CS219665B1 - Multicomponent disfunction catalyzer for catalytic hydroconversion of the hydrocarbons and method of making the same - Google Patents

Abstract

The subject of the invention is a catalyst suitable for the invention catalytic hydroconversion of hydrocarbons and processes production. The catalyst contains three aluminosilicate component and metal component. One Aluminosilicate the component is a synthetic mordenite with rhodium the molar ratio SiO2: A12O3, the second is synthetic metal-containing aluminosilicates its catalytic activity and the third component is a material selected from the group consisting of barbecue types i natural and synthetic aluminosilicates. and The metal component is selected from metals of the 6th and 8th periodic, group of elements. Catalyst production process includes a homogenization of aluminosilicates components containing a metal component and thermal processed under specified conditions. The catalyst can be used in hydroconversion hydrocarbons or mixtures of hydrocarbons such as hydrocracking, disproportionation, hydration roisomarization, hydrodearomatization, disalkylation transalkylation and the like.

Description

The invention relates to a new type of multi-component difunctional catalysts effective for catalytic hydroconversion of hydrocarbons or a mixture of hydrocarbons and a process for their preparation.

Hydroconversion is understood to mean the conversion of hydrocarbons or a mixture of hydrocarbons taking place in the presence of hydrogen or hydrogen-containing gas. Hydroconversion of hydrocarbons contemplated by the invention relates to hydrocracking, disproportionation, hydrodearomatization, hydroisomerization, desalkylation, catalytic reforming, transalkylation and similar processes taking place on difunctional catalysts.

More specifically, catalytic hydroconversions of hydrocarbons or mixtures of hydrocarbons are understood to mean the hydrotreating of petroleum distillates or hydrocarbon distillates obtained from coal processing; hydroisomerizing alkanes, cycloalkanes, alkylated aromatic hydrocarbons, alkenes, and / or mixtures thereof; hydrogenated dearomatization of motor and jet fuels;

disproportionation of alkenes, cycloalkenes and alkyl-substituted aromatic hydrocarbons; the de-alkylation of alkylaromatic hydrocarbons, the transalkylation of a mixture of aromatic hydrocarbons with different numbers of alkyl substituents, and catalytic reforming of hydrocarbon distillates boiling in the distillation range of gasoline. The hydrocarbons or hydrocarbon mixtures considered may or may not contain sulfuric and / or nitrogen compounds as accompanying substances.

In many chemical processes, natural or synthetic aluminosilicates, which are either amorphous or crystalline, are used as catalysts. These aluminosilicates together with metals. until

8. Periodic groups (e.g. Mo, Re, Pt, Pd, Ni, Co, Ir, etc.) in the form of difunctional catalysts are widely used in hydroprocesses such as hydrocracking, hydroisomerization, disproportionation, transalkylation and the like.

Thus, the difunctional catalysts comprise two active components; aluminosilicate (acid component) and metal, respectively. its compound (hydrogenation / dehydrogenation component). Difunctional catalysers containing crystalline zeolite as an acidic component are in most cases more active and selective than catalysts containing amorphous aluminosilicates. Among the most active difunctional catalysts are those containing the H-form of synthetic mordenite.

The present invention relates to a new type of difunctional catalysts which are more active and selective than difunctional catalysts containing, as an acidic component, the H-form of synthetic mordenite. The difunctional catalysts of the present invention described herein may be referred to as multi-component deafunctional catalysts in view of the phase composition of the acid component of these catalysts.

Multicomponent difunctional catalysts of the invention suitable for catalytic hydroconversion of hydrocarbons or mixtures of hydrocarbons are prepared by mixing the individual aluminosilts of the titanium components A, B and C, wherein component A is a synthetic layered aluminosilicate having an empirical formula ^; m SiO ₂ : n Al ₂ O ₃ : p QO: s DM: t H _? O in which SiO _{2 is} silica and Al ₂ O _{3 is} alumina

QO metal oxide or oxides selected from the group consisting of copper, beryllium, magnesium, zinc, 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 hydrogen, ammonium, alkali metal, alkaline earth metal,

H ₂ O water, wherein in molar ratios m 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% relative humidity.

Component B is a material selected from the group consisting of alumina.

¹ silica gel and / or crystalline aluminosilicates such as type X zeolites, type Y zeolites, halloyzite, natural or synthetic montmorillonite, kaolinite, natural mordenite, natural or synthetic clinoptilolite, mixtures thereof of natural or artificial or natural mixed structures.

Component C for the purposes of the invention is understood to be synthetic mordenite having a SiO ₂ : Al ₂ O ₃ molar ratio of from 9: 1 to 80: 1. The preparation of the catalysts according to the invention involves dry homogenization of the mixture of components A, B and C (e.g. milling) or wet-forming, shaping the homogenized mixture to obtain the catalyst in the form of desired dimensions and shapes such as matures, extrudates, tablets and others. The catalysts thus prepared according to the invention are further dried at > 80 ° C-150 ° C and calcined at a temperature of

150 ° C to 750 ° C.

In order to obtain difunctional catalysts, hydrogenation metals of the 6th and 8th period groups such as platinum, palladium, nickel, cobalt, iridium, rhenium, molybdenum and the like must be introduced into these components prior to mixing the aluminosilicate components A, B and C. or mixtures thereof by known methods, such as e.g. impregnation or ion exchange. Said hydrogenation metals may be; They can also be introduced after mixing components A, B and C, i.e. into ¹ mixture of components A, B and C. Both processes or a combination of both of them produce catalysts characterized by high activity and selectivity.

The final step in the preparation of the catalysts of the invention is to reduce the calcined catalyst in a hydrogen or hydrogen-containing gas stream to convert metals 7 and 8.

atomic group, which is usually done directly in the reactor.

The multicomponent difunctional catalysts of the invention comprise aluminosilicate components A, B and C, wherein the catalyst mixture comprises from 10% to 90% by weight of the composition. % of component A, from 1 to 80 wt. % of component B, from 1 to 80 wt. and, in the case of metals of the 7th and 8th groups, their content in the catalyst is from 0.01% to 6.5% by weight. and in the case of metals of the 6th period, from 0.5 to 25 wt. counting the total weight of the catalyst.

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,

Synthetic mordenite dealuminated with hydrochloric acid solution to a molar ratio of 17.8 SiO / AlO _; was subjected to ion exchange solutions of [Pd (NH ₃ ) ₄ ] (NO ₃ ) ₂ such that after drying at 120 ° C it contained 0.6% palladium. The natural halloyzite in which the alkali metal cations were removed with an ionic ammonium acetate solution was impregnated with a PdCT solution to contain 0.5% Pd. The Pd was dry blended and subsequently homogenized with the above-described synthetic mordenite and halloyzite in a ball mill for 2 hours and then wet for 6 hours. By extruding this homogenized mixture, a catalyst labeled A was prepared which, after drying and calcining at 480 ° C, contained 20 wt. synthetic mordenite, 30% halloyzite and 50% component A.

Example Ž.

Synthetic H-mordenite was treated with an ionic nickel nitrate solution to contain 2.2 wt. nickel. A homogeneous mixture was prepared from the treated mordenite, component A containing magnesium and nickel, and hydrochloric acid-activated clinoptilolite, which was impregnated with a H ₂ PtCl _{6 solution} and calcined in a muffle furnace at 500 ° C for 6 hours after drying. Catalyst B was prepared by tabletting the calcined mixture containing 30% of component A, 60% of clinoptilolite and 10% of H-mordenite.

Example 3.

A mixture of NH-form Y zeolite, synthetic mordenite and component A with structurally bound cobalt was impregnated with PdCl ₂ solution so that the dried catalyst C contained 50% mordenite, 35% NH ₄ -Y zeolite and 15% component A. Palladium content in a catalyst calcined at 480 ° C was 0.72 wt.

Example 4. 219665

Synthetic mordenite in H-form containing palladium (0.3% by weight) ion exchange procedure with a molar ratio of 24.8 SiO ₂ : Al ₂ O ₃ was mixed with component A containing nickel and natural mordenite, which was treated with hydrochloric acid activation . The resulting mixture was homogenized dry and then wet, impregnated with a solution of H ₂ PtCl ₆ to a total content of 0.4 wt. platinum. By extruding the homogenized mixture, Catalyst D was prepared which, after calcination at 500 ° C, contained 60% of component A, 15% of synthetic and 25% by weight. natural mordenite.

Example 5.

The catalytic activity of the difunctional catalysts of the invention in the hydrogenation cracking process was monitored on a conventional type flow microaparatrix at a pressure of 0.25 MPa on a n-hexane hydrocracking model reaction.

Synthetic mordenite in the H-form with a molar ratio of 17.6 SiO ₂ / Al ₂ O ₃ containing 0.8 wt. platinum. The spatial volume velocity of the injected n-hexane was 1.0 h ^-1 . The reaction products were analyzed by gas chromatography. As the results show experimentally (Table

1), the catalysts according to the invention are characterized by high activity, the same conversion of n-hexane with the catalysts according to the invention being achieved at 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 feed rate of 1.0 h ¹ and at a temperature range of 200-320 ° C. The industrial isomerization catalyst Pt / H-mordenite (0.4 wt% platinum) served as the comparative catalyst. The isomerisate was analyzed by gas chromatography. As shown experimentally (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 isomerisate.

The excellent hydroisomerization activity and selectivity of the catalysts according to the invention is best reflected in the selective conversion to dimethylbutanes parameter, which is 4.3 times greater than on the present industrial isomerization catalyst, as well as the selective conversion to iso-C ₅ / C ₆ catalyst. according to the invention

2.9 times the weight of a comparative industrial catalyst (see Table 2).

Table 2.

catalyst According to the invention Comparative industrial Pt / H-mordenite catalysis. C catalysis. D Temperature ° C 270 270 300 Product composition% wt. i-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 dimethylbutanes (DMB) selective. conversion to 16.93 17.25 8.47 DMB ^{* 1)} selective. conversion to 63.86 74.10 17.24 izoC ₅ / C ₆ ⁾ 2.65 3.11 0.98 Yield C ₅ ⁺ wt. 92.56 95.17 71.59

⁰ The selective conversion of the DMB% = (C, + C2 + C3 · -i ^- 4 + n Q) ²⁾ selective conversion of the isocil ₅ / N _N ~% ($ iC + iC ₍₊ cycloC _6)% (C + C 22 + C3 + C4 + nC ₅ + nC _(t )

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.