A process for the hydrogenation of epichlorohydrin catalyzed by a bimetallic catalyst

Abstract

The present application relates to a kind of bimetallic catalyst catalytic epichlorohydrin hydrogenation method, it is characterized in that, under the action of supported bimetallic catalyst, epichlorohydrin and hydrogen gas are reacted to generate 1-chloro-2 propanol and (or) 3-chloro-1 propanol;The supported bimetallic catalyst includes metal A, metal B and carrier material;The metal A is one or several of platinum, rhodium, ruthenium, palladium, iridium;The metal B is one or several of copper, cobalt, nickel, silver, zinc, chromium.The bimetallic catalyst used in the present application can effectively adjust catalytic performance, the conversion rate of epichlorohydrin is high, the selectivity of product molecule can be adjusted, especially the selectivity of 3-chloro-1-propanol is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for catalyzing the hydrogenation of epichlorohydrin by a bimetallic catalyst, belonging to the technical field of the method for catalyzing the hydrogenation of epichlorohydrin. BACKGROUND

[0002] As an important basic organic chemical raw material, epichlorohydrin can be converted into epoxy resin, glycerol, chlorohydrin rubber and other high value-added derivatives through various technical means. Among them, the catalytic hydrogenation technology has been widely used in industrial production due to its atom economy and green environmental protection. The catalytic hydrogenation of epichlorohydrin mainly generates two products: 1-chloro-2-propanol and 3-chloro-1-propanol, which are important intermediates for fine chemical industry and drug synthesis. As a kind of bifunctional compound, it has the typical chemical properties of alcohol hydroxyl and halogen atom. It has the reducing property and weak acidity of general alcohol, and can be converted into aldehyde, ketone or acid by catalytic oxidation, or can react with sodium to form an important reagent in organic synthesis-sodium alcohol.

[0003] Specifically, 1-chloro-2-propanol is mainly used for organic synthesis, and is often used for synthesizing chlorpromazine in medicine; it is often used as an oxidized propylene raw material and a hydroxypropylating agent in industry. While 3-chloro-1-propanol is mainly used for the synthesis of various drugs.

[0004] At present, there are few related researches on the catalytic hydrogenation of epichlorohydrin, and the catalysts used are mainly palladium / activated carbon, such as Wuwei's New Synthesis Route of Tenofovir Disoproxil Fumarate. However, the products reported by the existing catalytic hydrogenation reaction of epichlorohydrin are mostly 1-chloro-2-propanol, and no research report on the selective control of the catalytic hydrogenation reaction of epichlorohydrin has been found. The generation of 3-chloro-1-propanol requires the adjustment of the active site of the catalyst, which is difficult to achieve by using a single metal catalyst. In addition, the existing catalysts are prone to dechlorination during the catalytic hydrogenation process of epichlorohydrin. SUMMARY

[0005] The purpose of the present application is to solve the problems raised in the above background, and to provide a method for catalyzing the hydrogenation of epichlorohydrin by a bimetallic catalyst, which can not only catalyze the hydrogenation of epichlorohydrin efficiently, but also improve the yield of the target products 1-chloro-2-propanol and 3-chloro-1-propanol; at the same time, it can control the selectivity of the reaction to the target product, improve the selectivity of 3-chloro-1-propanol, inhibit dechlorination and reduce side reactions.

[0006] The purpose of the present application is to solve the problems raised in the above background, and to provide a method for catalyzing the hydrogenation of epichlorohydrin by a bimetallic catalyst, which can not only catalyze the hydrogenation of epichlorohydrin efficiently, but also improve the yield of the target products 1-chloro-2-propanol and 3-chloro-1-propanol; at the same time, it can control the selectivity of the reaction to the target product, improve the selectivity of 3-chloro-1-propanol, inhibit dechlorination and reduce side reactions.

[0007] The supported bimetallic catalyst comprises metal A, metal B and a carrier material.

[0008] The metal A is one or more of platinum, rhodium, ruthenium, palladium, iridium, and preferably platinum and / or ruthenium.

[0009] The metal B is one or more of copper, cobalt, nickel, silver, zinc, chromium, and preferably copper and / or cobalt.

[0010] The carrier material is one or more of activated carbon, zinc oxide, iron oxide, zirconium oxide, titanium dioxide or magnesium oxide, and preferably activated carbon.

[0011] The mass percentage of metal A in the supported bimetallic catalyst is 0.1-20%, and the mass percentage of metal B is 0.1-20%.

[0012] A method for catalyzing the hydrogenation of epichlorohydrin by a bimetallic catalyst, comprising the following steps:

[0013] (1) First, dissolve the substrate epichlorohydrin in a solvent or directly use reduced chloropropane as the reaction liquid at room temperature;

[0014] (2) Add the supported bimetallic catalyst to the reaction device, and then add the reactant in step (1);

[0015] (3) After sealing the reaction device, introduce H2to replace the air in the device, and then inject a certain pressure of H2into the device;

[0016] (4) Under stirring, increase the temperature to the required temperature, and after the reaction is completed, obtain the product.

[0017] In step (2), the mass ratio of the supported metal catalyst to epichlorohydrin is in the range of 1: (1-2000), and preferably 1: (1-500); in step (3), the hydrogen pressure or partial pressure is 0.005-15 MPa, and preferably 1-5 MPa; in step (4), the temperature of the hydrogenation reaction is -20-220°C, and preferably 20-120°C.

[0018] The reaction time is 20 min-40 h, and the concentration percentage of epichlorohydrin in the reactant is 0.1-100%.

[0019] The supported bimetallic catalyst has two preparation methods, and the steps are as follows:

[0020] Method one:

[0021] (1) Prepare a supported metal catalyst of metal A;

[0022] (2) Prepare an ammonia complex metal hydroxide solution of metal B;

[0023]

[0023] (3) mixing the supported metal catalyst of metal A obtained in step (1) with the ammonia complex metal hydroxide solution of metal B obtained in step (2) in a protective atmosphere, stirring uniformly at room temperature, and adding a reducing agent dropwise under the protection of an inert atmosphere, and stirring until the ammonia complex metal hydroxide solution of metal B is completely absorbed, to obtain a bimetallic catalyst.

[0024] According to the present application, the specific steps for preparing the supported metal catalyst of metal A in step (1) are as follows: preparing a metal nanoparticle colloid by using a polyol reduction method or a sol-gel method; dispersing a carrier material in a solvent, and then adding the metal nanoparticle colloid, performing solid-liquid separation after the reaction is completed, and obtaining the supported metal catalyst of metal A through vacuum freeze drying;

[0025] According to the present application, the specific steps for preparing the ammonia complex metal hydroxide solution of metal B in step (2) are as follows: dissolving a metal salt corresponding to metal B in a solvent, and then adding an alkaline solution to generate a hydroxide precipitate, performing solid-liquid separation, and then dissolving the precipitate in ammonia water to obtain the ammonia complex metal hydroxide solution;

[0026] According to the present application, the protective atmosphere in step (3) is any one or a combination of at least two of nitrogen, argon, or helium.

[0027] According to the present application, the reducing agent in step (3) is any one or a combination of at least two of sodium borohydride, hydrazine hydrate, lithium aluminum hydride, ascorbic acid, sodium hypophosphite, hydrogen iodide, sulfur, or hydrogen sulfide.

[0028] Preferably, in step (3), the supported metal catalyst of metal A is dispersed in a solvent before being mixed with the ammonia complex metal hydroxide solution of metal B, which can make metal B better adhere to the surface of the supported metal catalyst of metal A.

[0029] According to the present application, in step (3), the solvent is water or alcohol.

[0030] Preferably, the alcohol is any one or a combination of at least two of methanol, ethanol, or ethylene glycol.

[0031] The methods for preparing the supported metal catalyst of metal A in step (1) and the ammonia complex metal hydroxide solution of metal B in step (2) are selected from methods known in the art, and no special limitation is made thereto.

[0032] In particular, when metal A in step (1) of the present method for preparing the supported metal catalyst of metal A is palladium, an impregnation method known in the art is used, and no special limitation is made thereto.

[0033] Method two:

[0034] (1) preparing an ammonia complex metal hydroxide solution of metal B;

[0035] (2) preparing a nanoparticle colloid of metal A;

[0036] (3) mixing the ammonia complex metal hydroxide solution of metal B prepared in step (1) with a carrier, heating and drying under magnetic stirring until the liquid nearly disappears, and then adding a reducing agent dropwise to the obtained solid powder under protection of an inert atmosphere to prepare a supported metal catalyst of metal B;

[0037] (4) mixing the nanoparticle colloid of metal A prepared in step (2) with the supported metal catalyst of metal B prepared in step (3), and stirring until the colloid is completely adsorbed to obtain a supported bimetallic catalyst

[0038] According to the present application, the ammonia complex metal hydroxide solution of metal B prepared in step (1) is prepared by dissolving a metal salt corresponding to metal B in a solvent, adding a basic solution to generate a hydroxide precipitate, separating the solid from the liquid, and then adding the precipitate to ammonia water to dissolve and obtain the ammonia complex metal hydroxide solution;

[0039] According to the present application, the protective atmosphere in step (3) is any one or a combination of at least two of nitrogen, argon or helium;

[0040] According to the present application, the reducing agent in step (3) is any one or a combination of at least two of sodium borohydride, hydrazine hydrate, lithium aluminum hydride, ascorbic acid, sodium hypophosphite, hydrogen iodide, sulfur or hydrogen sulfide.

[0041] Preferably, in step (4), the supported metal catalyst of metal B is dispersed in a solvent before being mixed with the nanoparticle colloid of metal A, which can make metal A better adhere to the surface of the supported metal catalyst of metal B.

[0042] The methods for preparing the ammonia complex metal hydroxide solution of metal B in step (1) and the nanoparticle colloid of metal A in step (2) are selected from methods known in the art, and no special limitation is made.

[0043] In particular, when metal A is palladium in the preparation of the supported bimetallic catalyst according to the present application, the impregnation method known in the art is used, and no special limitation is made.

[0044] Compared with the prior art, the present application has the following advantages:

[0045] The application discloses a method for catalyzing hydrogenation of epichlorohydrin by using a bimetallic catalyst, and the bimetallic catalyst can effectively adjust the catalytic performance, and the conversion rate of the epichlorohydrin is high. The catalytic performance can be effectively adjusted by changing the ratio between the metals, and the epichlorohydrin can be efficiently catalyzed, and the yield of the target products 1-chloro-2-propanol and 3-chloro-1-propanol is improved. Meanwhile, the selectivity of the reaction to the target products can be regulated, and the selectivity of 3-chloro-1-propanol is improved. DETAILED DESCRIPTION

[0046] The application will be further described below by representative specific embodiments, but the content of the application is not limited to the following examples only.

[0047] Example 1

[0048] Application of platinum copper / activated carbon (3%Pt / C-0.1%Cu) catalyst in selective hydrogenation of epichlorohydrin

[0049] (1) 1g of H2PtCl6·6H2O (Pt≥37.0%) was completely dissolved in 50ml of ethylene glycol, 50ml of NaOH ethylene glycol solution (0.25mol / L) was added under continuous stirring at room temperature, and the mixture was heated to 160°C under protection of an inert atmosphere for 3h. After cooling to room temperature, Pt colloid (0.32wt%) was obtained. 2.0g of activated carbon was uniformly dispersed in 100ml of ethylene glycol, and 18.75g of the Pt colloid was added dropwise. After uniform stirring at room temperature for 2h, 300ml of deionized water was added, and the mixture was continuously stirred for 3h. After the reaction was completed, the sample was washed with an ethanol aqueous solution and centrifuged, and the obtained sample was dried in a vacuum freeze dryer for 20h to obtain a platinum / activated carbon (3%Pt / C) catalyst.

[0050] (2) 0.32g of anhydrous copper chloride was dissolved in 50ml of deionized water and ultrasonically dispersed for 1h, and 20ml of 0.1mol / L NaOH solution was added to obtain a blue precipitate which was continuously stirred for 10min. After centrifugation and water washing, 50ml of ammonia water (wt%=25.0%-28%) was added to the transferred precipitate, and the mixture was magnetically stirred until completely dissolved to obtain a deep blue copper ammonia solution (0.003g / ml).

[0051] (3) The platinum / activated carbon catalyst prepared in step (1) was dispersed in 50ml of deionized water, and 0.67ml of the copper ammonia solution was added dropwise. The mixture was heated to near disappearance of the liquid at 60°C, and then cooled to room temperature. 50ml of 0.1mol / L NaOH solution was added, and the mixture was uniformly stirred at room temperature. 50ml of 0.27mol / L NaBH4 solution was added under protection of an inert atmosphere, and the mixture was reacted for 2h. After water washing, the mixture was vacuum freeze-dried to obtain a platinum copper / activated carbon (3%Pt / C-0.1%Cu) catalyst.

[0052] (4) Put 0.05 g of the prepared platinum copper / activated carbon (3% Pt / C-0.1% Cu) catalyst, 10.00 g of epichlorohydrin, and 30 ml of cyclohexane into a 100 ml high-pressure reaction kettle, replace the air with hydrogen for 6 times, then charge 4 MPa of hydrogen, and then start stirring to heat to 90°C for 2 h, cool down, filter, and use gas chromatography to perform qualitative and quantitative analysis on the hydrogenated filtrate.

[0053] Example 2

[0054] Application of platinum copper / activated carbon (0.5% Pt / C-0.3% Cu) catalyst in selective hydrogenation of epichlorohydrin

[0055] (1) Dissolve 1 g of H2PtCl6·6H2O (Pt≥37.0%) completely in 50 ml of ethylene glycol, add 50 ml of a NaOH ethylene glycol solution (0.25 mol / L) under continuous stirring at room temperature, heat to 160°C under inert atmosphere protection for 3 h, and then cool to room temperature to obtain Pt colloid (0.32 wt%). Disperse 2.0 g of activated carbon in 100 ml of ethylene glycol, and then add 3.125 g of the Pt colloid dropwise, uniformly stir for 2 h at room temperature, add 300 ml of deionized water, and continue to stir for 3 h. After the reaction is completed, wash with an ethanol aqueous solution and centrifuge, and then dry the obtained sample in a vacuum freeze dryer for 20 h to obtain a platinum / activated carbon (0.5% Pt / C) catalyst.

[0056] (2) Dissolve 0.32 g of anhydrous copper chloride in 50 ml of deionized water and ultrasonically disperse for 1 h, add 20 ml of a 0.1 mol / L NaOH solution, and obtain a blue precipitate. Continue to stir for 10 min, wash with water after centrifugation, add 50 ml of ammonia water (wt%=25.0%-28%) to the transferred precipitate, and magnetically stir until completely dissolved to obtain a deep blue copper ammonia solution (0.003 g / ml).

[0057] (3) Disperse the platinum / activated carbon catalyst prepared in step (1) into 50 ml of deionized water, add 2.01 ml of the copper ammonia solution dropwise, and dry at 60°C until the liquid nearly disappears. Cool to room temperature, add 50 ml of a 0.1 mol / L NaOH solution, and uniformly stir at room temperature. Add 50 ml of a 0.27 mol / L NaBH4 solution under inert atmosphere protection, react for 2 h, wash with water, and vacuum freeze dry to obtain a platinum copper / activated carbon (0.5% Pt / C-0.3% Cu) catalyst.

[0058] (4) Put 0.05 g of the prepared platinum copper / activated carbon (0.5% Pt / C-0.3% Cu) catalyst, 10.00 g of epichlorohydrin, and 30 ml of cyclohexane into a 100 ml high-pressure reaction kettle, replace the air with hydrogen for 6 times, then charge 4 MPa of hydrogen, and then start stirring and heating to 90°C for 2 h, then cool down, filter, and use gas chromatography to perform qualitative and quantitative analysis on the hydrogenated filtrate.

[0059] Example 3

[0060] Application of platinum copper / activated carbon (15% Pt / C-18% Cu) catalyst in selective hydrogenation of epichlorohydrin

[0061] (1) Dissolve 2 g of H2PtCl6·6H2O (Pt≥37.0%) completely in 100 ml of ethylene glycol, add 100 ml of a NaOH ethylene glycol solution (0.25 mol / L) under continuous stirring at room temperature, heat to 160°C under inert atmosphere protection for 3 h, and then cool to room temperature to obtain Pt colloid (0.32 wt%). Disperse 2.0 g of activated carbon uniformly in 200 ml of ethylene glycol, and then add 93.75 Pt colloid dropwise, uniformly stir for 2 h at room temperature, add 300 ml of deionized water, and continue stirring for 3 h. After the reaction is completed, wash with an ethanol aqueous solution and centrifuge, and then dry the obtained sample in a vacuum freeze dryer for 20 h to obtain a platinum / activated carbon (15% Pt / C) catalyst.

[0062] (2) Dissolve 0.96 g of anhydrous copper chloride in 150 ml of deionized water and ultrasonically disperse for 1 h, add 60 ml of a 0.1 mol / L NaOH solution, and obtain a blue precipitate. Continue stirring for 10 min, wash with water after centrifugation, add 150 ml of ammonia water (wt%=25.0%-28%) to the transferred precipitate, and magnetically stir until completely dissolved to obtain a deep blue copper ammonia solution (0.003 g / ml).

[0063] (3) Disperse the platinum / activated carbon catalyst prepared in step (1) into 50 ml of deionized water, add 120.6 ml of the copper ammonia solution dropwise, and dry at 60°C until the liquid nearly disappears. Cool to room temperature, add 50 ml of a 0.1 mol / L NaOH solution, and uniformly stir at room temperature. Add 50 ml of a 0.27 mol / L NaBH4 solution under inert atmosphere protection, react for 2 h, wash with water, and vacuum freeze dry to obtain a platinum copper / activated carbon (15% Pt / C-18% Cu) catalyst.

[0064] (4) Put 0.05 g of the prepared platinum copper / activated carbon (15% Pt / C-18% Cu) catalyst, 10.00 g of epichlorohydrin, and 30 ml of cyclohexane into a 100 ml high-pressure reaction kettle, replace the air with hydrogen for 6 times, then charge 4 MPa of hydrogen, and then start stirring to heat to 90°C for 2 h, cool down, filter, and use gas chromatography to analyze the hydrogenated filtrate.

[0065] Example 4

[0066] Application of platinum copper / activated carbon (3% Pt / C-0.1% Cu) catalyst in selective hydrogenation of epichlorohydrin

[0067] (1) Dissolve 1 g of H2PtCl6·6H2O (Pt≥37.0%) completely in 50 ml of ethylene glycol, add 50 ml of a NaOH ethylene glycol solution (0.25 mol / L) under continuous stirring at room temperature, heat to 160°C under inert atmosphere protection for 3 h, and then cool to room temperature to obtain Pt colloid (0.32 wt%). Disperse 2.0 g of activated carbon in 100 ml of ethylene glycol, and then add 18.75 g of the Pt colloid dropwise, uniformly stir at room temperature for 2 h, add 300 ml of deionized water, and continue to stir for 3 h. After the reaction is completed, wash with an ethanol aqueous solution and centrifuge, and then dry the obtained sample in a vacuum freeze dryer for 20 h to obtain a platinum / activated carbon (3% Pt / C) catalyst.

[0068] (2) Dissolve 0.32 g of anhydrous copper chloride in 50 ml of deionized water and ultrasonically disperse for 1 h, add 20 ml of a 0.1 mol / L NaOH solution, and obtain a blue precipitate. Continue to stir for 10 min, wash with water after centrifugation, add 50 ml of ammonia water (wt%=25.0%-28%) to the transferred precipitate, and magnetically stir until completely dissolved to obtain a deep blue copper ammonia solution (0.003 g / ml).

[0069] (3) Disperse the platinum / activated carbon catalyst prepared in step (1) into 50 ml of deionized water, add 0.67 ml of the copper ammonia solution dropwise, and dry at 60°C until the liquid nearly disappears. Cool to room temperature, add 50 ml of a 0.1 mol / L NaOH solution, and uniformly stir at room temperature. Add 50 ml of a 0.27 mol / L NaBH4 solution under inert atmosphere protection, react for 2 h, wash with water, and vacuum freeze dry to obtain a platinum copper / activated carbon (3% Pt / C-0.1% Cu) catalyst.

[0070] (4) Put 5 g of the prepared platinum copper / activated carbon (3% Pt / C-0.1% Cu) catalyst, 5 g of epichlorohydrin, and 30 ml of cyclohexane into a 100 ml high-pressure reaction kettle, replace the air with hydrogen for 6 times, then fill in 4 MPa of hydrogen, and then start stirring to heat to 90°C for 30 min, cool down, filter, and use gas chromatography to perform qualitative and quantitative analysis on the hydrogenated filtrate.

[0071] Example 5

[0072] Application of platinum copper / activated carbon (3% Pt / C-0.1% Cu) catalyst in selective hydrogenation of epichlorohydrin

[0073] (1) Dissolve 1 g of H2PtCl6·6H2O (Pt≥37.0%) completely in 50 ml of ethylene glycol, add 50 ml of a NaOH ethylene glycol solution (0.25 mol / L) under continuous stirring at room temperature, heat to 160°C under inert atmosphere protection for 3 h, and then cool to room temperature to obtain Pt colloid (0.32 wt%). Disperse 2.0 g of activated carbon uniformly in 100 ml of ethylene glycol, and then add 18.75 g of the Pt colloid dropwise, uniformly stir for 2 h at room temperature, add 300 ml of deionized water, and continue to stir for 3 h. After the reaction is completed, wash with an ethanol aqueous solution and centrifuge, and then dry the obtained sample in a vacuum freeze dryer for 20 h to obtain a platinum / activated carbon (3% Pt / C) catalyst.

[0074] (2) Dissolve 0.32 g of anhydrous copper chloride in 50 ml of deionized water and ultrasonically disperse for 1 h, add 20 ml of a 0.1 mol / L NaOH solution, and obtain a blue precipitate. Continue to stir for 10 min, wash with water after centrifugation, add 50 ml of ammonia water (wt%=25.0%-28%) to the transferred precipitate, and magnetically stir until completely dissolved to obtain a deep blue copper ammonia solution (0.003 g / ml).

[0075] (3) Disperse the platinum / activated carbon catalyst prepared in step (1) into 50 ml of deionized water, add 0.67 ml of the copper ammonia solution dropwise, and dry at 60°C until the liquid nearly disappears. Cool to room temperature, add 50 ml of a 0.1 mol / L NaOH solution, and uniformly stir at room temperature. Add 50 ml of a 0.27 mol / L NaBH4 solution under inert atmosphere protection, react for 2 h, wash with water, and vacuum freeze dry to obtain a platinum copper / activated carbon (3% Pt / C-0.1% Cu) catalyst.

[0076] (4) Put 0.05 g of the prepared platinum copper / activated carbon (3% Pt / C-0.1% Cu) catalyst, 90.00 g of epichlorohydrin, and 200 ml of cyclohexane into a 500 ml high-pressure reaction kettle, replace the air with hydrogen for 6 times, then charge 4 MPa of hydrogen, and then start stirring to heat to 90°C for 40 h, cool down, filter, and use gas chromatography to analyze the hydrogenated filtrate.

[0077] Example 6

[0078] Application of copper platinum / activated carbon (0.1% Cu / C-3% Pt) catalyst in selective hydrogenation of epichlorohydrin

[0079] (1) Dissolve 0.32 g of anhydrous copper chloride in 50 ml of deionized water and ultrasonically disperse for 1 h, add 20 ml of 0.1 mol / L NaOH solution, and obtain a blue precipitate. Continue stirring for 10 min, centrifuge, and wash with water. Add 50 ml of ammonia water (wt%=25.0%-28%) to the transferred precipitate, and magnetically stir until completely dissolved to obtain a deep blue copper ammonia solution (0.003 g / ml).

[0080] (2) Disperse 2.0 g of activated carbon carrier into 50 ml of deionized water, drop 0.67 ml of copper ammonia solution, and bake at 60°C until the liquid is almost gone. Cool to room temperature, add 50 ml of 0.1 mol / L NaOH solution, and stir uniformly at room temperature. Add 50 ml of 0.27 mol / L NaBH4 solution under inert atmosphere protection, react for 2 h, wash with water, and vacuum freeze dry to obtain a copper / activated carbon (0.1% Cu / C) catalyst.

[0081] (3) Dissolve 1 g of H2PtCl6·6H2O (Pt≥37.0%) completely in 50 ml of ethylene glycol, and continuously stir at room temperature. Add 50 ml of NaOH ethylene glycol solution (0.25 mol / L), heat to 160°C for 3 h under inert atmosphere protection, cool to room temperature to obtain Pt colloid (0.32 wt%). Disperse the obtained copper / activated carbon (0.1% Cu / C) uniformly in 100 ml of ethylene glycol, and drop 18.75 g of Pt colloid into it drop by drop. Stir uniformly at room temperature for 2 h, then add 300 ml of deionized water, and continue stirring for 3 h. After the reaction is completed, wash with an ethanol aqueous solution and centrifuge. Dry the obtained sample in a vacuum freeze dryer for 20 h to obtain a platinum copper / activated carbon (0.1% Cu / C-3% Pt) catalyst.

[0082] (4) The prepared platinum copper / activated carbon (0.1% Cu / C-3% Pt) catalyst 0.05 g, 10.00 g of epichlorohydrin, 30 ml of cyclohexane were added into a 100 ml high-pressure reaction kettle, hydrogen was used to replace air for 6 times, 4 MPa of hydrogen was filled, then stirring was started, the temperature was raised to 90°C, and the reaction was carried out for 2 h, then the temperature was lowered, filtration was carried out, and the hydrogenated filtrate was subjected to qualitative and quantitative analysis by gas chromatography

[0083] Example 7

[0084] Application of platinum cobalt / activated carbon (3% Pt / C-0.1% Co) catalyst in selective hydrogenation of epichlorohydrin

[0085] The preparation process of the specific catalyst, the reaction process and the detection method are the same as those in Example 1, except that the anhydrous copper chloride in step (2) is changed to the corresponding mass ratio of anhydrous cobalt chloride, and the catalyst is changed to 3% Pt / C-0.1% Co.

[0086] Example 8

[0087] Application of platinum nickel / activated carbon (3% Pt / C-0.1% Ni) catalyst in selective hydrogenation of epichlorohydrin

[0088] The preparation process of the specific catalyst, the reaction process and the detection method are the same as those in Example 1, except that the anhydrous copper chloride in step (2) is changed to the corresponding mass ratio of anhydrous cobalt chloride, and the catalyst is changed to 3% Pt / C-0.1% Co.

[0089] Example 9

[0090] Application of platinum zinc / activated carbon (3% Pt / C-0.1% Zn) catalyst in selective hydrogenation of epichlorohydrin

[0091] The preparation process of the specific catalyst, the reaction process and the detection method are the same as those in Example 1, except that the anhydrous copper chloride in step (2) is changed to the corresponding mass ratio of anhydrous cobalt chloride, and the catalyst is changed to 3% Pt / C-0.1% Co.

[0092] Example 10

[0093] Application of platinum silver / activated carbon (3% Pt / C-0.1% Ag) catalyst in selective hydrogenation of epichlorohydrin

[0094] The preparation process of the specific catalyst, the reaction process and the detection method are the same as those in Example 1, except that the anhydrous copper chloride in step (2) is changed to the corresponding mass ratio of anhydrous cobalt chloride, and the catalyst is changed to 3% Pt / C-0.1% Co.

[0095] Example 11

[0096] Application of platinum-chromium / activated carbon (3%Pt / C-0.1%Cr) catalyst in selective hydrogenation of epichlorohydrin

[0097] The preparation process, reaction process and detection method of the specific catalyst are the same as those in Example 1, except that the anhydrous copper chloride in step (2) is changed to the corresponding mass ratio of chromium chloride, and the catalyst is changed to 3%Pt / C-0.1%Cr.

[0098] Example 12

[0099] Application of ruthenium-copper / titanium dioxide (3%Ru / TiO2-0.1%Cu) catalyst in selective hydrogenation of epichlorohydrin

[0100] (1) Dissolve 1 g of RuCl3.xH2O completely in 50 ml of ethylene glycol, add 50 ml of NaOH ethylene glycol solution (0.25 mol / L) under continuous stirring at room temperature, heat to 160°C under inert atmosphere protection for 3 h, and cool to room temperature to obtain Ru colloid. Disperse 2.0 g of titanium dioxide uniformly in 100 ml of ethylene glycol, and add 18.75 g of Ru colloid dropwise, uniformly stir at room temperature for 2 h, then add 300 ml of deionized water, continue to stir for 3 h, after the reaction is complete, wash with an ethanol aqueous solution and centrifuge, and dry the obtained sample in a vacuum freeze dryer for 20 h to obtain a ruthenium / titanium dioxide catalyst.

[0101] (2) Dissolve 0.32 g of anhydrous copper chloride in 50 ml of deionized water and ultrasonically disperse for 1 h, add 20 ml of 0.1 mol / L NaOH solution, and obtain a blue precipitate which is continuously stirred for 10 min, washed with water after centrifugation, and add 50 ml of ammonia water (wt%=25.0%-28%) to the transferred precipitate, magnetically stir until completely dissolved, and obtain a deep blue copper ammonia solution (0.003 g / ml).

[0102] (3) Disperse the ruthenium / titanium dioxide catalyst into 50 ml of deionized water, add 0.67 ml of copper ammonia solution dropwise, and bake at 60°C until the liquid is almost gone, cool to room temperature, add 50 ml of 0.1 mol / L NaOH solution, and stir uniformly at room temperature. Add 50 ml of 0.27 mol / L NaBH4 solution under inert atmosphere protection, react for 2 h, wash with water, and vacuum freeze dry to obtain a ruthenium-copper / titanium dioxide (3%Ru / TiO2-0.1%Cu) catalyst.

[0103] (4) The prepared ruthenium copper / titanium dioxide (3% Ru / TiO2-0.1% Cu) catalyst 0.05 g, 10.00 g of epichlorohydrin, 30 ml of cyclohexane were added into a 100 ml high-pressure reactor, and the air was replaced by hydrogen for 6 times, then 4 MPa of hydrogen was filled, and then the stirring was started, the temperature was raised to 90°C, and the reaction was carried out for 2 h, then the temperature was lowered, the filter was added, and the hydrogen filter was analyzed by gas chromatography.

[0104] Example 13

[0105] Application of rhodium copper / zinc oxide (3% Rh / ZnO-0.1% Cu) catalyst in selective hydrogenation of epichlorohydrin

[0106] The preparation process, reaction process and detection method of the specific catalyst are the same as those of Example 12, except that RuCl3.xH2O in step (1) is changed to the corresponding mass ratio of RhCl3.3H2O, 2.0 g of TiO2 carrier is changed to 2.0 g of ZnO carrier, and the catalyst is changed to 3% Rh / ZnO-0.1% Cu.

[0107] Example 14

[0108] Application of iridium copper / magnesium oxide (3% Ir / MgO-0.1% Cu) catalyst in selective hydrogenation of epichlorohydrin

[0109] The preparation process, reaction process and detection method of the specific catalyst are the same as those of Example 12, except that RuCl3.xH2O in step (1) is changed to the corresponding mass ratio of IrCl3.xH2O, 2.0 g of TiO2 carrier is changed to 2.0 g of MgO carrier, and the catalyst is changed to 3% Rh / MgO-0.1% Cu.

[0110] Example 15

[0111] Application of palladium copper / iron oxide and zirconium oxide (3% Pd / Fe2O3-ZrO2-0.1% Cu) catalyst in selective hydrogenation of epichlorohydrin

[0112] (1) 0.18 g of H2PdCl6 was dissolved in 100 ml of deionized water, and after complete dissolution, 1 g of iron oxide and 1 g of zirconium oxide carrier were mixed, and after 24 h of immersion, centrifugation and drying, a palladium / iron oxide and zirconium oxide (3% Pd / Fe2O3-ZrO2) catalyst was obtained.

[0113] (2) 0.32 g of anhydrous copper chloride was dissolved in 50 ml of deionized water and ultrasonically dispersed for 1 h, 20 ml of 0.1 mol / L NaOH solution was added, a blue precipitate was obtained, and stirring was continued for 10 min. After centrifugation, the precipitate was washed with water, 50 ml of ammonia water (wt% = 25.0%-28%) was added to the transferred precipitate, and magnetic stirring was performed until complete dissolution, to obtain a deep blue copper ammonia solution (0.003 g / ml).

[0114] (3) The palladium / iron oxide and zirconium oxide catalyst was dispersed in 50 ml of deionized water, 0.67 ml of the copper ammonia solution was added dropwise, and the liquid was heated to near disappearance at 60°C, and then cooled to room temperature. 50 ml of 0.1 mol / L NaOH solution was added and stirred uniformly at room temperature. 50 ml of 0.27 mol / L NaBH4 solution was added under inert atmosphere protection, and the reaction was carried out for 2 h. After washing with water, vacuum freeze-drying was performed to obtain the palladium copper / iron oxide and zirconium oxide (3%Pd / Fe2O3-ZrO2-0.1%Cu) catalyst.

[0115] (4) The palladium copper / iron oxide and zirconium oxide (3%Pd / Fe2O3-ZrO2-0.1%Cu) catalyst prepared above was added to 10.00 g of epichlorohydrin, 30 ml of cyclohexane, and 100 ml of a high-pressure reaction kettle, and the air was replaced with hydrogen for 6 times, and then 4 MPa of hydrogen was filled. Then, stirring was started, and the temperature was raised to 90°C, and the reaction was carried out for 2 h. After cooling, filtration was performed, and the hydrogenation filtrate was analyzed qualitatively and quantitatively by gas chromatography.

[0116] Comparative Example 1

[0117] The platinum / activated carbon (3%Pt / C) catalyst was prepared as follows: 1 g of H2PtCl6·6H2O (Pt≥37.0%) was completely dissolved in 50 ml of ethylene glycol, and 50 ml of a NaOH ethylene glycol solution (0.25 mol / L) was added under continuous stirring at room temperature. The mixture was heated to 160°C for 3 h under inert atmosphere protection, and then cooled to room temperature to obtain Pt colloid (0.32 wt%). 2.0 g of activated carbon was uniformly dispersed in 100 ml of ethylene glycol, and 18.75 g of the Pt colloid was added dropwise. After uniform stirring at room temperature for 2 h, 300 ml of deionized water was added, and stirring was continued for 3 h. After the reaction was completed, the sample was washed with an ethanol aqueous solution and centrifuged, and then dried in a vacuum freeze-drying machine for 20 h to obtain the platinum / activated carbon (3%Pt / C) catalyst.

[0118] The platinum / activated carbon (3%Pt / C) catalyst prepared above was added to 10.00 g of epichlorohydrin, 30 ml of cyclohexane, and 100 ml of a high-pressure reaction kettle, and the air was replaced with hydrogen for 6 times, and then 4 MPa of hydrogen was filled. Then, stirring was started, and the temperature was raised to 90°C, and the reaction was carried out for 2 h. After cooling, filtration was performed, and the hydrogenation filtrate was analyzed qualitatively and quantitatively by gas chromatography.

[0119] Comparative Example 2

[0120] A Ni-Pt / SBA-15 bimetallic catalyst was prepared by using the method for synthesizing a Ni-Pt bimetallic catalyst disclosed in CN107088435A, and the carrier was SBA-15 molecular sieve, wherein the Ni loading was 17.3%, and the Pt loading was 5.7%.

[0121] 0.05 g of the 17.3%Ni-5.7%Pt / SBA-15 catalyst prepared above, 10.00 g of epichlorohydrin, and 30 ml of cyclohexane were added into a 100 ml high-pressure reactor, air was replaced by hydrogen for 6 times, 4 MPa of hydrogen was then filled, and then stirring was started, the temperature was raised to 90°C, and the reaction was carried out for 2 h, then the temperature was lowered, filtration was carried out, and the hydrogenated filtrate was subjected to qualitative and quantitative analysis by using gas chromatography.

[0122] The product of the comparative example was subjected to qualitative and quantitative analysis by using gas chromatography, and the experimental results are shown in Table 1.

[0123] No. Catalyst Epichlorohydrin conversion (%) 1-Chloro-2-propanol selectivity (%) 3-Chloro-1-propanol selectivity (%) Dechlorination byproduct selectivity (%) Comparative Example 1 3% Pt / C 70.3 67.9 0.3 31.8 Comparative Example 2 17.3% Ni-5.7% Pt / SBA-15 65.5 60.7 0.1 39.2 Example 1 3% Pt / C-0.1% Cu 100 87.4 3.9 8.7 Example 2 0.5% Pt / C-0.3% Cu 98 89.5 4.0 6.5 Example 3 15% Pt / C-18% Cu 92.0 91.4 3.8 4.8 Example 4 3% Pt / C-0.1% Cu 100 91.0 3.3 5.7 Example 5 3% Pt / C-0.1% Cu 96.5 85.5 4.3 10.2 Example 6 0.1% Cu / C-3% Pt 98.0 74.0 14.5 11.5 Example 7 3% Pt / C-0.1% Co 94.0 58.8 30.1 11.1 Example 8 3% Pt / C-0.1% Ni 99.6 89.4 2.3 8.3 Example 9 3% Pt / C-0.1% Zn 99.3 87.5 2.7 9.8 Example 10 3% Pt / C-0.1% Ag 97.0 85.2 4.6 10.2 Example 11 3% Pt / C-0.1% Cr 87.4 70.9 23.6 5.5 Example 12 3% Ru / TiO2-0.1% Cu 92.0 89.9 2.9 7.2 Example 13 3% Rh / ZnO-0.1% Cu 99.2 86.1 5.5 8.4 Example 14 3% Ir / MgO-0.1% Cu 96.9 88.8 4.3 6.9 Example 15 3% Rh / ZnO-0.1% Cu 3% Pd / Fe203-Zr02-0.1% Cu 95.1 90.1 3.5 6.4

[0124] As shown in Table 1, each type of catalyst has high activity for the selective catalytic hydrogenation of epichlorohydrin; in addition, compared with Comparative Example 1, the introduction of the second metal changes the selectivity of the reaction to the target product, and the dechlorination byproduct is reduced. This shows that the method not only can efficiently catalyze the hydrogenation of epichlorohydrin, effectively inhibit the occurrence of dechlorination side reactions, and improve the yield of the target products 1-chloro-2-propanol and 3-chloro-1-propanol; but also can regulate the selectivity of the reaction to the target product, and improve the selectivity of 3-chloro-1-propanol.

[0125] The above only describes typical embodiments of the present application and is not intended to limit the present application in other forms. It should be noted that modifications and equivalent replacements can be made by those skilled in the art based on the disclosed technical content, and these still belong to the protection scope of the present application.

Claims

1. A process for the catalytic hydrogenation of epichlorohydrin with a bimetallic catalyst, characterized in that: Under the action of the supported bimetallic catalyst, epichlorohydrin and hydrogen react to generate 1-chloro-2-propanol and / or 3-chloro-1-propanol; The supported bimetallic catalyst comprises metal A, metal B and a carrier material; The metal A is one or more of platinum, rhodium, ruthenium, palladium and iridium; the metal B is one or more of copper, cobalt, nickel, silver, zinc and chromium; The mass percentage of the metal A in the supported bimetallic catalyst is 0.1-20%; the mass percentage of the metal B is 0.1-20%; The preparation of the supported bimetallic catalyst comprises the following steps: (1) preparing a supported metal catalyst of metal A; (2) preparing an ammonia-coordinated metal hydroxide solution of metal B; (3) mixing the supported metal catalyst of metal A obtained in step (1) with the ammonia-coordinated metal hydroxide solution of metal B obtained in step (2) in a protective atmosphere, stirring uniformly at room temperature, adding a reducing agent dropwise under the protection of inert atmosphere, and obtaining the bimetallic catalyst after the ammonia-coordinated metal hydroxide solution of metal B is completely adsorbed.

2. A process for the hydrogenation of epichlorohydrin catalyzed by a bimetallic catalyst, characterized in that: Under the action of the supported bimetallic catalyst, epichlorohydrin and hydrogen react to generate 1-chloro-2-propanol and / or 3-chloro-1-propanol; The supported bimetallic catalyst comprises metal A, metal B and a carrier material; The metal A is one or more of platinum, rhodium, ruthenium, palladium and iridium; the metal B is one or more of copper, cobalt, nickel, silver, zinc and chromium; The mass percentage of the metal A in the supported bimetallic catalyst is 0.1-20%; the mass percentage of the metal B is 0.1-20%; The preparation of the supported bimetallic catalyst comprises the following steps: (1) preparing an ammonia-coordinated metal hydroxide solution of metal B; (2) preparing a nanoparticle colloid of metal A; (3) mixing the ammonia-coordinated metal hydroxide solution of metal B obtained in step (1) with a carrier, heating and drying under magnetic stirring, adding a reducing agent dropwise to the obtained solid powder under the protection of inert atmosphere, and preparing a supported metal catalyst of metal B; (4) mixing the nanoparticle colloid of metal A obtained in step (2) with the supported metal catalyst of metal B obtained in step (3), stirring until the colloid is completely adsorbed, and obtaining the supported bimetallic catalyst.

3. A process for the hydrogenation of epichlorohydrin catalyzed by a bimetallic catalyst according to claim 1 or 2, characterized in that: The carrier material is one or more of activated carbon, zinc oxide, iron oxide, zirconium oxide, titanium dioxide or magnesium oxide.

4. The process according to claim 1 or 2, wherein the process is a process for the hydrogenation of epichlorohydrin catalyzed by a bimetallic catalyst. The method comprises the following steps: (1) first dissolving the substrate epichlorohydrin in a solvent at room temperature or directly using epichlorohydrin as the reaction liquid; (2) adding the supported bimetallic catalyst into a reaction device, and then adding the reactant in step (1); (3) sealing the reaction device, introducing H2 to replace the air in the device, and then injecting a certain pressure of H2 into the device; (4) increasing the temperature to the required temperature under stirring, and obtaining the product after the reaction is completed.

5. The process of claim 4 wherein the catalyst is a bimetallic catalyst. The mass ratio of the supported metal catalyst and epichlorohydrin in the step (2) ranges from 1: (1-2000); the hydrogen pressure or partial pressure in the step (3) ranges from 0.005-15 MPa; and the temperature of the hydrogenation reaction in the step (4) ranges from -20-220℃.

6. The process of claim 1 wherein the catalyst is a bimetallic catalyst. The specific steps for preparing the supported metal catalyst of metal A are as follows: preparing the nanoparticle colloid of metal by using the polyol reduction method or the sol-gel method; dispersing the carrier material in a solvent, then adding the nanoparticle colloid of metal, and after the reaction is completed, performing solid-liquid separation and vacuum freeze-drying to obtain the supported metal catalyst of metal A.

7. The process according to claim 1 or 2, wherein the catalyst is a bimetallic catalyst. The specific steps for preparing the ammonia-coordinated metal hydroxide solution of metal B are as follows: dissolving the metal salt corresponding to metal B in a solvent, then adding an alkaline solution to generate a hydroxide precipitate, performing solid-liquid separation, and then adding the precipitate into ammonia water to dissolve and obtain the ammonia-coordinated metal hydroxide solution.

8. The process according to claim 1 or 2, wherein the catalyst is a bimetallic catalyst. The reducing agent in the step (3) is any one or several of sodium borohydride, hydrazine hydrate, lithium aluminum hydride, ascorbic acid, sodium hypophosphite, hydrogen iodide, sulfur, and hydrogen sulfide.