.

Catalyst According to the Invention Comparative Pt / H-mordenite Catalyst A Catalyst B Temperature ° C Conversion of n-hexane (wt%) 220 40.38 35.85 14.95 240 64.81 54.18 29.67 260 74.63 69 , 78 45.91 280 82.72 79.73 63.77 300 88.56 91.71 79.27 320 95.48 96.11 86.71 Example 6.

The catalytic activity of the catalysts according to the invention in the process of hydroisomerization of n-hexane was investigated under a hydrogen atmosphere at a pressure of 0.25 MPa, a bulk volume velocity of 1.0 h -1a at a temperature range of 200-320 ° C. isomerization catalyst Pt / H-mordenite (0.4 wt% platinum) The isomerisate was analyzed by gas chromatography, as shown by experimental results (Table 2), the catalysts of the invention are characterized by high activity and selectivity mainly due to the production of dimethylbutanes, which, due to their high octane number, are the most valuable hydrocarbons in the isomer, the excellent hydroisomerization activity and the selectivity of the catalysts of the present invention are best measured

Claims (2)

5, the selective conversion to dimethylbutane, which is 4.3 times higher than the current industrial isomerization catalyst, and also the selectivity conversion to nais-C5 / C6, which in the invention is 2.9 times higher than at comparative industrial catalyst (see Table 2). Table 2. Catalyst According to the Invention Comparison of industrial Pt / H-mordenite catalysis. C catalysis. D Temperature ° C 270 270 300 Product yield% w / w pentane 1,31 1,57 5,65 n-pentane 0,87 0,88 1,42 2,2-dimethylbutane 8,60 10,01 3,73 2,3-dimethylbutane 8,33 7,24 4,74 2-Methylpentane 32,84 34,39 21,02 3-methylpentane 19,98 21,16 13,45 n-hexane 18,07 18,45 20,73 methylcyclopentane 1.25 1.20 0.62 benzene 0.05 0.03 0.07 cyclohexane 0.26 0.25 0.14 dimethylbutane (DMB) selective. conversion to 16.93 17.25 8.47 DMB * 1) selective. conversion to 63.86 74.10 17.24 isoC5 / C6 2) 2.65 3.11 0.98 Yield C5 + wt. 92,56 95,17 71,59 0 Selective conversion to DMB =% (C, + · C2 + C3 C4 + nQ) 2) Selective conversion to isoC5 / C? -% (iC5 + iC (, + cycloC6)% ( Cj + C 2 + C 3 + C 4 + n C 5 + n + 1) The object of the invention A multi-component difunctional catalyst for catalytic hydroconversion of hydrocarbons or hydrocarbon mixtures such as hydrogenation cracking, hydroisomerization, disproportionation, dealkylation, hydrodearomatization, catalytic reforming, transalkylation, characterized in that it comprises aluminum silicate components A, B and C, and a metal component, wherein component A is a synthetic layered aluminosilicate with a summary empirical formula - m SiCL: n ALO: p QO: with DM: t Η Ό in which Si Si silicon dioxide A12O3 alumina QO metal oxide or oxides selected from 219665 including honey, beryllium, magnesium, zinc, nickel, cobalt, D equivalent of anions selected from the group consisting of a hydroxyl anion, fluoride anion, chloride anion, an oxygen anion M equivalent to a exchangeable cation or cation selected from the group consisting of hydrogen, ammonium, alkali metal, alkaline earth metal, H 2 O water, rmm has a value from 2.01 to 3.97 n has a value from 0.02 to 2.96 p has a value from 0.03 to 3.50 s has a value from 0.03 to 1.00 t has a value from 3, 50 to 5.10 at 60% of the restorative moisture, component B contains substances from the group such as alumina, silica gel, crystalline aluminosilicates, zeolites X, zeolites Y, halloyzite, natural morphorilonite, synthetic montmorillonite, kaolinite, natural mordenite, clinoptilolite, component C is a synthetic mordenite with a SiO2: A12O3 molar ratio in the range of 9: 1 to 80: 1, with the component A content of the catalyst being from 10% to 90% by weight, component B being from 1% to 80% by weight. the content of component C is from 1% to 80% by weight, and the metal component in the metal atom in the atomic state or in the form of its oxide or sulphide is selected from groups 6-8 of the preferred group including platinum, palladium, nickel, cobalt, iridium, rhenium, molybdenum, the metal content of the catalyst being in the case of metals of the 7th and 8th periodical from 0.01% to 6.5% by weight; and in the case of the 6th periodic group, from 0.5 to 25% by weight. 2. A method for producing a multi-component difunctional catalytic hydrocarbon conversion catalyst according to claim 1, characterized in that it comprises homogenizing the aluminosilicate constituents A, B and C in a dry or wet state, further forming a homogenized mixture of components A, B and C into particles, drying these particles at a temperature of from 70 ° C to 150 ° C, calcination of the dried particles at a temperature of from 150 ° C to 750 ° C, preferably from 350 ° C to 600 ° C, and heat treatment in the presence of hydrogen or hydrogen-containing gas at a temperature of 200 ° C to 650 ° C, preferably from 320 ° C to 480 ° C, wherein the metal component is introduced into the individual aluminosilicate components A, B and C prior to mixing, or into the mixture of components A, B and C during or after homogenization thereof, but before the heat treatment proceeding in hydrogen or hydrogen-containing gas.