Silicon hydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention provides a silicon hydrogenation catalyst as well as a preparation method and application thereof, and relates to the field of catalysts. The catalyst comprises, by mass, 15-30% of an active component and 70-85% of a catalyst carrier, and the catalyst carrier is SiO2 (at) molecular sieve microspheres having a core-shell structure; the preparation method comprises the following steps: preparing a catalyst carrier, performing alkali etching on silochrom, adding inorganic aluminum salt and an organic ammonium template agent, uniformly mixing, performing hydrothermal crystallization treatment in a reaction kettle, and performing post-treatment on a product to obtain the catalyst carrier; and impregnating the active component on the carrier to obtain the catalyst. The prepared catalyst is applied to a reaction for preparing isononyl alcohol through isononyl aldehyde hydrogenation, the conversion rate of isononyl aldehyde reaches 99% or above, the selectivity of isononyl alcohol reaches 99% or above, and the catalyst has excellent activity, selectivity and stability and is beneficial to industrial application and popularization.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and in particular to a silicon-based hydrogenation catalyst and a preparation method and application thereof. Background Art

[0002] Isononanol, full name 7-methyl-1-octanol, molecular formula is C9H 20 O, with a relative molecular mass of 144.25, is mainly used to react with phthalic anhydride to produce diisononyl phthalate (DINP), a plasticizer for PVC. With the market's gradual recognition of the safety of DINP, the demand for DINP as an environmentally friendly substitute for DOP will grow rapidly, thereby driving the rapid increase in the consumption of isononanol. At present, the production of isononanol plasticizers in my country is almost blank and has always relied on imports, which are not only small in quantity but also expensive, thus restricting the development of plastic processing and the improvement of quality.

[0003] The preparation of isononyl alcohol includes two main steps. The first step is the hydroformylation of octenes to produce isononyl aldehyde, and the second step is the hydrogenation reduction of isononyl aldehyde to produce isononyl alcohol. At present, there are only two isononyl alcohol manufacturers in China, one is Maoming Petrochemical, which cooperates with BASF, and the other is Zibo Qixiang Tengda Chemical Co., Ltd., which cooperates with Exxon, Dow, and Johnson Matthey. All technologies come from foreign countries. In recent years, Chinese researchers have made certain progress in the research on the preparation of high-carbon carbonyl alcohols. The research scope has involved three main catalytic systems for the hydroformylation of high-carbon olefins: homogeneous catalytic system, water / organic two-phase catalytic system, and solid-supported water-phase catalytic system. However, there are few reports in China on the catalyst for hydrogenation of isononyl aldehyde to isononyl alcohol.

[0004] CN112898122A discloses a method for preparing isononyl alcohol from mixed octenes, wherein the active components of the aldehyde hydrogenation catalyst mentioned in the scheme are Ni, Mg, and Na, and one or more of Co, Ca, Sr, and Ba metal elements are used as additives, and one or more of alumina, silicon dioxide, and diatomaceous earth treated with ammonia are used as carriers to obtain the isononyl alcohol. The 3,5,5-trimethyl-1-hexanal hydrogenation catalyst mentioned in the isononyl alcohol preparation method disclosed in CN111995496A includes one or more mixtures of nickel, copper, platinum, or palladium. However, the above-mentioned catalyst has poor stability and low selectivity for isononyl alcohol. Summary of the invention

[0005] The present invention aims to provide a silicon-based hydrogenation catalyst and a preparation method and application thereof. The catalyst is used in the reaction of hydrogenating isononanal to produce isononanol. The catalyst carrier is prepared by covering the surface of coarse-pore silica gel with molecular sieves. The activity of the carrier is improved, and the technical effects of promoting the dispersion of active components and improving the selectivity of isononanol by utilizing the shape selectivity of the catalyst pore size are achieved.

[0006] To achieve the above object, the present invention proposes the following technical solutions:

[0007] In a first aspect, the present invention discloses a method for preparing a silicon-based hydrogenation catalyst, comprising the following preparation steps:

[0008] 1) preparing a catalyst carrier, wherein the catalyst carrier is SiO2@molecular sieve microspheres with a core-shell structure;

[0009] 2) The catalyst support is modified with an organic acid to remove most of the non-framework aluminum in the molecular sieve and make the molecular sieve H-type;

[0010] 3) The active components are loaded on the modified catalyst carrier by impregnation;

[0011] 4) The impregnated product is dried and calcined to obtain a silicon-based hydrogenation catalyst.

[0012] Furthermore, the process of preparing the catalyst carrier in step 1) comprises the following steps:

[0013] 2.1) Using alkaline solution to expand the pores of the macroporous silica gel;

[0014] 2.2) adding an organic ammonium template and an inorganic aluminum salt to the pore expansion treatment solution, stirring evenly to obtain a carrier precursor solution; wherein the inorganic aluminum salt is one of aluminum sulfate, aluminum nitrate, aluminum chloride, and aluminum hydroxide;

[0015] 2.3) Under temperature control conditions, subjecting the carrier precursor to hydrothermal crystallization treatment in a reactor;

[0016] 2.4) The product of the hydrothermal crystallization treatment is washed, filtered, dried, granulated, calcined, and then extruded with water and a binder to obtain SiO2@molecular sieve microspheres with a core-shell structure.

[0017] Furthermore, the organic acid in step 2) is citric acid, tartaric acid or acetic acid.

[0018] Furthermore, the alkali in the alkali solution in step 2.1) is NaOH or KOH.

[0019] Furthermore, in step 2.2), the organic ammonium template is tetrabutylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium hydroxide or tetrapropylammonium hydroxide.

[0020] Furthermore, the temperature of the temperature control condition in step 2.3) is 140-240°C, and the time of the hydrothermal crystallization treatment is 24-120 hours.

[0021] Furthermore, in step 2.4), the calcination temperature is 450-550° C., and the calcination time is 4-8 hours.

[0022] In a second aspect, the present invention discloses a silicon-based hydrogenation catalyst, which is prepared by the preparation method of the silicon-based hydrogenation catalyst described in the claim; wherein the silicon-based hydrogenation catalyst comprises an active component and a catalyst carrier, and the content of the catalyst carrier is 70-85% and the content of the active component is 15-30% by mass percentage.

[0023] Furthermore, the catalyst carrier is a SiO2@molecular sieve microsphere with a core-shell structure, the core layer is a SiO2 sphere with a particle size of 30 to 100 meshes, the shell layer is a molecular sieve with a Si / Al ratio of 70 to 140, and the thickness of the molecular sieve is 20-50nm; the active ingredient in the active component is metal Ni and / or metal Cu, and the active ingredient is attached to the catalyst carrier in the form of oxide.

[0024] In a third aspect, the present invention discloses the use of the above silicon-based hydrogenation catalyst in the reaction of hydrogenating aldehydes to produce alcohols, specifically in the reaction of hydrogenating isononanal to produce isononanol.

[0025] It can be seen from the above technical solutions that the technical solutions of the present invention have the following beneficial effects:

[0026] The silicon-based hydrogenation catalyst provided by the present invention and its preparation method and application relate to the field of catalysts; during preparation, silicon spheres are used as the core of the catalyst carrier, and the surface of the carrier is etched by alkali treatment; the obtained sodium silicate solution is treated by hydrothermal crystallization by adding a template, an aluminum source, etc., to generate a molecular sieve structure on the surface of the silicon sphere; and then the silicon-based hydrogenation catalyst is obtained by impregnating active components. The design scheme of the present invention enables the catalyst to obtain a suitable pore structure while giving full play to the shape-selective effect of the molecular sieve, and also makes the active components more evenly dispersed, thereby ensuring the activity, selectivity and stability of the catalyst. The advantages include the following:

[0027] (1) The present invention utilizes the method of covering the surface of coarse-pore silica gel with molecular sieves to improve the activity of the catalyst carrier, promote the dispersion of the active components, and utilize the shape selectivity of the molecular sieve pore size on the catalyst surface to improve the selectivity of isononanol;

[0028] (2) The present invention adopts an etching and recrystallization treatment method when preparing the catalyst carrier to achieve the splicing of multifunctional catalyst carriers, which is more conducive to improving the universality of the catalyst;

[0029] (3) The technical method adopted by the present invention is simple, conducive to industrial application and promotion, and has important social and economic significance;

[0030] (4) The catalyst prepared by the present invention is used in the reaction of hydrogenating isononanal to produce isononanol, and the isononanal conversion rate reaches more than 99%, and the isononanol selectivity reaches more than 99%. That is, the prepared catalyst has excellent activity, selectivity and stability.

[0031] It should be appreciated that all combinations of the foregoing concepts, as well as additional concepts described in greater detail below, may be considered to be part of the inventive subject matter of the present disclosure, provided such concepts are not mutually inconsistent.

[0032] The foregoing and other aspects, embodiments and features of the present invention can be more fully understood from the following description in conjunction with the accompanying drawings. Other additional aspects of the present invention, such as the features and / or beneficial effects of the exemplary embodiments, will be apparent from the following description or learned from the practice of the specific embodiments according to the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The accompanying drawings are not drawn to scale according to actual reference objects. In the accompanying drawings, each identical or nearly identical component shown in various figures may be represented by the same reference numeral. For the sake of clarity, not every component is labeled in each figure. Now, embodiments of various aspects of the present invention will be described by way of example and with reference to the accompanying drawings, in which:

[0034] Figure 1 The present invention is a process for preparing the silicon-based hydrogenation catalyst;

[0035] Figure 2 The present invention is a process for preparing the catalyst carrier. DETAILED DESCRIPTION

[0036] In order to make the purpose, technical solution and advantages of the embodiment of the present invention clearer, the technical solution of the embodiment of the present invention will be clearly and completely described below in conjunction with the drawings of the embodiment of the present invention. Obviously, the described embodiment is a part of the embodiment of the present invention, not all of the embodiments. Based on the described embodiment of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein should be the common meaning understood by people with general skills in the field to which the present invention belongs.

[0037] The words "first", "second" and similar words used in the patent application specification and claims of the present invention do not indicate any order, quantity or importance, but are only used to distinguish different components. Similarly, unless the context clearly indicates otherwise, the singular forms of "a", "an" or "the" and other similar words do not indicate a quantitative limitation, but indicate the existence of at least one. Words such as "include" or "comprise" mean that the elements or objects appearing before "include" or "comprise" cover the features, wholes, steps, operations, elements and / or components listed after "include" or "comprise", and do not exclude the existence or addition of one or more other features, wholes, steps, operations, elements, components and / or their collections. "Up", "down", "left", "right" and the like are only used to indicate relative positional relationships. When the absolute position of the described object changes, the relative positional relationship may also change accordingly.

[0038] Based on the increasing consumption of isononanol, the current domestic isononanol plasticizer mainly relies on imports, with extremely low self-production, and the key technology for producing isononanol is also from foreign countries. The catalyst used in the hydrogenation of isononanal to isononanol reported in the prior art is few, and the stability of the disclosed catalyst and the selectivity to isononanol are not high. The present invention aims to propose a silicon-based hydrogenation catalyst used in the reaction of hydrogenating isononanal to isononanol and a preparation method thereof, which not only has excellent activity and stability, but also has high selectivity to isononanol.

[0039] Specifically, the present invention discloses a method for preparing a silicon-based hydrogenation catalyst, such as Figure 1 As shown, the method comprises the following preparation steps: S1, preparing a catalyst carrier, wherein the catalyst carrier is a SiO2@ molecular sieve microsphere with a core-shell structure; S2, modifying the catalyst carrier with an organic acid; the organic acid is citric acid, tartaric acid or acetic acid; S3, loading the active component on the modified catalyst carrier by impregnation; S4, drying and calcining the impregnated product to obtain a silicon-based hydrogenation catalyst; the silicon-based hydrogenation catalyst comprises, by mass percentage, an active component with a content of 15 to 30% and a content of 70-85% of the catalyst carrier; wherein the catalyst carrier is a SiO2@molecular sieve microsphere with a core-shell structure, the core layer is a SiO2 ball with a particle size of 30-100 meshes, the shell layer is a molecular sieve with a Si / Al ratio of 70-140, and the thickness of the molecular sieve is 20-50nm; the active ingredient in the active component is metal Ni and / or metal Cu, and the active ingredient is attached to the catalyst carrier in the form of oxide; when the catalyst is used, it needs to be reduced to obtain metal Ni and / or metal Cu.

[0040] Combination Figure 2As shown, the preparation process of the catalyst carrier includes the following steps: S2.1, using an alkaline solution to expand the pores of the coarse-pore silica gel, the alkali of the alkaline solution is NaOH or KOH; S2.2, adding an organic ammonium template and an inorganic aluminum salt to the pore expansion treatment solution, stirring evenly to obtain a carrier precursor solution; wherein the organic ammonium template is tetrabutylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium hydroxide or tetrapropylammonium hydroxide, and the inorganic aluminum salt is one of aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum hydroxide; S2.3, under the temperature control condition of 140 to 240°C, the carrier precursor is subjected to a hydrothermal crystallization treatment in a reactor for 24 to 120 hours; S2.4, washing the product of the hydrothermal crystallization treatment, filtering, drying, granulating, calcining, and then extruding with water and a binder to obtain SiO2@molecular sieve microspheres with a core-shell structure; wherein the calcination treatment temperature is 450 to 550°C, and the treatment time is 4 to 8 hours.

[0041] The silicon-based hydrogenation catalyst disclosed in the present invention and its preparation method and application are further specifically introduced below in conjunction with specific embodiments.

[0042] Example 1

[0043] Weigh 200 g of 80-mesh coarse-pore silica gel, dissolve 40 g of NaOH in 1000 ml of deionized water to prepare a 1 mol / L NaOH solution, add the coarse-pore silica gel to the alkaline solution, stir for 20 min, and obtain a mixture a; weigh 2.02 g of aluminum nitrate nonahydrate and 11.40 g of tetrapropylammonium bromide, add them to the mixture a, and stir for reaction at 70°C for 30 min; put the obtained catalyst carrier precursor into a reactor, and perform hydrothermal crystallization treatment at 160°C for 48 h; pour out the product, wash, filter, dry, granulate, and calcine at 500°C for 4 h, and finally add water and a binder to form tablets to obtain a catalyst carrier.

[0044] Weigh 50 g of the catalyst carrier, treat it in 500 ml of 0.2 mol / L tartaric acid solution for 2 h, and then dry it. Then weigh 29.4 g of Cu(NO3)2 to prepare a solution, impregnate it at 120°C for 6 h, dry it, and calcine it at 350°C for 2 h to obtain catalyst C1.

[0045] Example 2

[0046] Weigh 200 g of 40-mesh coarse-pore silica gel, dissolve 40 g of NaOH in 1000 ml of deionized water to prepare a 1 mol / L NaOH solution, add the coarse-pore silica gel to the alkaline solution, stir for 30 min, and obtain a mixture a; weigh 0.52 g of aluminum hydroxide and 9.66 g of tetrabutylammonium bromide, add them to the mixture a, and stir for reaction at 70°C for 30 min; put the obtained catalyst carrier precursor into a reactor, and perform hydrothermal crystallization treatment at 180°C for 60 h; pour out the product, wash, filter, dry, granulate, and calcine at 450°C for 8 h, and finally add water and a binder to form tablets to obtain a catalyst carrier.

[0047] Weigh 50 g of the catalyst carrier, treat it in 500 ml of 0.2 mol / L citric acid solution for 2 h, and then dry it. Then weigh 50.4 g of Cu(NO3)2 to prepare a solution, impregnate it at 120°C for 6 h, dry it, and calcine it at 350°C for 2 h to obtain catalyst C2.

[0048] Example 3

[0049] Weigh 200g of 30-mesh coarse-pore silica gel, dissolve 56g of KOH in 1000ml of deionized water to prepare a 1mol / LKOH solution, add the coarse-pore silica gel to the alkaline solution, stir for 30min, and obtain a mixture a; weigh 1.26g of aluminum chloride and 11.10g of tetrabutylammonium bromide, add them to the mixture a, stir and react at 70°C for 30min; put the obtained catalyst carrier precursor into a reactor, and perform hydrothermal crystallization treatment at 240°C for 120h; pour out the product, wash, filter, dry, granulate, and calcine at 550°C for 4h, finally add water and a binder to form tablets to obtain a catalyst carrier.

[0050] Weigh 50 g of the catalyst carrier, treat it in 500 ml of 0.2 mol / L acetic acid solution for 2 h, and then dry it. Weigh 21.5 g of Ni(NO3)2 to make a solution and impregnate the carrier for 2 h. After drying, calcine at 400°C for 2 h to obtain catalyst C3.

[0051] Example 4

[0052] Weigh 200 g of 100-mesh coarse-pore silica gel, dissolve 56 g of KOH in 1000 ml of deionized water to prepare a 1 mol / L KOH solution, add the coarse-pore silica gel to the alkaline solution, stir for 30 min, and obtain a mixture a; weigh 1.42 g of aluminum sulfate and 9.72 g of tetrabutylammonium hydroxide, add them to the mixture a, and stir for reaction at 70°C for 30 min; put the obtained catalyst carrier precursor into a reactor, and perform hydrothermal crystallization treatment at 200°C for 24 h; pour out the product, wash, filter, dry, granulate, and calcine at 480°C for 5 h, and finally add water and a binder to form tablets to obtain a catalyst carrier.

[0053] Weigh 50 g of the catalyst carrier, treat it in 500 ml of 0.2 mol / L acetic acid solution for 2 h, and then dry it. Weigh 52.1 g of Ni(NO3)2 to make a solution and impregnate the carrier for 2 h. After drying, calcine at 400°C for 2 h to obtain catalyst C4.

[0054] Example 5

[0055] Weigh 200 g of 50-mesh coarse-pore silica gel, dissolve 40 g of NaOH in 1000 ml of deionized water to prepare a 1 mol / L NaOH solution, add the coarse-pore silica gel to the alkaline solution, stir for 30 min, and obtain a mixture a; weigh 3.57 g of aluminum nitrate nonahydrate and 8.70 g of tetrapropylammonium hydroxide, add them to the mixture a, and stir for reaction at 70°C for 30 min; put the obtained catalyst carrier precursor into a reactor, and perform hydrothermal crystallization treatment at 160°C for 96 h; pour out the product, wash, filter, dry, granulate, and calcine at 520°C for 6 h, and finally add water and a binder to form tablets to obtain a catalyst carrier.

[0056] Weigh 50 g of the catalyst carrier, treat it in 500 ml of 0.2 mol / L acetic acid solution for 2 h, and then dry it. Weigh 40.3 g of Ni(NO3)2 to make a solution and impregnate the carrier for 2 h. After drying, calcine at 400°C for 2 h to obtain catalyst C5.

[0057] Example 6

[0058] Weigh 200g of 70-mesh coarse-pore silica gel, dissolve 46g of KOH in 1000ml of deionized water to prepare a 1mol / LKOH solution, add the coarse-pore silica gel to the alkaline solution, stir for 30min, and obtain a mixture a; weigh 1.79g of aluminum nitrate nonahydrate and 4.35g of tetrapropylammonium hydroxide, add them to the mixture a, and stir for reaction at 70°C for 30min; put the obtained catalyst carrier precursor into a reactor, and perform hydrothermal crystallization treatment at 140°C for 120h; pour out the product, wash, filter, dry, granulate, and calcine at 550°C for 4h, and finally add water and a binder to form tablets to obtain a catalyst carrier.

[0059] Weigh 50 g of the catalyst carrier, treat it in 500 ml of 0.2 mol / L citric acid solution for 2 h, and then dry it. Then weigh 14.7 g of Cu(NO3)2 and 15.2 g of Ni(NO3)2 to make a solution and impregnate the carrier for 2 h. After drying, calcine at 320°C for 2 h to obtain catalyst C6.

[0060] Example 7

[0061] Weigh 200 g of 50-mesh coarse-pore silica gel, dissolve 40 g of NaOH in 1000 ml of deionized water to prepare a 1 mol / L NaOH solution, add the coarse-pore silica gel to the alkaline solution, stir for 30 min, and obtain a mixture a; weigh 0.95 g of aluminum sulfate and 6.65 g of tetrapropylammonium bromide, add them to the mixture a, and stir for reaction at 70°C for 30 min; put the obtained catalyst carrier precursor into a reactor, and perform hydrothermal crystallization treatment at 200°C for 24 h; pour out the product, wash, filter, dry, granulate, and calcine at 480°C for 5 h, and finally add water and a binder to form tablets to obtain a catalyst carrier.

[0062] Weigh 50g of catalyst carrier, treat it in 500ml 0.2mol / L tartaric acid solution for 2h, dry it, add 12.5g Cu(NO3)2, weigh 48.4g Ni(NO3)2 to make a solution and impregnate the carrier for 2h, dry it and calcine it at 340℃ for 2h to obtain catalyst C7.

[0063] Example 8

[0064] The catalyst was applied to the hydrogenation of isononanal to produce isononanol.

[0065] Take 50 ml of each C1-C7 catalyst and load it into a fixed bed reactor. Before the reaction, reduce the catalyst at 180°C, 0.2 MPa, and 5% hydrogen concentration nitrogen and hydrogen atmosphere for 12 hours, cool to 160°C, reaction pressure 3 MPa, and feed isononaldehyde at a rate of 0.6 h -1 , H2 flow rate 300ml / min, the results are shown in Table 1. At the same time, the catalyst was prepared in the preparation method of isononanal hydrogenation catalyst mentioned in invention patent CN112898122A to obtain catalyst C8, the use conditions were the same as above, the results are shown in Table 1.

[0066] Table 1 Catalyst activity evaluation results

[0067] Serial number Isononanal conversion rate / % Isononanol selectivity / % C1 99.7 99.5 C2 99.6 99.2 C3 99.5 99.1 C4 99.6 99.0 C5 99.3 99.2 C6 99.4 99.0 C7 99.2 99.3 C8 95.4 96.2

[0068] From the data in Table 1, it can be seen that when the catalyst designed by the technical scheme of the present invention is applied to the reaction of hydrogenating isononanal to produce isononanol, the conversion rate of isononanal reaches more than 99%, the selectivity of isononanol reaches more than 99%, and the catalyst performance is good; compared with the catalyst disclosed in the existing patents, the catalyst prepared by this scheme has significantly improved the conversion rate of isononanal and the selectivity of isononanol, and basically achieves 100% conversion.

[0069] Example 9

[0070] Take 50 ml of C1 and C8 catalysts and load them into a fixed bed reactor. Before the reaction, reduce the catalysts at 180°C, 0.2 MPa, and 5% hydrogen concentration in nitrogen and hydrogen atmosphere for 12 h. Then raise the temperature to 250°C, the reaction pressure to 3 MPa, and the isononanal feed rate to 0.6 h. -1 , H2 flow rate 300ml / min, the results are shown in Table 2 and Table 3 respectively.

[0071] Example 10

[0072] Take 50 ml of C1 and C8 catalysts and load them into a fixed bed reactor. Before the reaction, reduce the catalysts at 180°C, 0.2 MPa, and 5% hydrogen concentration in nitrogen and hydrogen atmosphere for 12 h, cool to 120°C, reaction pressure 4 MPa, and feed isononaldehyde at a rate of 0.6 h. -1 , H2 flow rate 300ml / min, the results are shown in Table 2 and Table 3 respectively.

[0073] Table 2 Effect of reaction conditions on the evaluation results of C1 catalyst activity

[0074]

[0075] Table 3 Effect of reaction conditions on the evaluation results of C8 catalyst activity

[0076]

[0077] It can be seen from Table 2 that at a reaction temperature of 120 to 250° C. and a reaction pressure of 3 to 4 MPa, the catalyst exhibits an excellent catalytic effect and has excellent stability, while the catalytic performance of the existing disclosed catalysts shows a downward trend at lower reaction temperatures; this fully demonstrates that the catalyst prepared by this scheme is suitable for industrial reaction conditions and is conducive to industrial promotion.

[0078] Table 4 Catalyst BET characterization data

[0079]

[0080]

[0081] Furthermore, catalysts C1 to C8 are analyzed from the perspective of microstructure to explain why the catalysts prepared by this scheme have superior performance compared to the catalysts disclosed in the existing patents; the specific surface area, pore size and pore volume of the catalysts prepared by this scheme undergo significant changes in their microstructure, for example, the specific surface area increases exponentially, and the wide specific surface area is more conducive to the dispersion of active components, thereby increasing the reaction active sites and improving the reaction activity of the catalyst.

[0082] As shown in Tables 1, 2, 3 and 4, the silicon-based hydrogenation catalyst prepared by the above preparation method of the present invention shows a high conversion rate of isononanal and a high selectivity for isononanol when applied to the reaction of hydrogenating isononanal to isononanol; the reason is that during the preparation, SiO2@molecular sieve microspheres with a core-shell structure are obtained by etching silicon macrospheres and then hydrothermally crystallizing them with a template, an aluminum source, etc., and then the silicon-based hydrogenation catalyst is obtained by impregnating active components, so that the surface layer of the prepared catalyst has a suitable pore structure, which plays a shape-selective role of the molecular sieve in the catalytic reaction of isononanal and improves the selectivity for isononanol; at the same time, the suitable pore structure also promotes a more uniform dispersion of the active components, further improving the activity of the catalyst.

[0083] Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. A person with ordinary knowledge in the technical field to which the present invention belongs may make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be determined by the definition of the claims.

Claims

1. A method for preparing a silicon-based hydrogenation catalyst, characterized in that: The method comprises the following preparation steps: 1) preparing a catalyst carrier, wherein the catalyst carrier is SiO2@molecular sieve microspheres with a core-shell structure; 2) The catalyst support is modified with an organic acid to remove most of the non-framework aluminum in the molecular sieve and make the molecular sieve H-type; 3) The active components are loaded on the modified catalyst carrier by impregnation; 4) The impregnated product is dried and calcined to obtain a silicon-based hydrogenation catalyst.

2. The method for preparing a silicon-based hydrogenation catalyst according to claim 1, characterized in that: The process of preparing the catalyst support in step 1) comprises the following steps: 2.1) Using alkaline solution to expand the pores of the macroporous silica gel; 2.2) adding an organic ammonium template and an inorganic aluminum salt to the pore expansion treatment solution, stirring evenly to obtain a carrier precursor solution; wherein the inorganic aluminum salt is one of aluminum sulfate, aluminum nitrate, aluminum chloride, and aluminum hydroxide; 2.3) Under temperature control conditions, subjecting the carrier precursor to hydrothermal crystallization treatment in a reactor; 2.4) The product of the hydrothermal crystallization treatment is washed, filtered, dried, granulated, calcined, and then extruded with water and a binder to obtain SiO2@molecular sieve microspheres with a core-shell structure.

3. The method for preparing a silicon-based hydrogenation catalyst according to claim 1, characterized in that: The organic acid in step 2) is citric acid, tartaric acid or acetic acid.

4. The method for preparing a silicon-based hydrogenation catalyst according to claim 2, characterized in that: The alkali in the alkali solution in step 2.1) is NaOH or KOH.

5. The method for preparing a silicon-based hydrogenation catalyst according to claim 2, characterized in that: In the step 2.2), the organic ammonium template is tetrabutylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium hydroxide or tetrapropylammonium hydroxide.

6. The method for preparing a silicon-based hydrogenation catalyst according to claim 2, characterized in that: The temperature of the temperature control condition in the step 2.3) is 140-240° C., and the time of the hydrothermal crystallization treatment is 24-120 hours.

7. The method for preparing a silicon-based hydrogenation catalyst according to claim 2, characterized in that: The calcination temperature in step 2.4) is 450-550° C. and the calcination time is 4-8 hours.

8. A silicon-based hydrogenation catalyst, characterized in that: The method for preparing a silicon-based hydrogenation catalyst according to any one of claims 1 to 7 is adopted; wherein the silicon-based hydrogenation catalyst comprises an active component and a catalyst carrier, and the content of the catalyst carrier is 70-85% and the content of the active component is 15-30% by weight.

9. The silicon-based hydrogenation catalyst according to claim 8, characterized in that The catalyst carrier is a SiO2@molecular sieve microsphere with a core-shell structure, the core layer is a SiO2 sphere with a particle size of 30 to 100 meshes, the shell layer is a molecular sieve with a Si / Al ratio of 70 to 140, and the thickness of the molecular sieve is 20-50nm; the active ingredient in the active component is metal Ni and / or metal Cu, and the active ingredient is attached to the catalyst carrier in the form of oxide.

10. Use of the silicon-based hydrogenation catalyst according to claim 8 or 9 in the reaction of hydrogenating aldehydes to produce alcohols.

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