A zero-hydrogen hydrogenolysis catalyst with composite multi-interface characteristics, a preparation method and application thereof

Abstract

The application provides a zero-hydrogen hydrogenolysis catalyst with composite multi-interface characteristics and a preparation method and application thereof, and belongs to the technical field of catalyst preparation. The method comprises the following steps: dissolving a metal precursor in water to obtain a precursor aqueous solution; dropwise adding the precursor aqueous solution to a carrier for isometric impregnation to obtain a slurry; performing auxiliary impregnation by using a strengthening means, aging at room temperature, drying, and crushing to obtain powder A; placing the powder A in a container, performing high-temperature calcination, and obtaining powder B after cooling; placing the powder B in a container, introducing hydrogen, heating to 150-600 DEG C for reduction treatment, and cooling to obtain the catalyst. By reasonably selecting active components and a proper catalyst carrier in a specific proportion, the prepared catalyst has the multi-interface characteristics, can realize efficient catalysis of biomass multi-sugar alcohol hydrogenolysis for preparing low-carbon polyhydric alcohol, and can be recycled multiple times.

Description

Technical Field

[0001] This invention belongs to the field of catalyst preparation technology, specifically relating to a zero-hydrogenation hydrogenolysis catalyst with composite multi-interface characteristics, its preparation method, and its application. Background Technology

[0002] Low-carbon polyols, such as propylene glycol, butanediol, and glycerol, play a vital role in the petrochemical industry. They are essential raw materials for manufacturing polyester materials, antifreeze, lubricants, plasticizers, high-energy fuels, and pharmaceutical synthesis. Traditional methods for preparing low-carbon polyols rely heavily on resources such as petroleum and natural gas, typically involving petroleum cracking, epoxidation of ethylene, propylene, and butene, and hydration reactions. However, this approach suffers from drawbacks such as complex processes, numerous byproducts, and severe environmental pollution.

[0003] Biomass polyols, derived from renewable resources such as agricultural and forestry waste, help reduce the use of oil and natural gas. However, biomass polyols suffer from over-functionalization, with each carbon atom carrying an oxygen atom, which restricts their industrial application and development. Currently, the hydrogenation catalytic conversion of over-functionalized polyols is a synthetic route that has attracted significant attention from both academia and industry. However, existing synthetic techniques suffer from drawbacks such as low hydrogenation deoxygenation efficiency of biomass polyols and the monofunctional nature of traditional hydrogenation deoxygenation catalysts.

[0004] Therefore, the present invention aims to provide a method for preparing a polyol hydrogenation catalyst with multi-interface characteristics. Summary of the Invention

[0005] In view of this, the present invention provides a method for preparing a zero-hydrogenation hydrogenolysis catalyst with composite multi-interface properties, comprising the following steps:

[0006] (1) Dissolve the metal precursor in deionized water to obtain an aqueous precursor solution for later use;

[0007] (2) Add the precursor aqueous solution to the carrier dropwise and impregnate it with an equal volume to obtain a slurry;

[0008] (3) The slurry is subjected to strengthening measures to assist impregnation for 0.5-2 hours, followed by aging at room temperature for 2-12 hours, and then dried and pulverized to obtain powder A;

[0009] (4) Place powder A in a reaction vessel, heat it to 400-600℃, calcine it at high temperature for 2-6 hours, and then cool it down to obtain powder B.

[0010] (5) Place powder B in a reaction vessel, introduce hydrogen gas, and heat to 150-600℃ for reduction treatment. After cooling, the powder is obtained.

[0011] Preferably, the metal in step (1) is at least one of Pt, Pd, Ru, Rh, Co, Ni, Fe, Cu, Ca, W, and Re, and the metal precursor is at least one of chloroplatinic acid, chloropalladium acid, ruthenium chloride, rhodium chloride, cobalt chloride hexahydrate, nickel nitrate hexahydrate, ferric nitrate nonahydrate, copper nitrate trihydrate, calcium nitrate trihydrate, ammonium tungstate, ammonium metatungstate, sodium tungstate, tungstic acid, phosphotungstic acid, and ammonium perrhenate. The molar concentration of the metal ions in the aqueous solution of the precursor is in the range of 0.005-1.5 mol / L. More preferably, the molar concentration of the metal ions in the aqueous solution of the precursor is in the range of 0.02-0.4 mol / L.

[0012] Preferably, the carrier in step (2) is a metal oxide, and the metal oxide is at least one of aluminum oxide, titanium oxide, cerium oxide, silicon oxide, zirconium oxide, and activated carbon. Preferably, the metal oxide is a nano-sized oxide powder. The mass ratio of the carrier to the metal ions in the precursor aqueous solution is 1:0.02-0.5. More preferably, the mass ratio of the carrier to the metal ions in the precursor aqueous solution is 1:0.06-0.2.

[0013] Preferably, the enhancement method in step (3) includes at least one of microwave, ultraviolet and ultrasound.

[0014] Preferably, the time for the strengthening means to assist in impregnation in step (3) is 0.5h, 1h, 1.5h or 2h, and the aging time in step (3) is 2h, 6h or 10h.

[0015] Preferably, the drying temperature in step (3) is 70-110°C, more preferably, the drying temperature is 70°C, 90°C or 110°C, and the drying time is 8-24h, more preferably, the drying time is 8h, 16h or 24h.

[0016] Preferably, after step (4), the following steps are set: the chloroplatinic acid precursor solution is dropped onto powder B, and the powder is impregnated with an equal volume to obtain a slurry. Steps (3)-(4) are repeated to obtain powder D. Then, powder D is placed in a reaction vessel, hydrogen gas is introduced, and the temperature is raised to 150-600℃ for reduction treatment. After cooling, the chloroplatinic acid precursor solution is obtained. The concentration of the chloroplatinic acid precursor solution is 0.01-0.5 mol / L.

[0017] Preferably, the roasting temperature in step (4) is 300℃, 400℃, 450℃, 500℃, or 600℃, and the roasting time is 2h, 4h, or 6h.

[0018] Preferably, the heating rate is 2-10℃ / min, more preferably, the heating rate is 2℃ / min, 5℃ / min or 10℃ / min, the reduction treatment time in step (5) is 1-12h, more preferably, the reduction treatment time is 1h, 2h, 3h or 5h, and the reduction treatment temperature in step (5) is 300℃, 400℃, 450℃, 500℃ or 600℃.

[0019] The present invention also provides a zero-hydrogenation hydrogenolysis catalyst with composite multi-interface properties prepared by the method, and the application of the catalyst in the hydrogenolysis reaction of polyols.

[0020] Preferably, the application of the catalyst in the hydrogenolysis reaction of polyols includes the following steps: mixing the polyol solution and the catalyst in a high-pressure reactor, purging with hydrogen or nitrogen 3-6 times, carrying out a catalytic hydrogenation reaction at a temperature of 140-280°C for 3-48 hours, cooling to 25-40°C after the reaction, separating the mixture obtained after the reaction to obtain a bio-based long-chain alcohol.

[0021] Preferably, the reaction temperature for catalytic hydrogenation is 140-220°C, and the reaction time for catalytic hydrogenation is 6-24 hours.

[0022] Preferably, the hydrogen pressure inside the high-pressure reactor is 1-8 MPa.

[0023] Preferably, the polyol is a C2-C6 long-chain alcohol. More preferably, the C2-C6 long-chain alcohol includes, but is not limited to, ethylene glycol, glycerol, erythritol, xylitol, arabinitol, sorbitol, and mannitol; the long-chain alcohol is 1,2-propanediol, 1,3-propanediol, n-propanol, isopropanol, 1,2,4-butanetriol, 1,2,3-butanetriol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, n-pentanol, sec-pentanol, 1,4-pentanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, and 1,2,3-hexanetriol.

[0024] Preferably, the concentration of the polyol solution is 2wt%-80wt%, the solvent of the polyol solution is deionized water, or a mixture of deionized water and ethanol or isopropanol, and the mass ratio of the polyol solution to the catalyst is 50-180:1.

[0025] Preferably, the stirring speed during catalytic hydrogenation is 200-1000 r / min.

[0026] Preferably, the separation method includes, but is not limited to, vacuum distillation.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) By rationally selecting a specific proportion of active components and an appropriate catalyst support, the present invention enables the prepared catalyst to have multi-interface characteristics, which can achieve efficient catalytic hydrogenolysis of biomass polysaccharide alcohols to prepare low-carbon polyols, and can be recycled multiple times.

[0029] (2) By changing the reduction temperature and reduction time, the present invention selectively adjusts the acid-base pair on the surface of the catalyst support and the active component. By selecting different supports and changing the impregnation time and aging time, the dispersion of the active component is improved, thereby improving the catalyst’s performance in selectively removing secondary hydroxyl groups from polyols.

[0030] (3) In the process of catalyst preparation, the present invention uses microwave, ultraviolet and ultrasonic methods to enhance impregnation, which can greatly improve the catalyst preparation efficiency, shorten the catalyst preparation time and improve the catalyst performance.

[0031] (4) This invention can efficiently catalytically hydrogenate high-concentration biomass polysaccharides to prepare low-carbon polyols, which has the characteristics of high efficiency, few by-products, and easy separation and purification. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0033] Unless otherwise specified, the test methods or experimental methods described in the following examples are all conventional methods; unless otherwise specified, the raw materials and additives are obtained from conventional commercial sources or prepared by conventional methods.

[0034] Example 1:

[0035] A Pt / WO x The preparation method of Al2O3 catalyst, with specific steps as follows:

[0036] (1) Dissolve ammonium metatungstate in deionized water to obtain a precursor aqueous solution with a metal ion molar concentration of 0.3 mol / L, for later use;

[0037] (2) Add the precursor aqueous solution dropwise to the alumina support, wherein the mass ratio of the alumina support to the metal ions in the precursor aqueous solution is 1:0.15, stir until the mixture is in a "paste mixture" state, and complete the equal volume impregnation to obtain slurry a;

[0038] (3) Microwave-enhanced impregnation was applied to slurry a for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 6 hours, dried at 110°C for 8 hours, and pulverized to obtain powder A.

[0039] (4) Place powder A in a muffle furnace and calcine it in an air atmosphere. The temperature is increased to 600°C at a heating rate of 2°C / min and maintained for 4 hours. Then, the powder B is obtained by natural cooling.

[0040] (5) Add the 0.25 mol / L chloroplatinic acid precursor solution dropwise to powder B, stir until it reaches the state of "paste mixture", and complete the equal volume impregnation to obtain slurry b;

[0041] (6) Microwave-enhanced impregnation was applied to slurry b for 2 hours, the power of which was 180W. Then, the slurry was aged at room temperature for 6 hours, dried at 110°C for 8 hours, and pulverized to obtain powder C.

[0042] (7) Place powder C in a muffle furnace and calcine it in an air atmosphere. Heat it to 400°C at a heating rate of 2°C / min and maintain it for 4 hours. Then cool it down naturally to obtain powder D.

[0043] (8) Powder D is transferred into a tube furnace, hydrogen is introduced, and the temperature is raised to 300°C at a heating rate of 2°C / min for reduction treatment for 5 hours. The catalyst is then naturally cooled to room temperature.

[0044] Example 2

[0045] The difference from Example 1 is that the metal precursor and the carrier are different.

[0046] A Pt / WO x The preparation method of / ZrO2 catalyst, the specific steps are as follows:

[0047] (1) Dissolve sodium tungstate in deionized water to obtain a precursor aqueous solution with a metal ion molar concentration of 0.3 mol / L, for later use;

[0048] (2) Add the precursor aqueous solution dropwise to the zirconia support, wherein the mass ratio of the zirconia support to the metal ions in the precursor aqueous solution is 1:0.15, stir until the mixture is in a "paste mixture" state, and complete the equal volume impregnation to obtain slurry a;

[0049] (3) Microwave-enhanced impregnation was applied to slurry a for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 6 hours, dried at 110°C for 8 hours, and pulverized to obtain powder A.

[0050] (4) Place powder A in a muffle furnace and calcine it in an air atmosphere. The temperature is increased to 600°C at a heating rate of 2°C / min and maintained for 4 hours. Then, the powder B is obtained by natural cooling.

[0051] (5) Add the 0.25 mol / L chloroplatinic acid precursor solution dropwise to powder B, stir until it reaches the state of "paste mixture", and complete the equal volume impregnation to obtain slurry b;

[0052] (6) Microwave-enhanced impregnation was applied to slurry b for 2 hours, the power of which was 180W. Then, the slurry was aged at room temperature for 6 hours, dried at 110°C for 8 hours, and pulverized to obtain powder C.

[0053] (7) Place powder C in a muffle furnace and calcine it in an air atmosphere. Heat it to 400°C at a heating rate of 2°C / min and maintain it for 4 hours. Then cool it down naturally to obtain powder D.

[0054] (8) Powder D is transferred into a tube furnace, hydrogen is introduced, and the temperature is raised to 300°C at a heating rate of 2°C / min for reduction treatment for 5 hours. The catalyst is then naturally cooled to room temperature.

[0055] Example 3

[0056] The difference from Example 1 is that the metal precursor and the carrier are different.

[0057] A Pt / WO x The preparation method of / SiO2 catalyst, the specific steps are as follows:

[0058] (1) Dissolve sodium tungstate in deionized water to obtain a precursor aqueous solution with a metal ion molar concentration of 0.3 mol / L, for later use;

[0059] (2) The precursor aqueous solution is added dropwise to the silica support, wherein the mass ratio of the silica support to the metal ions in the precursor aqueous solution is 1:0.15. The mixture is stirred until it reaches the state of "paste mixture" and the equal volume impregnation is completed to obtain slurry a.

[0060] (3) Microwave-enhanced impregnation was applied to slurry a for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 6 hours, dried at 110°C for 8 hours, and pulverized to obtain powder A.

[0061] (4) Place powder A in a muffle furnace and calcine it in an air atmosphere. The temperature is increased to 600°C at a heating rate of 2°C / min and maintained for 4 hours. Then, the powder B is obtained by natural cooling.

[0062] (5) Add the 0.25 mol / L chloroplatinic acid precursor solution dropwise to powder B, stir until it reaches the state of "paste mixture", and complete the equal volume impregnation to obtain slurry b;

[0063] (6) Microwave-enhanced impregnation was applied to slurry b for 2 hours, the power of which was 180W. Then, the slurry was aged at room temperature for 6 hours, dried at 110°C for 8 hours, and pulverized to obtain powder C.

[0064] (7) Place powder C in a muffle furnace and calcine it in an air atmosphere. Heat it to 400°C at a heating rate of 2°C / min and maintain it for 4 hours. Then cool it down naturally to obtain powder D.

[0065] (8) Powder D is transferred into a tube furnace, hydrogen is introduced, and the temperature is raised to 300°C at a heating rate of 2°C / min for reduction treatment for 5 hours. The catalyst is then naturally cooled to room temperature.

[0066] Example 4

[0067] The difference from Example 1 is that the metal precursor is different.

[0068] A method for preparing a Pt / PW / Al2O3 catalyst, the specific steps of which are as follows:

[0069] (1) Dissolve phosphotungstic acid in deionized water to obtain a precursor aqueous solution, wherein the molar concentration of metal ions in the precursor aqueous solution is 0.3 mol / L, for later use;

[0070] (2) The precursor aqueous solution is added dropwise to the alumina support, wherein the mass ratio of the alumina support to the metal ions in the precursor aqueous solution is 1:0.15. The mixture is stirred until it reaches the state of "paste mixture" and the equal volume impregnation is completed to obtain slurry a.

[0071] (3) Microwave-enhanced impregnation was applied to slurry a for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 6 hours, dried at 110°C for 8 hours, and pulverized to obtain powder A.

[0072] (4) Place powder A in a muffle furnace and calcine it in an air atmosphere. The temperature is increased to 600°C at a heating rate of 2°C / min and maintained for 4 hours. Then, the powder B is obtained by natural cooling.

[0073] (5) Add the 0.25 mol / L chloroplatinic acid precursor solution dropwise to powder B, stir until it reaches the state of "paste mixture", and complete the equal volume impregnation to obtain slurry b;

[0074] (6) Microwave-enhanced impregnation was applied to slurry b for 2 hours, the power of which was 180W. Then, the slurry was aged at room temperature for 6 hours, dried at 110°C for 8 hours, and pulverized to obtain powder C.

[0075] (7) Place powder C in a muffle furnace and calcine it in an air atmosphere. Heat it to 400°C at a heating rate of 2°C / min and maintain it for 4 hours. Then cool it down naturally to obtain powder D.

[0076] (8) Powder D is transferred into a tube furnace, hydrogen is introduced, and the temperature is raised to 300°C at a heating rate of 2°C / min for reduction treatment for 5 hours. The catalyst is then naturally cooled to room temperature.

[0077] Example 5

[0078] The difference from Example 1 is that the metal precursor is different.

[0079] A method for preparing a Pt / W / Al2O3 catalyst, the specific steps of which are as follows:

[0080] (1) Dissolve tungstic acid in deionized water to obtain a precursor aqueous solution with a metal ion molar concentration of 0.3 mol / L, for later use;

[0081] (2) The precursor aqueous solution is added dropwise to the alumina support, wherein the mass ratio of the alumina support to the metal ions in the precursor aqueous solution is 1:0.15. The mixture is stirred until it reaches the state of "paste mixture" and the equal volume impregnation is completed to obtain slurry a.

[0082] (3) Microwave-enhanced impregnation was applied to slurry a for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 6 hours, dried at 110°C for 8 hours, and pulverized to obtain powder A.

[0083] (4) Place powder A in a muffle furnace and calcine it in an air atmosphere. The temperature is increased to 600°C at a heating rate of 2°C / min and maintained for 4 hours. Then, the powder B is obtained by natural cooling.

[0084] (5) Add the 0.25 mol / L chloroplatinic acid precursor solution dropwise to powder B, stir until it reaches the state of "paste mixture", and complete the equal volume impregnation to obtain slurry b;

[0085] (6) Microwave-enhanced impregnation was applied to slurry b for 2 hours, the power of which was 180W. Then, the slurry was aged at room temperature for 6 hours, dried at 110°C for 8 hours, and pulverized to obtain powder C.

[0086] (7) Place powder C in a muffle furnace and calcine it in an air atmosphere. Heat it to 400°C at a heating rate of 2°C / min and maintain it for 4 hours. Then cool it down naturally to obtain powder D.

[0087] (8) Powder D is transferred into a tube furnace, hydrogen is introduced, and the temperature is raised to 300°C at a heating rate of 2°C / min for reduction treatment for 5 hours. The catalyst is then naturally cooled to room temperature.

[0088] Example 6

[0089] The difference from Example 1 lies in the strengthening method and the auxiliary impregnation time.

[0090] A Pt / WO x The preparation method of Al2O3-UV catalyst is as follows:

[0091] (1) Dissolve ammonium metatungstate in deionized water to obtain a precursor aqueous solution with a metal ion molar concentration of 0.3 mol / L, for later use;

[0092] (2) The precursor aqueous solution is added dropwise to the alumina support, wherein the mass ratio of the alumina support to the metal ions in the precursor aqueous solution is 1:0.15. The mixture is stirred until it reaches the state of "paste mixture" and the equal volume impregnation is completed to obtain slurry a.

[0093] (3) Apply ultraviolet light to slurry a for 0.5 h to assist in impregnation, then age at room temperature for 6 h, dry at 110 °C for 8 h, and pulverize to obtain powder A;

[0094] (4) Place powder A in a muffle furnace and calcine it in an air atmosphere. The temperature is increased to 600°C at a heating rate of 2°C / min and maintained for 4 hours. Then, the powder B is obtained by natural cooling.

[0095] (5) Add the 0.25 mol / L chloroplatinic acid precursor solution dropwise to powder B, stir until it reaches the state of "paste mixture", and complete the equal volume impregnation to obtain slurry b;

[0096] (6) Apply UV enhancement to slurry b for 0.5 h to assist in impregnation, then age at room temperature for 6 h, dry at 110 °C for 8 h, and pulverize to obtain powder C;

[0097] (7) Place powder C in a muffle furnace and calcine it in an air atmosphere. Heat it to 400°C at a heating rate of 2°C / min and maintain it for 4 hours. Then cool it down naturally to obtain powder D.

[0098] (8) Powder D is transferred into a tube furnace, hydrogen is introduced, and the temperature is raised to 300°C at a heating rate of 2°C / min for reduction treatment for 5 hours. The catalyst is then naturally cooled to room temperature.

[0099] Example 7

[0100] The difference from Example 1 is that the aging time and reduction temperature are different.

[0101] A Pt / WO x The preparation method of Al2O3 catalyst, with specific steps as follows:

[0102] (1) Dissolve ammonium metatungstate in deionized water to obtain a precursor aqueous solution with a metal ion molar concentration of 0.3 mol / L, for later use;

[0103] (2) The precursor aqueous solution is added dropwise to the alumina support, wherein the mass ratio of the alumina support to the metal ions in the precursor aqueous solution is 1:0.15. The mixture is stirred until it reaches the state of "paste mixture" and the equal volume impregnation is completed to obtain slurry a.

[0104] (3) Microwave-enhanced impregnation was applied to slurry a for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 12 hours, dried at 110°C for 8 hours, and pulverized to obtain powder A.

[0105] (4) Place powder A in a muffle furnace and calcine it in an air atmosphere. The temperature is increased to 600°C at a heating rate of 2°C / min and maintained for 4 hours. Then, the powder B is obtained by natural cooling.

[0106] (5) Add the 0.25 mol / L chloroplatinic acid precursor solution dropwise to powder B, stir until it reaches the state of "paste mixture", and complete the equal volume impregnation to obtain slurry b;

[0107] (6) Microwave-enhanced impregnation was applied to slurry b for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 12 hours, dried at 110°C for 8 hours, and pulverized to obtain powder C.

[0108] (7) Place powder C in a muffle furnace and calcine it in an air atmosphere. Heat it to 400°C at a heating rate of 2°C / min and maintain it for 4 hours. Then cool it down naturally to obtain powder D.

[0109] (8) Powder D is transferred into a tube furnace, hydrogen is introduced, and the temperature is raised to 400°C at a heating rate of 2°C / min for reduction treatment for 5 hours. The catalyst is then naturally cooled to room temperature.

[0110] Example 8

[0111] The difference from Example 1 is that the aging time, reduction temperature, and reduction time are different.

[0112] A Pt / WO x The preparation method of Al2O3 catalyst, with specific steps as follows:

[0113] (1) Dissolve ammonium metatungstate in deionized water to obtain a precursor aqueous solution with a metal ion molar concentration of 0.3 mol / L, for later use;

[0114] (2) The precursor aqueous solution is added dropwise to the alumina support, wherein the mass ratio of the alumina support to the metal ions in the precursor aqueous solution is 1:0.15. The mixture is stirred until it reaches the state of "paste mixture" and the equal volume impregnation is completed to obtain slurry a.

[0115] (3) Microwave-enhanced impregnation was applied to slurry a for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 12 hours, dried at 110°C for 8 hours, and pulverized to obtain powder A.

[0116] (4) Place powder A in a muffle furnace and calcine it in an air atmosphere. The temperature is increased to 600°C at a heating rate of 2°C / min and maintained for 4 hours. Then, the powder B is obtained by natural cooling.

[0117] (5) Add the 0.25 mol / L chloroplatinic acid precursor solution dropwise to powder B, stir until it reaches the state of "paste mixture", and complete the equal volume impregnation to obtain slurry b;

[0118] (6) Microwave-enhanced impregnation was applied to slurry b for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 12 hours, dried at 110°C for 8 hours, and pulverized to obtain powder C.

[0119] (7) Place powder C in a muffle furnace and calcine it in an air atmosphere. Heat it to 400°C at a heating rate of 2°C / min and maintain it for 4 hours. Then cool it down naturally to obtain powder D.

[0120] (8) Powder D is transferred into a tube furnace, hydrogen is introduced, and the temperature is raised to 300°C at a heating rate of 2°C / min for 3 hours for reduction treatment. The catalyst is then naturally cooled to room temperature.

[0121] Example 9

[0122] The difference from Example 1 is that the aging time, reduction temperature, and reduction time are different.

[0123] A Pt / WO x The preparation method of Al2O3 catalyst, with specific steps as follows:

[0124] (1) Dissolve ammonium metatungstate in deionized water to obtain a precursor aqueous solution with a metal ion molar concentration of 0.3 mol / L, for later use;

[0125] (2) The precursor aqueous solution is added dropwise to the alumina support, wherein the mass ratio of the alumina support to the metal ions in the precursor aqueous solution is 1:0.15. The mixture is stirred until it reaches the state of "paste mixture" and the equal volume impregnation is completed to obtain slurry a.

[0126] (3) Microwave-enhanced impregnation was applied to slurry a for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 12 hours, dried at 110°C for 8 hours, and pulverized to obtain powder A.

[0127] (4) Place powder A in a muffle furnace and calcine it in an air atmosphere. The temperature is increased to 600°C at a heating rate of 2°C / min and maintained for 4 hours. Then, the powder B is obtained by natural cooling.

[0128] (5) Add the 0.25 mol / L chloroplatinic acid precursor solution dropwise to powder B, stir until it reaches the state of "paste mixture", and complete the equal volume impregnation to obtain slurry b;

[0129] (6) Microwave-enhanced impregnation was applied to slurry b for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 12 hours, dried at 110°C for 8 hours, and pulverized to obtain powder C.

[0130] (7) Place powder C in a muffle furnace and calcine it in an air atmosphere. Heat it to 400°C at a heating rate of 2°C / min and maintain it for 4 hours. Then cool it down naturally to obtain powder D.

[0131] (8) Transfer powder D into a tube furnace, introduce hydrogen gas, heat it to 300°C at a heating rate of 2°C / min for 1 hour for reduction treatment, and then cool it naturally to room temperature to obtain the catalyst.

[0132] Example 10

[0133] The difference from Example 1 is that the metal precursor, reduction temperature, and reduction time are all different.

[0134] A method for preparing a Pt-Fe / ZrO2 catalyst, the specific steps of which are as follows:

[0135] (1) Dissolve ferric nitrate nonahydrate and chloroplatinic acid in deionized water to obtain a precursor aqueous solution. The molar concentrations of iron and platinum ions in the precursor aqueous solution are 1.5 mol / L and 0.25 mol / L, respectively.

[0136] (2) The precursor aqueous solution is added dropwise to the zirconia support, wherein the mass ratio of the metal ions iron and platinum in the zirconia support and the precursor aqueous solution is 1:0.2 and 1:0.04, respectively. The mixture is stirred until it reaches the state of "paste mixture" and the equal volume impregnation is completed to obtain slurry a.

[0137] (3) Microwave-enhanced impregnation was applied to slurry a for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 10 hours, dried at 110°C for 8 hours, and pulverized to obtain powder A.

[0138] (4) Place powder A in a muffle furnace and calcine it in an air atmosphere. The temperature is increased to 600°C at a heating rate of 2°C / min and maintained for 4 hours. Then, the powder B is obtained by natural cooling.

[0139] (8) Powder B is transferred into a tube furnace, hydrogen is introduced, and the temperature is raised to 200°C at a heating rate of 2°C / min for 12 hours for reduction treatment. The catalyst is then naturally cooled to room temperature.

[0140] Application Example 1-10

[0141] The catalysts prepared in Examples 1-10 were used to hydrogenate erythritol to prepare low-carbon polyols. The specific process is as follows: 0.2g of catalyst was weighed and placed in a reactor, and 15ml of 25wt% erythritol was added. The reactor was then sealed. Before the reaction, the reactor was purged with hydrogen three times to achieve a final reaction pressure of 6MPa hydrogen. The reaction time was set to 24h. The stirrer was turned on and the speed was adjusted to 200r / min. When the temperature of the high-pressure reactor reached 180℃, the stirrer speed was adjusted to 1000r / min to carry out the catalytic hydrogenation reaction. After the reaction, the reaction solution was processed by high-performance liquid chromatography (HPLC). The HPLC system was equipped with a differential refractive index detector (RID-20A) and a Rezex ROA-OrganicAcid H+ (8%) 300*7.7mm column. A 5mmol / L dilute sulfuric acid aqueous solution was used as the mobile phase at a flow rate of 0.8mL / min, and the column temperature was 60℃. The results are shown in Table 1.

[0142] Table 1

[0143]

[0144]

[0145] As shown in Table 1, the synthesized catalysts in Examples 1-10 exhibited high catalytic performance and selectivity. Analysis of the data from Examples 1-3 in Table 1 reveals that, during catalyst preparation, the interface formed by the Pt-W-Al2O3 catalyst prepared using Al2O3 as the support in Example 1 showed the best performance for the hydrogenolysis of erythritol to 1,4-butanediol, resulting in the highest yield of 1,4-butanediol.

[0146] Analysis of the data from Examples 1, 4, 5, and 10 in Table 1 shows that the precursor of the combination of ammonium metatungstate and chloroplatinic acid in Example 1 is the optimal one in the catalyst preparation process, and the catalyst prepared from it has the highest yield of 1,4-butanediol.

[0147] Analysis of the data in Examples 1 and 6 in Table 1 shows that the catalyst prepared by the ultrasonic-enhanced impregnation method in Example 1 is the best, and the yield of 1,4-butanediol prepared by it is the highest.

[0148] Analysis of the data in Examples 1, 7, 8 and 9 in Table 1 shows that the optimal reduction temperature of 300℃ and reduction time of 5h in Example 1 were used in the catalyst preparation process, and the catalyst prepared by it had the highest yield of 1,4-butanediol.

[0149] The results of catalyst stability tests using the catalyst from Example 1 are shown in Table 2 below:

[0150] Table 2

[0151]

[0152]

[0153] Application Example 11

[0154] The application of catalysts in the hydrogenolysis reaction of polyols involves the following specific steps:

[0155] (1) Accurately weigh 12g of glycerol, 3g of deionized water and 0.2g of the catalyst from Example 1 and mix them in a high-pressure reactor. Seal the high-pressure reactor and replace it with hydrogen three times to keep the pressure at 6MPa.

[0156] (2) Turn on the stirrer and adjust the speed of the stirrer to 200 r / min. When the temperature of the high-pressure reactor rises to 180℃, adjust the speed of the stirrer to 1000 r / min to carry out the catalytic hydrogenation reaction. The reaction time is 48 h.

[0157] (3) After the reaction is completed, the catalyst and the solution after the reaction are removed and filtered to obtain the filtrate. Isopropanol, n-propanol, 1,2-propanediol and unreacted glycerol in the filtrate are removed by vacuum distillation to obtain 1,3-propanediol with a yield of 67%.

[0158] Application Example 12

[0159] The application of catalysts in the hydrogenolysis reaction of polyols involves the following specific steps:

[0160] (1) Accurately weigh 5g of erythritol, 15g of deionized water and 0.2g of the catalyst from Example 1 and mix them in a high-pressure reactor. Seal the high-pressure reactor and replace it with hydrogen three times to keep the pressure at 6MPa.

[0161] (2) Turn on the stirrer and adjust the speed of the stirrer to 200 r / min. When the temperature of the high-pressure reactor rises to 180℃, adjust the speed of the stirrer to 1000 r / min to carry out the catalytic hydrogenation reaction. The reaction time is 24 h.

[0162] (3) After the reaction is complete, the mixture is naturally cooled to room temperature. The catalyst and the solution after the reaction are removed. The solution after the reaction is filtered to obtain the filtrate. The yield of glycerol in the filtrate is 37% (1,2,4-butanetriol is 22% and 1,2,3-butanetriol is 10%) and the yield of butanediol is 49% (1,4-butanediol is 38%, 1,2-butanediol is 8%, 1,3-butanediol is 1% and 2,3-butanediol is 2%).

[0163] Application Example 13

[0164] The application of catalysts in the hydrogenolysis reaction of polyols involves the following specific steps:

[0165] (1) Accurately weigh 3g of erythritol, 12g of deionized water, 2g of ethanol or isopropanol and 0.3g of the catalyst from Example 2 and mix them in a high-pressure reactor. Seal the high-pressure reactor and replace it with nitrogen three times to keep the pressure at 2MPa.

[0166] (2) Turn on the stirrer and adjust the speed of the stirrer to 200 r / min. When the temperature of the high-pressure reactor rises to 200℃, adjust the speed of the stirrer to 1000 r / min to carry out the catalytic hydrogenation reaction. The reaction time is 12 h.

[0167] (3) After the reaction is completed, the mixture is naturally cooled to room temperature. The catalyst and the solution after the reaction are removed. The solution after the reaction is filtered to obtain the filtrate, in which the yield of glycerol is 21% (1,2,4-glycerol is 13% and 1,2,3-glycerol is 8%) and the yield of butanediol is 58% (1,4-butanediol is 38%, 1,2-butanediol is 4%, 1,3-butanediol is 3% and 2,3-butanediol is 2%).

[0168] Application Example 14

[0169] The application of catalysts in the hydrogenolysis reaction of polyols involves the following specific steps:

[0170] (1) Accurately weigh 3g of erythritol, 12g of deionized water and 0.3g of the catalyst from Example 3 and mix them in a high-pressure reactor. Seal the high-pressure reactor and replace it with nitrogen three times to keep the pressure at 2MPa.

[0171] (2) Turn on the stirrer and adjust the speed of the stirrer to 200 r / min. When the temperature of the high-pressure reactor rises to 220℃, adjust the speed of the stirrer to 1000 r / min to carry out the catalytic hydrogenation reaction. The reaction time is 18 h.

[0172] (3) After the reaction is completed, the mixture is naturally cooled to room temperature. The catalyst and the solution after the reaction are removed. The solution after the reaction is filtered to obtain the filtrate, in which the yield of 1,4-anhydride-erythritol is 48%.

[0173] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. The application of a composite multi-interface hydrogenolysis catalyst with zero hydronium-dependent properties in the hydrogenolysis reaction of erythritol, characterized in that, The preparation method of the catalyst includes the following specific steps: (1) Dissolve sodium tungstate in deionized water to obtain a precursor aqueous solution with a metal ion molar concentration of 0.3 mol / L, and set aside for later use; (2) The precursor aqueous solution is added dropwise to the silica support, wherein the mass ratio of the silica support to the metal ions in the precursor aqueous solution is 1:0.

15. The mixture is stirred until it reaches the state of "paste mixture" and the equal volume impregnation is completed to obtain slurry a. (3) Microwave-enhanced impregnation was applied to slurry a for 2 h, the power of which was 180W. Then, it was aged at room temperature for 6 h, dried at 110°C for 8 h, and pulverized to obtain powder A. (4) Place powder A in a muffle furnace and calcine it in an air atmosphere. The temperature is increased to 600°C at a heating rate of 2°C / min and maintained for 4 h. Then, the powder B is obtained by natural cooling. (5) Add the 0.25 mol / L chloroplatinic acid precursor solution dropwise to powder B, stir until it reaches the state of "paste mixture", and complete the equal volume impregnation to obtain slurry b; (6) Microwave-enhanced impregnation was applied to slurry b for 2 hours, the power of which was 180W. Then, it was aged at room temperature for 6 hours, dried at 110°C for 8 hours, and pulverized to obtain powder C. (7) Place powder C in a muffle furnace and calcine it in an air atmosphere. Heat it to 400°C at a heating rate of 2°C / min and maintain it for 4 h. Then let it cool naturally to obtain powder D. (8) Powder D is transferred into a tube furnace, hydrogen is introduced, and the temperature is raised to 300 °C at a heating rate of 2 °C / min for reduction treatment for 5 h. The powder is then naturally cooled to room temperature to obtain the catalyst. The specific steps of the application are as follows: ① Accurately weigh 3g of erythritol, 12g of deionized water and 0.3g of the catalyst and mix them in a high-pressure reactor. Seal the high-pressure reactor and replace it with nitrogen three times to maintain the pressure at 2MPa. ② Turn on the stirrer and adjust the speed of the stirrer to 200 r / min. When the temperature of the high-pressure reactor rises to 220℃, adjust the speed of the stirrer to 1000 r / min to carry out the catalytic hydrogenation reaction. The reaction time is 18 h. ③ After the reaction is complete, the mixture is allowed to cool naturally to room temperature. The catalyst and the solution after the reaction are removed. The solution after the reaction is filtered to obtain the filtrate, in which the yield of 1,4-anhydride-erythritol is 48%.

Images