Catalyst for preparing saturated ketone through selective hydrogenation of ketene as well as preparation method and application of catalyst

Abstract

The invention discloses a catalyst for preparing saturated ketone through selective hydrogenation of ketene as well as a preparation method and application of the catalyst. The catalyst is used for preparing corresponding saturated ketone through selective hydrogenation of ketene, has higher activity, can inhibit the ketene from being excessively hydrogenated into saturated alcohol, and reduces side reaction selectivity.

Description

Technical Field

[0001] The invention belongs to the technical field of catalytic hydrogenation of ketene, and relates to a catalyst for preparing saturated ketone by selective hydrogenation of ketene, and a preparation method and application thereof. Background Art

[0002] At present, palladium-based catalysts are commonly used in industry to promote the selective hydrogenation of ketenes. This is because the transition metal palladium (Pd) has good activation performance for hydrogen, and the surface of the transition metal Pd can be passivated to inhibit the reduction of the ketone group, thereby improving the reaction selectivity. The Lindlar catalyst mainly used in the selective hydrogenation of ketenes in industrial production adopts a surface passivation strategy, using additives such as lead and bismuth to modify the Pd / C catalyst. However, the Lindlar catalyst still has the disadvantages of high toxicity, high cost, and insufficient selectivity. It is urgent to develop a more efficient, stable, and inexpensive catalyst for the selective hydrogenation of ketenes.

[0003] Compared with traditional processing technology, electrochemical hydrogenation can effectively regulate the hydrogen evolution rate and hydrogenation degree, and this process is greener and more environmentally friendly. Catalysts play a decisive role in the hydrogenation process. Inspired by the hydrogen overflow effect, a new type of metal-support electrocatalyst was proposed. During the hydrogen production process, H* is adsorbed on the metal (ΔGH-metal <0), hydrogen overflow from the metal to the support, and H* is desorbed on the support (ΔGH-support >0). Afterwards, the metal sites are released and quickly re-exposed for the next H* adsorption, ultimately improving the utilization of the metal.

[0004] Tungsten sulfide has a unique graphene-like structure and favorable electrochemical properties, economic benefits and high activity. The ΔGH on its basal plane can be adjusted by introducing sulfur vacancies, which is easy to control and modify, making it an ideal catalyst carrier. It is of profound research significance to prepare a low-cost, high-activity novel ketone selective hydrogenation catalyst by modifying the additive and optimizing the carrier.

[0005] CN101518734A discloses a catalyst for catalytic combustion of low calorific value gas, which contains 60-80% of γ-Al2O3, 19.9-39.5% of La or Mn oxides or combinations thereof, and the remaining component is Pd, which improves the high-temperature activity of the catalyst. However, the catalyst has a high metal content, and the oxidized metal additive cannot improve the catalyst hydrogenation selectivity. After testing, the catalyst is applied to ketene hydrogenation substrate conversion rate is low, and the ketone group is also reduced during the reaction, the ketene polymer exceeds 5%, and the product selectivity is low.

[0006] CN110479297A discloses a catalyst for continuously producing pentanone by hydrogenation of ketene, comprising an active component, an auxiliary agent and a carrier, wherein the active component comprises components A and B, wherein component A is Ni, component B is at least one element selected from Mo, Wu and Cr, the auxiliary agent comprises components C, D and E, component C is at least one element selected from V, Zn and Cu, component D is at least one element selected from lanthanide elements, component E is at least one element selected from P, B or N, the carrier is amorphous pseudo-boehmite, and pentanone is prepared by a continuous hydrogenation process. The catalyst components are complex, the preparation process is cumbersome, and it is difficult to achieve large-scale production.

[0007] CN110075887A discloses a palladium-supported catalyst for methanol catalytic combustion, which mainly solves the problem of high noble metal content and easy deactivation of catalysts prepared by the prior art. It is prepared by an impregnation precipitation method, including components such as active component Pd, auxiliary agents such as manganese nitrate, sodium dihydrogen phosphate and an activated alumina carrier. The catalyst has high activity and selectivity in the process of methanol catalytic combustion, and the noble metal is not easy to agglomerate and deactivate. However, the catalyst has a low hydrogenation substrate conversion rate and poor selectivity in the ketene hydrogenation reaction, and the ketone group is also reduced during the reaction. Summary of the invention

[0008] Pd / C catalyst is often used in the hydrogenation reaction of ketene, which is expensive. In addition, in the hydrogenation reaction, since the raw materials have unsaturated bonds such as carbon-carbon double bonds and carbon-oxygen double bonds, Pd / C catalyst is easy to cause excessive hydrogenation of the product to generate saturated alcohol, which reduces the selectivity of the hydrogenation product.

[0009] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a catalyst for the selective hydrogenation of ketene to prepare saturated ketones. The catalyst is applied to electrochemical hydrogenation. During the reaction process, the degree of hydrogenation reaction of the raw materials can be limited by selecting the current density and the catalytic electrode to avoid excessive hydrogenation.

[0010] In a first aspect, the present invention provides a catalyst for selective hydrogenation of ketene to prepare saturated ketone, comprising a carrier tungsten disulfide and an active component;

[0011] Based on the mass of the carrier tungsten disulfide as 100wt%, the active component comprises or consists of the following:

[0012] Palladium 0.2-1wt%;

[0013] 0.5-6 wt% of nitride of terbium, cerium, yttrium and / or lutetium, calculated as terbium, cerium, yttrium and / or lutetium elements;

[0014] 0.5-6wt% of hydride of cobalt, molybdenum, nickel and / or zinc, calculated as cobalt, molybdenum, nickel and / or zinc elements.

[0015] In some embodiments, in the above catalyst, the specific surface area of ​​the carrier tungsten disulfide is 40 to 120 m 2 / g, pore volume is 0.4~0.7cm 3 / g.

[0016] In a second aspect, the present invention provides an electrocatalytic electrode, the surface of which is loaded (eg, coated) with any one of the above-mentioned catalysts.

[0017] In some embodiments, the electrode is a graphite electrode, a platinum electrode, or a copper electrode.

[0018] In a third aspect, the present invention provides a method for preparing any of the above-mentioned electrocatalytic electrodes, comprising the following steps:

[0019] S1, preparing nitride by nitriding at least one of a terbium source, a cerium source, a yttrium source, and a lutetium source with ammonia, and obtaining nitride particles after grinding;

[0020] S2, preparing a hydride by hydrogenating at least one of a cobalt source, a molybdenum source, a nickel source, and a zinc source with hydrogen, and obtaining hydride particles after grinding;

[0021] S3, adding water to tungsten trioxide monohydrate, stirring to make it slurry, and then adding nitric acid to acidify to obtain tungsten sol;

[0022] S4, adding the nitride particles prepared in step S1 and the hydride particles prepared in step S2 to the tungsten sol prepared in step S3, and adding an aqueous solution of urea, stirring, and then adding kerosene and fatty alcohol polyoxyethylene ether dropwise under stirring to obtain a sol;

[0023] S5, coating the sol obtained in step S4 on the surface of the electrode, drying, and calcining in a H2S atmosphere to obtain an electrode precursor loaded with tungsten disulfide;

[0024] S6, using an aqueous solution containing a palladium compound to saturate the electrode precursor obtained in step S5, and then drying and calcining in an air atmosphere to obtain the electrocatalytic electrode;

[0025] Wherein, in step S4, the amount of the nitride particles added is 0.5-6.0wt% of the carrier tungsten disulfide, calculated based on the terbium, cerium, yttrium and / or lutetium elements contained in the nitride particles; the amount of the hydride particles added is 0.5-6.0wt% of the carrier tungsten disulfide, calculated based on the cobalt, molybdenum, nickel and / or zinc elements contained in the hydride particles;

[0026] In step S6, the palladium element in the aqueous solution containing the palladium compound is 0.2-1 wt% of the carrier tungsten disulfide;

[0027] The tungsten trioxide monohydrate in step S3 is the tungsten source of the carrier tungsten disulfide.

[0028] In some embodiments, in the above method, in step S1, the terbium source, cerium source, yttrium source, and lutetium source are one or more of oxides, acetates, and hydrochlorides of terbium, cerium, yttrium, and lutetium, preferably one or more of nano-terbium oxide, nano-cerium oxide, nano-yttrium oxide, and lutetium acetate;

[0029] The conditions of the nitridation reaction are: potassium hydroxide is used as a catalyst, and the mass space velocity is 0.1 to 10 h -1 , the reaction temperature is 500-800°C, the reaction pressure is 1-3MPa, and the reaction time is 80-150h; and / or

[0030] The particle size of the nitride particles is 0.01-1.0 mm.

[0031] In some embodiments, in any of the above methods, in step S2, the cobalt source, molybdenum source, nickel source, and zinc source are one or more of oxides, acetates, and hydrochlorides of cobalt, molybdenum, nickel, and zinc, preferably one or more of cobalt oxide, nano-molybdenum oxide, nickel acetate, and nano-zinc oxide;

[0032] The conditions of the hydrogenation reaction are: zinc acetate is used as a catalyst, and the mass space velocity is 0.1 to 10 h -1 , the reaction temperature is 200-800°C, the reaction pressure is 1-3MPa, and the reaction time is 2-15h; and / or

[0033] The particle size of the hydride particles is 0.02-1.0 mm.

[0034] In some embodiments, in any of the above methods, in step S1 and step S2, the grinding is performed under a nitrogen atmosphere.

[0035] In some embodiments, in any of the above methods, in step S3, the ratio of tungsten trioxide monohydrate to water is 1 g: (0.8-1.2) mL, for example, 1 g: 1 mL, and the volume of nitric acid is 1 / 8-1 / 12 of the volume of water, for example, 1 / 10.

[0036] In some embodiments, in any of the above methods, in step S4, the added amounts of urea, kerosene and fatty alcohol polyoxyethylene ether are in the range of 10:(2-4):(2-4):(0.2-0.4) in the mass ratio of tungsten trioxide monohydrate:urea:kerosene:fatty alcohol polyoxyethylene ether, for example, 10:3:3:0.3; the volume of the aqueous solution of urea is in the range of 10g:(4-6)mL in the ratio of the volume of the aqueous solution of tungsten trioxide monohydrate:urea, for example, 10g:5mL.

[0037] In some embodiments, in any of the above methods, in step S5, the coating thickness is 1 to 5 mm;

[0038] The drying conditions are: drying at 50-70°C for 2-6 hours, and then drying at 110-130°C for 4-14 hours; for example, drying at 60°C for 4 hours, and then drying at 120°C for 10 hours;

[0039] The calcination conditions are: calcination at 450-1100°C for 4-10h; and / or

[0040] The specific surface area of ​​the tungsten disulfide is 40 to 120 m 2 / g, pore volume is 0.4~0.7cm 3 / g.

[0041] In some embodiments, in any of the above methods, in step S6, the palladium-containing compound is chloropalladic acid and / or ammonium chloropalladate;

[0042] The concentration of the aqueous solution containing the palladium compound is 0.5 to 20 g / L;

[0043] The conditions of the saturated impregnation are: liquid / solid ratio of 1.0-2.0 mL / g, immersion at 20-70° C. for 0.5-5 h;

[0044] The drying conditions are: drying at 100-300°C for 1-20h; and / or

[0045] The calcination conditions are: calcination at 500-630° C. for 1-20 hours.

[0046] In some embodiments, in any of the above methods, the electrode is a graphite electrode, a platinum electrode or a copper electrode.

[0047] In a fourth aspect, the present invention provides use of any of the above-mentioned catalysts and / or any of the above-mentioned electrocatalytic electrodes in the selective hydrogenation of ketene to prepare saturated ketone.

[0048] In some embodiments, in the above application, the enone is one or more of pseudoionone, tetrahydrofarnesyl ketone, farnesyl acetone, 6,10-dimethyl-4,5,9-undecatrien-2-one, 6,10,14-trimethyl-4,5-pentadecadien-2-one, more preferably farnesyl acetone.

[0049] In a fifth aspect, the present invention provides a method for preparing a saturated ketone by selective hydrogenation of an ene ketone, comprising the steps of preparing the corresponding saturated ketone by an electrochemical method using water as a hydrogen source under the action of any of the above-mentioned catalysts and / or any of the above-mentioned electrocatalytic electrodes;

[0050] Preferably, the enone is one or more of pseudoionone, tetrahydrofarnesyl ketone, farnesyl acetone, 6,10-dimethyl-4,5,9-undecatrien-2-one, 6,10,14-trimethyl-4,5-pentadecadien-2-one, more preferably farnesyl acetone.

[0051] In some embodiments, the method comprises: dissolving ketene and potassium hydroxide aqueous solution through a surfactant, using any of the above electrocatalytic electrodes as a cathode, a DSA electrode as an anode, and potassium hydroxide aqueous solution as an electrolyte solution, with a current density of 400-1000 A / m 2 (For example, 500A / m 2 ), performing electrochemical reduction of ketene in an H-type electrolytic cell;

[0052] Preferably, the potassium hydroxide aqueous solution has a pH ≥ 8, preferably a pH of 8 to 9;

[0053] Preferably, the mass of the ketene is 1 to 4 times the mass of the potassium hydroxide aqueous solution;

[0054] Preferably, the surfactant is one or more of polyvinyl pyrrolidone (PVP), sodium dodecyl sulfate (SDS), cetyl trimethyl ammonium bromide (CTAB), preferably PVP.

[0055] The method for preparing saturated ketone by electrochemical selective hydrogenation of ketene using the catalyst of the present invention can achieve a reaction conversion rate of 100.0% and a selectivity of 99.8%.

[0056] The beneficial effects of the present invention are:

[0057] 1. Efficient electrochemical water splitting through hydrogen overflow catalyst improves the efficient utilization of H*, and selective hydrogenation of ketene is achieved by adjusting the voltage potential. Specifically, the catalyst is coated on the surface of the graphite electrode, and the carrier tungsten sulfide has a unique graphene-like structure, favorable electrochemical properties, economic benefits and high activity, and by introducing terbium, cerium, yttrium, lutetium, cobalt, molybdenum, nickel, and zinc as additives, the ΔGH of the carrier base is adjusted to enable the adsorption of H* on the metal (ΔGH-metal <0), the overflow of hydrogen from the metal to the carrier, and the desorption of H* on the carrier (ΔGH-support>0), after which the metal site is released and quickly re-exposed for the next H* adsorption, ultimately improving the utilization of the metal. By effectively regulating the hydrogen evolution rate and the degree of hydrogenation, the amount of active component Pd can be reduced, and this process is greener and more environmentally friendly.

[0058] 2. The catalyst of the present invention is used for selective hydrogenation of ketene to produce corresponding saturated ketone, has higher activity, can inhibit excessive hydrogenation of ketene to form saturated alcohol, and reduce the selectivity of side reactions.

[0059] 3. The present invention can reduce coking and carbon deposition on the electrode and increase the life of the electrode. DETAILED DESCRIPTION

[0060] The present invention will be further described below in conjunction with specific examples. It should be understood that the following examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. Unless otherwise specified, the technical means used in the examples are conventional operations in the art, or according to the experimental methods recommended by the kit and instrument manufacturers. The reagents and biological materials used in the examples can be obtained from commercial sources unless otherwise specified.

[0061] Chloropaldic acid (H2PdCl4), ammonium chloropalladate ((NH4)2PdCl4), nano terbium oxide (nano Tb2O3, particle size 200-300nm), nano cerium oxide (nano CeO2, particle size 400-500nm), nano yttrium oxide (nano Y2O3, particle size 90-200nm), cobalt oxide (CoO), nano molybdenum oxide (nano MoO3, particle size 20-100nm), nickel acetate (Ni(CH3COO)2), and nano zinc oxide (nano ZnO, particle size 20-90nm) are all Aladdin products.

[0062] Farnesyl acetone is a product of Yantai Haichuan Chemical Products Co., Ltd.

[0063] Lutetium acetate (Lu(CH3COO)3) and polyvinylpyrrolidone (PVP) (molecular weight 111.14) are both products of China National Pharmaceutical Group Corporation.

[0064] Test method for phytosterone and farnesyl acetone content:

[0065] Gas chromatograph: Agilent 7820A, chromatographic column: HP-5 capillary column (30m×320μm×0.25μm), injection port temperature: 80℃; FID detector temperature: 260℃; split ratio 30:1; carrier gas: nitrogen, 1.5mL / min; air flow: 400mL / min; hydrogen flow: 40mL / min; injection volume: 1μL; heating program: 40℃ for 1min, heating to 80℃ at 10℃ / min, holding for 0min, then heating to 180℃ at 5℃ / min, holding for 0min, then heating to 260℃ at 30℃ / min, holding for 5min. The contents of phytosterone and farnesyl acetone were obtained by external standard method.

[0066] Example 1

[0067] 1. Take 10g of nano-terbium oxide and react it with ammonia gas for nitridation, using potassium hydroxide as catalyst and the mass space velocity is 5h -1, reaction temperature 700 ° C, reaction pressure 2.5 MPa, reaction time 120 h, the obtained product was placed in a metal ball grinder, and ground for 3 hours under a nitrogen atmosphere to obtain TbN particles with a particle size of 0.08 mm.

[0068] 2. Take 10g of cobalt oxide and hydrogen for hydrogenation reaction, use zinc acetate as catalyst, and the mass space velocity is 4h -1 , reaction temperature 600 ° C, reaction pressure 2.5 MPa, reaction time 12 h, the obtained product was placed in a metal ball mill, and ground for 3 h under a nitrogen atmosphere to obtain CoH2 particles with a particle size of 0.08 mm.

[0069] 3. Take 20g of tungsten trioxide monohydrate, add 20mL of deionized water, stir for 1h to make it slurry, and then add 2mL of nitric acid to acidify it to obtain tungsten sol.

[0070] 4. Add the TbN particles prepared in step 1 to the tungsten sol so that the TbN content (in terms of Tb element) is 3.0wt% of the carrier tungsten disulfide (converted from tungsten), add the CoH2 particles prepared in step 2 so that the CoH2 content (in terms of Co element) is 3.0wt% of the carrier tungsten disulfide, and add 10mL of an aqueous solution containing 6g of urea, stir for 1h, continue stirring and add 6g of kerosene and 0.6g of fatty alcohol polyoxyethylene ether dropwise thereto to obtain a sol.

[0071] 5. Take 10g of sol and coat it on the surface of graphite electrode with a thickness of 3mm. Dry it at 60℃ for 4h, then at 120℃ for 10h. Calcinate the obtained electrode at 650℃ in H2S atmosphere for 8h to obtain an electrode precursor loaded with tungsten disulfide. The specific surface area of ​​tungsten disulfide is 80m 2 / g, pore volume is 0.6cm 3 / g.

[0072] 6. Use 10 g / L chloropalladic acid aqueous solution to saturate impregnate the electrode precursor obtained in step 5, so that the content of chloropalladic acid (calculated as Pd element) is 0.5 wt % of the carrier tungsten disulfide, the liquid / solid ratio is 1.6 mL / g, the impregnation temperature is 40°C, the impregnation time is 4 h, and then dried at 140°C for 10 h; the obtained electrode is calcined at 550°C in air atmosphere for 10 h to obtain ketene selective hydrogenation electrode A.

[0073] In the ketene selective hydrogenation electrode A, based on the mass of the carrier tungsten disulfide being 100wt%, the Pd content is 0.5wt%, the TbN content (calculated as Tb element) is 3.0wt%, and the CoH2 content (calculated as Co element) is 3.0wt%.

[0074] Example 2

[0075] 1. Take 10g of nano-cerium oxide and conduct nitridation reaction with ammonia, using potassium hydroxide as catalyst and the mass space velocity is 1h -1 , reaction temperature 600 ° C, reaction pressure 1.5 MPa, reaction time 90 h, the obtained product was placed in a metal ball mill, and ground for 3 h under a nitrogen atmosphere to obtain CeN particles with a particle size of 0.02 mm.

[0076] 2. Take 10g of cobalt oxide and hydrogen for hydrogenation reaction, use zinc acetate as catalyst, and the mass space velocity is 4h -1 , reaction temperature 600 ° C, reaction pressure 2.5 MPa, reaction time 12 h, the obtained product was placed in a metal ball mill, and ground for 3 h under a nitrogen atmosphere to obtain CoH2 particles with a particle size of 0.08 mm.

[0077] 3. Take 20g of tungsten trioxide monohydrate, add 20mL of deionized water, stir for 1h to make it slurry, and then add 2mL of nitric acid to acidify it to obtain tungsten sol.

[0078] 4. Add the CeN particles prepared in step 1 to the tungsten sol so that the CeN content (calculated as Ce element) is 2.0wt% of the carrier tungsten disulfide, add the CoH2 particles prepared in step 2 so that the CoH2 content (calculated as Co element) is 3.0wt% of the carrier tungsten disulfide, and add 10mL of an aqueous solution containing 6g of urea, stir for 1h, continue stirring and add 6g of kerosene and 0.6g of fatty alcohol polyoxyethylene ether dropwise thereto to obtain a sol.

[0079] 5. Take 10g of sol and coat it on the surface of graphite electrode with a thickness of 3mm. Dry it at 60℃ for 4h, then at 120℃ for 10h. Calcinate the obtained electrode at 650℃ in H2S atmosphere for 8h to obtain an electrode precursor loaded with tungsten disulfide. The specific surface area of ​​tungsten disulfide is 60m 2 / g, pore volume is 0.5cm 3 / g.

[0080] 6. Use 10 g / L chloropalladic acid aqueous solution to saturate impregnate the electrode precursor obtained in step 5, so that the content of chloropalladic acid (in terms of Pd element) is 0.5 wt % of the carrier tungsten disulfide, the liquid / solid ratio is 1.6 mL / g, the impregnation temperature is 40°C, the impregnation time is 4 h, and then dried at 140°C for 10 h; the obtained electrode is calcined at 550°C in air atmosphere for 10 h to obtain ketene selective hydrogenation electrode B.

[0081] In the ketene selective hydrogenation electrode B, based on the mass of the carrier tungsten disulfide being 100 wt%, the Pd content is 0.5 wt%, the CeN content (calculated as Ce element) is 2.0 wt%, and the CoH2 content (calculated as Co element) is 3.0 wt%.

[0082] Example 3

[0083] 1. Take 10g of nano-cerium oxide and conduct nitridation reaction with ammonia, using potassium hydroxide as catalyst and the mass space velocity is 1h -1 , reaction temperature 600 ° C, reaction pressure 1.5 MPa, reaction time 90 h, the obtained product was placed in a metal ball mill, and ground for 3 h under a nitrogen atmosphere to obtain CeN particles with a particle size of 0.02 mm.

[0084] 2. Take 10g of nano-molybdenum oxide and hydrogen for hydrogenation reaction, use zinc acetate as catalyst, and the mass space velocity is 1h -1 , reaction temperature 400 ° C, reaction pressure 1.5 MPa, reaction time 4h, the obtained product was placed in a metal ball grinder, and ground for 3h under a nitrogen atmosphere to obtain MoH2 particles with a particle size of 0.08mm.

[0085] 3. Take 20g of tungsten trioxide monohydrate, add 20mL of deionized water, stir for 1h to make it slurry, and then add 2mL of nitric acid to acidify it to obtain tungsten sol.

[0086] 4. Add the CeN particles prepared in step 1 to the tungsten sol so that the CeN content (calculated as Ce element) is 2.0wt% of the carrier tungsten disulfide, add the MoH2 particles prepared in step 2 so that the MoH2 content (calculated as Mo element) is 2.0wt% of the carrier tungsten disulfide, and add 10mL of an aqueous solution containing 6g of urea, stir for 1h, continue stirring and add 6g of kerosene and 0.6g of fatty alcohol polyoxyethylene ether dropwise thereto to obtain a sol.

[0087] 5. Take 10g of sol and coat it on the surface of graphite electrode with a thickness of 3mm. Dry it at 60℃ for 4h, then at 120℃ for 10h. Calcinate the obtained electrode at 650℃ in H2S atmosphere for 8h to obtain an electrode precursor loaded with tungsten disulfide. The specific surface area of ​​tungsten disulfide is 60m 2 / g, pore volume is 0.5cm 3 / g.

[0088] 6. Use 3 g / L chloropalladic acid aqueous solution to saturate impregnate the electrode precursor obtained in step 5, so that the content of chloropalladic acid (calculated as Pd element) is 0.3 wt % of the carrier tungsten disulfide, the liquid / solid ratio is 1.2 mL / g, the impregnation temperature is 25 ° C, the impregnation time is 3 h, and then dried at 100 ° C for 4 h; the obtained electrode is calcined at 500 ° C in air atmosphere for 4 h to obtain ketene selective hydrogenation electrode C.

[0089] In the ketene selective hydrogenation electrode C, based on the mass of the carrier tungsten disulfide being 100 wt%, the Pd content is 0.3 wt%, the CeN (calculated as Ce element) content is 2.0 wt%, and the MoH2 (calculated as Mo element) content is 2.0 wt%.

[0090] Example 4

[0091] 1. Take 10g of nano yttrium oxide and conduct nitridation reaction with ammonia, using potassium hydroxide as catalyst and the mass space velocity is 0.1h -1 , reaction temperature 500°C, reaction pressure 1.0MPa, reaction time 80h, the obtained product was placed in a metal ball mill, and ground for 3h under a nitrogen atmosphere to obtain YN particles with a particle size of 0.01mm.

[0092] 2. Take 10g of nickel acetate and hydrogen for hydrogenation reaction, use zinc acetate as catalyst, and the mass space velocity is 0.1h -1 , reaction temperature 200 ° C, reaction pressure 1.0 MPa, reaction time 2h, the obtained product was placed in a metal ball grinder, and ground for 3h under a nitrogen atmosphere to obtain NiH2 particles with a particle size of 0.02mm.

[0093] 3. Take 20g of tungsten trioxide monohydrate, add 20mL of deionized water, stir for 1h to make it slurry, and then add 2mL of nitric acid to acidify it to obtain tungsten sol.

[0094] 4. Add the YN particles prepared in step 1 to the tungsten sol so that the YN content (calculated as Y element) is 2.0wt% of the carrier tungsten disulfide, add the NiH2 particles prepared in step 2 so that the NiH2 content (calculated as Ni element) is 2.0wt% of the carrier tungsten disulfide, and add 10mL of an aqueous solution containing 6g of urea, stir for 1h, continue stirring and add 6g of kerosene and 0.6g of fatty alcohol polyoxyethylene ether dropwise thereto to obtain a sol.

[0095] 5. Take 10g of sol and coat it on the surface of graphite electrode with a thickness of 3mm. Dry it at 60℃ for 4h, then at 120℃ for 10h. Calcinate the obtained electrode at 1100℃ in H2S atmosphere for 6h to obtain an electrode precursor loaded with tungsten disulfide. The specific surface area of ​​tungsten disulfide is 40m 2 / g, pore volume is 0.4cm 3 / g.

[0096] 6. Use 3 g / L ammonium chloropalladate aqueous solution to saturate impregnate the electrode precursor obtained in step 5, so that the content of ammonium chloropalladate (in terms of Pd element) is 0.3 wt % of the carrier tungsten disulfide, the liquid / solid ratio is 1.2 mL / g, the impregnation temperature is 25 ° C, the impregnation time is 3 h, and then dried at 100 ° C for 4 h; the obtained electrode is calcined at 500 ° C in air atmosphere for 4 h to obtain ketene selective hydrogenation electrode D.

[0097] In the ketene selective hydrogenation electrode D, based on the mass of the carrier tungsten disulfide being 100 wt%, the Pd content is 0.3 wt%, the YN content (calculated as Y element) is 2.0 wt%, and the NiH2 content (calculated as Ni element) is 2.0 wt%.

[0098] Example 5

[0099] 1. Take 10g of lutetium acetate and react it with ammonia for nitridation, using potassium hydroxide as catalyst and the mass space velocity is 0.1h -1 , reaction temperature 500°C, reaction pressure 1.0MPa, reaction time 80h, the obtained product was placed in a metal ball mill, and ground for 3h under a nitrogen atmosphere to obtain LuN particles with a particle size of 0.01mm.

[0100] 2. Take 10g of nano zinc oxide and hydrogen for hydrogenation reaction, use zinc acetate as catalyst, and the mass space velocity is 0.1h -1 , reaction temperature 200 ° C, reaction pressure 1.0 MPa, reaction time 2h, the obtained product was placed in a metal ball grinder, and ground for 3h under a nitrogen atmosphere to obtain ZnH2 particles with a particle size of 0.02mm.

[0101] 3. Take 20g of tungsten trioxide monohydrate, add 20mL of deionized water, stir for 1h to make it slurry, and then add 2mL of nitric acid to acidify it to obtain tungsten sol.

[0102] 4. Add the LuN particles prepared in step 1 to the tungsten sol so that the LuN content (calculated as Lu element) is 4.0wt% of the carrier tungsten disulfide, add the ZnH2 particles prepared in step 2 so that the ZnH2 content (calculated as Zn element) is 4.0wt% of the carrier tungsten disulfide, and add 10mL of an aqueous solution containing 6g of urea, stir for 1h, continue stirring and add 6g of kerosene and 0.6g of fatty alcohol polyoxyethylene ether dropwise thereto to obtain a sol.

[0103] 5. Take 10g of sol and coat it on the surface of graphite electrode with a thickness of 3mm. Dry it at 60℃ for 4h, then at 120℃ for 10h. Calcinate the obtained electrode at 1100℃ in H2S atmosphere for 6h to obtain an electrode precursor loaded with tungsten disulfide. The specific surface area of ​​tungsten disulfide is 40m 2 / g, pore volume is 0.4cm3 / g.

[0104] 6. Use 0.5 g / L ammonium chloropalladate aqueous solution to saturate impregnate the electrode precursor obtained in step 5, so that the content of ammonium chloropalladate (in terms of Pd element) is 0.2 wt % of the carrier tungsten disulfide, the liquid / solid ratio is 1.0 mL / g, the impregnation temperature is 20°C, the impregnation time is 0.5 h, and then dried at 100°C for 1 h; the obtained electrode is calcined at 500°C in air atmosphere for 4 h to obtain an ene-selective hydrogenation electrode E loaded with ketone.

[0105] In the ketene selective hydrogenation electrode E, based on the mass of the carrier tungsten disulfide being 100 wt%, the Pd content is 0.2 wt%, the LuN content (calculated as Lu element) is 4.0 wt%, and the ZnH2 content (calculated as Zn element) is 4.0 wt%.

[0106] Example 6

[0107] 1. Take 10g of nano-terbium oxide and react it with ammonia gas for nitridation, using potassium hydroxide as catalyst and the mass space velocity is 5h -1 , reaction temperature 700 ° C, reaction pressure 2.5 MPa, reaction time 120 h, the obtained product was placed in a metal ball grinder, and ground for 3 hours under a nitrogen atmosphere to obtain TbN particles with a particle size of 0.08 mm.

[0108] 2. Take 10g of cobalt oxide and hydrogen for hydrogenation reaction, use zinc acetate as catalyst, and the mass space velocity is 4h -1 , reaction temperature 600 ° C, reaction pressure 2.5 MPa, reaction time 12 h, the obtained product was placed in a metal ball mill, and ground for 3 h under a nitrogen atmosphere to obtain CoH2 particles with a particle size of 0.08 mm.

[0109] 3. Take 20g of tungsten trioxide monohydrate, add 20mL of deionized water, stir for 1h to make it slurry, and then add 2mL of nitric acid to acidify it to obtain tungsten sol.

[0110] 4. Add the TbN particles prepared in step 1 to the tungsten sol so that the content of TbN (in terms of Tb element) is 3.0wt% of the carrier tungsten disulfide, add the CoH2 particles prepared in step 2 so that the content of CoH2 (in terms of Co element) is 3.0wt% of the carrier tungsten disulfide, and add 10mL of an aqueous solution containing 6g of urea, stir for 1h, continue stirring and add 6g of kerosene and 0.6g of fatty alcohol polyoxyethylene ether dropwise thereto to obtain a sol.

[0111] 5. Take 10g of sol and coat it on the surface of graphite electrode with a thickness of 3mm. Dry it at 60℃ for 4h, then at 120℃ for 10h. Calcinate the obtained electrode at 650℃ in H2S atmosphere for 8h to obtain an electrode precursor loaded with tungsten disulfide. The specific surface area of ​​tungsten disulfide is 80m 2 / g, pore volume is 0.6cm 3 / g.

[0112] 6. Use 20 g / L chloropalladic acid aqueous solution to saturate the electrode precursor obtained in step 5, so that the content of chloropalladic acid (in terms of Pd element) is 0.5 wt % of the carrier tungsten disulfide, the liquid / solid ratio is 2.0 mL / g, the impregnation temperature is 70°C, the impregnation time is 5 h, and then dried at 300°C for 20 h; the obtained electrode is calcined at 630°C in air atmosphere for 20 h to obtain ketene selective hydrogenation electrode F.

[0113] In the ketene selective hydrogenation electrode F, based on the mass of the carrier tungsten disulfide being 100 wt%, the Pd content is 0.5 wt%, the TbN content (calculated as Tb element) is 3.0 wt%, and the CoH2 content (calculated as Co element) is 3.0 wt%.

[0114] Example 7

[0115] 1. Take 10g of nano-terbium oxide and react it with ammonia gas for nitridation, using potassium hydroxide as catalyst and the mass space velocity is 10h -1 , reaction temperature 800 ° C, reaction pressure 3.0 MPa, reaction time 150 h, the obtained product was placed in a metal ball mill, and ground for 3 hours under a nitrogen atmosphere to obtain TbN particles with a particle size of 0.08 mm.

[0116] 2. Take 10g of cobalt oxide and hydrogen for hydrogenation reaction, use zinc acetate as catalyst, and the mass space velocity is 10h -1 , reaction temperature 800 ° C, reaction pressure 3.0 MPa, reaction time 15 h, the obtained product was placed in a metal ball mill, and ground for 3 h under a nitrogen atmosphere to obtain CoH2 particles with a particle size of 0.08 mm.

[0117] 3. Take 20g of tungsten trioxide monohydrate, add 20mL of deionized water, stir for 1h to make it slurry, and then add 2mL of nitric acid to acidify it to obtain tungsten sol.

[0118] 4. Add the TbN particles prepared in step 1 to the tungsten sol so that the content of TbN (in terms of Tb element) is 3.0wt% of the carrier tungsten disulfide, add the CoH2 particles prepared in step 2 so that the content of CoH2 (in terms of Co element) is 3.0wt% of the carrier tungsten disulfide, and add 10mL of an aqueous solution containing 6g of urea, stir for 1h, continue stirring and add 6g of kerosene and 0.6g of fatty alcohol polyoxyethylene ether dropwise thereto to obtain a sol.

[0119] 5. Take 10g of sol and coat it on the surface of graphite electrode with a thickness of 3mm. Dry it at 60℃ for 4h, then at 120℃ for 10h. Calcinate the obtained electrode at 650℃ in H2S atmosphere for 8h to obtain an electrode precursor loaded with tungsten disulfide. The specific surface area of ​​tungsten disulfide is 120m 2 / g, pore volume is 0.7cm 3 / g.

[0120] 6. Use 10 g / L chloropalladic acid aqueous solution to saturate impregnate the electrode precursor obtained in step 5, so that the content of chloropalladic acid (calculated as Pd element) is 0.5 wt % of the carrier tungsten disulfide, the liquid / solid ratio is 1.6 mL / g, the impregnation temperature is 40°C, the impregnation time is 4 h, and then dried at 140°C for 10 h; the obtained electrode is calcined at 550°C in air atmosphere for 10 h to obtain ketene selective hydrogenation electrode G.

[0121] In the ketene selective hydrogenation electrode G, based on the mass of the carrier tungsten disulfide being 100wt%, the Pd content is 0.5wt%, the TbN content (calculated as Tb element) is 3.0wt%, and the CoH2 content (calculated as Co element) is 3.0wt%.

[0122] Example 8

[0123] 1. Take 10g of nano-terbium oxide and react it with ammonia gas for nitridation, using potassium hydroxide as catalyst and the mass space velocity is 5h -1 , reaction temperature 700 ° C, reaction pressure 2.5 MPa, reaction time 120 h, the obtained product was placed in a metal ball grinder, and ground for 3 h under a nitrogen atmosphere to obtain TbN particles with a particle size of 1.0 mm.

[0124] 2. Take 10g of cobalt oxide and hydrogen for hydrogenation reaction, use zinc acetate as catalyst, and the mass space velocity is 4h -1 , reaction temperature 600 ° C, reaction pressure 2.5 MPa, reaction time 12 h, the obtained product was placed in a metal ball mill, and ground for 3 h under a nitrogen atmosphere to obtain CoH2 particles with a particle size of 1.0 mm.

[0125] 3. Take 20g of tungsten trioxide monohydrate, add 20mL of deionized water, stir for 1h to make it slurry, and then add 2mL of nitric acid to acidify it to obtain tungsten sol.

[0126] 4. Add the TbN particles prepared in step 1 to the tungsten sol so that the TbN content (in terms of Tb element) is 0.5wt% of the carrier tungsten disulfide, add the CoH2 particles prepared in step 2 so that the CoH2 content (in terms of Co element) is 0.5wt% of the carrier tungsten disulfide, and add 10mL of an aqueous solution containing 6g of urea, stir for 1h, continue stirring and add 6g of kerosene and 0.6g of fatty alcohol polyoxyethylene ether dropwise thereto to obtain a sol.

[0127] 5. Take 10g of sol and coat it on the surface of graphite electrode with a thickness of 3mm. Dry it at 60℃ for 4h, then at 120℃ for 10h. Calcinate the obtained electrode at 450℃ in H2S atmosphere for 4h to obtain an electrode precursor loaded with tungsten disulfide. The specific surface area of ​​tungsten disulfide is 80m 2 / g, pore volume is 0.6cm 3 / g.

[0128] 6. Use 10 g / L chloropalladic acid aqueous solution to saturate impregnate the electrode precursor obtained in step 5, so that the content of chloropalladic acid (in terms of Pd element) is 0.5 wt % of the carrier tungsten disulfide, the liquid / solid ratio is 1.6 mL / g, the impregnation temperature is 40°C, the impregnation time is 4 h, and then dried at 140°C for 10 h; the obtained electrode is calcined at 550°C in air atmosphere for 1 h to obtain ketene selective hydrogenation electrode H.

[0129] In the ketene selective hydrogenation electrode H, based on the mass of the carrier tungsten disulfide being 100wt%, the Pd content is 0.5wt%, the TbN content (calculated as Tb element) is 0.5wt%, and the CoH2 content (calculated as Co element) is 0.5wt%.

[0130] Example 9

[0131] 1. Take 10g of nano-terbium oxide and react it with ammonia gas for nitridation, using potassium hydroxide as catalyst and the mass space velocity is 5h -1 , reaction temperature 700 ° C, reaction pressure 2.5 MPa, reaction time 120 h, the obtained product was placed in a metal ball grinder, and ground for 3 hours under a nitrogen atmosphere to obtain TbN particles with a particle size of 0.08 mm.

[0132] 2. Take 10g of cobalt oxide and hydrogen for hydrogenation reaction, use zinc acetate as catalyst, and the mass space velocity is 4h -1, reaction temperature 600 ° C, reaction pressure 2.5 MPa, reaction time 12 h, the obtained product was placed in a metal ball mill, and ground for 3 h under a nitrogen atmosphere to obtain CoH2 particles with a particle size of 0.08 mm.

[0133] 3. Take 20g of tungsten trioxide monohydrate, add 20mL of deionized water, stir for 1h to make it slurry, and then add 2mL of nitric acid to acidify it to obtain tungsten sol.

[0134] 4. Add the TbN particles prepared in step 1 to the tungsten sol so that the content of TbN (in terms of Tb element) is 6.0wt% of the carrier tungsten disulfide, add the CoH2 particles prepared in step 2 so that the content of CoH2 (in terms of Co element) is 6.0wt% of the carrier tungsten disulfide, and add 10mL of an aqueous solution containing 6g of urea, stir for 1h, continue stirring and add 6g of kerosene and 0.6g of fatty alcohol polyoxyethylene ether dropwise thereto to obtain a sol.

[0135] 5. Take 10g of sol and coat it on the surface of graphite electrode with a thickness of 3mm. Dry it at 60℃ for 4h, then at 120℃ for 10h. Calcinate the obtained electrode at 650℃ in H2S atmosphere for 10h to obtain an electrode precursor loaded with tungsten disulfide. The specific surface area of ​​tungsten disulfide is 80m 2 / g, pore volume is 0.6cm 3 / g.

[0136] 6. Use 10 g / L chloropalladic acid aqueous solution to saturate impregnate the electrode precursor obtained in step 5, so that the content of chloropalladic acid (calculated as Pd element) is 1.0 wt % of the carrier tungsten disulfide, the liquid / solid ratio is 1.6 mL / g, the impregnation temperature is 40°C, the impregnation time is 4 h, and then dried at 140°C for 10 h; the obtained electrode is calcined at 550°C in air atmosphere for 10 h to obtain ketene selective hydrogenation electrode I.

[0137] In the ketene selective hydrogenation electrode I, based on the mass of the carrier tungsten disulfide as 100wt%, the Pd content is 1.0wt%, the TbN content (calculated as Tb element) is 6.0wt%, and the CoH2 content (calculated as Co element) is 6.0wt%.

[0138] Comparative Example 1

[0139] The comparison catalyst is Pd / CaCO3 catalyst, a product of Jiangsu Xinnoko Catalyst Co., Ltd.

[0140] In the comparative catalyst, the Pd content is 5 wt %, based on the mass of the CaCO 3 carrier being 100 wt %.

[0141] Test example: Selective hydrogenation of farnesyl acetone to produce phytosterone

[0142] 50g of farnesyl acetone and 50g of 15wt% potassium hydroxide aqueous solution (pH=8) were mutually dissolved by a surfactant polyvinylpyrrolidone (PVP), and the ketene selective hydrogenation electrode prepared in the embodiment was used as the cathode, the DSA electrode was used as the anode, and the 15wt% potassium hydroxide aqueous solution was used as the electrolyte solution. The current density was 500A / m 2 , electrochemical reduction of ketene was carried out in an H-type electrolytic cell.

[0143] The reaction equation is as follows:

[0144]

[0145] Conversion rate (%) = (n (farnesyl acetone before reaction) - n (farnesyl acetone after reaction)) / n (farnesyl acetone before reaction) × 100%

[0146] Selectivity (%) = n (phytosterone after reaction) / (n (farnesyl acetone before reaction) - n (farnesyl acetone after reaction)) × 100%

[0147] In the conversion rate and selectivity calculation formula, n is the amount of substance.

[0148] The results are shown in Table 1.

[0149] 50 g of farnesyl acetone and 0.50 g of comparative catalyst were added into a high-pressure reactor, and replaced with nitrogen and hydrogen three times respectively. The temperature was raised to the reaction temperature, and the hydrogenation reaction was carried out at a reaction temperature of 60° C. and a reaction pressure of 2 MPaG.

[0150] The reaction equation is as follows:

[0151]

[0152] The conversion and selectivity calculation formulas are shown above.

[0153] The results are shown in Table 1.

[0154] Table 1 Test results

[0155] catalyst Conversion rate (%) Selectivity (%) Ketene Selective Hydrogenation Electrode A 100.0 99.8 Ketene Selective Hydrogenation Electrode B 100.0 99.7 Ketene Selective Hydrogenation Electrode C 100.0 99.7 Ketene Selective Hydrogenation Electrode D 100.0 99.6 Ketene Selective Hydrogenation Electrode E 100.0 99.7 Ketene Selective Hydrogenation Electrode F 100.0 99.7 Ketene Selective Hydrogenation Electrode G 100.0 99.8 Ketene Selective Hydrogenation Electrode H 100.0 99.7 Ketene Selective Hydrogenation Electrode I 100.0 99.6 Comparison of catalysts 95.2 84.5

Claims

1. A catalyst for selective hydrogenation of ketene to prepare saturated ketone, comprising a carrier tungsten disulfide and an active component; Based on the mass of the carrier tungsten disulfide as 100wt%, the active component comprises: Palladium 0.2-1wt%; 0.5-6 wt% of nitride of terbium, cerium, yttrium and / or lutetium, calculated as terbium, cerium, yttrium and / or lutetium elements; 0.5-6wt% of hydride of cobalt, molybdenum, nickel and / or zinc, calculated as cobalt, molybdenum, nickel and / or zinc elements.

2. The catalyst according to claim 1, characterized in that: The specific surface area of ​​the carrier tungsten disulfide is 40 to 120 m 2 / g, pore volume is 0.4~0.7cm 3 / g.

3. An electrocatalytic electrode, the surface of which is loaded with the catalyst according to claim 1 or 2; Preferably, the electrode is a graphite electrode, a platinum electrode or a copper electrode.

4. A method for preparing the electrocatalytic electrode according to claim 3, comprising the following steps: S1, preparing nitride by nitriding at least one of a terbium source, a cerium source, a yttrium source, and a lutetium source with ammonia, and obtaining nitride particles after grinding; S2, preparing a hydride by hydrogenating at least one of a cobalt source, a molybdenum source, a nickel source, and a zinc source with hydrogen, and obtaining hydride particles after grinding; S3, adding water to tungsten trioxide monohydrate, stirring to make it slurry, and then adding nitric acid to acidify to obtain tungsten sol; S4, adding the nitride particles prepared in step S1 and the hydride particles prepared in step S2 to the tungsten sol prepared in step S3, and adding an aqueous solution of urea, stirring, and then adding kerosene and fatty alcohol polyoxyethylene ether dropwise under stirring to obtain a sol; S5, coating the sol obtained in step S4 on the surface of the electrode, drying, and calcining in a H2S atmosphere to obtain an electrode precursor loaded with tungsten disulfide; S6, using an aqueous solution containing a palladium compound to saturate the electrode precursor obtained in step S5, and then drying and calcining in an air atmosphere to obtain the electrocatalytic electrode; in, In step S4, the amount of the nitride particles added is 0.5-6.0wt% of the carrier tungsten disulfide, calculated based on the terbium, cerium, yttrium and / or lutetium elements contained in the nitride particles; the amount of the hydride particles added is 0.5-6.0wt% of the carrier tungsten disulfide, calculated based on the cobalt, molybdenum, nickel and / or zinc elements contained in the hydride particles; In step S6, the palladium element in the aqueous solution containing the palladium compound is 0.2-1 wt% of the carrier tungsten disulfide; The tungsten trioxide monohydrate in step S3 is the tungsten source of the carrier tungsten disulfide.

5. The method according to claim 4, characterized in that: In step S1, the terbium source, cerium source, yttrium source, and lutetium source are one or more of oxides, acetates, and hydrochlorides of terbium, cerium, yttrium, and lutetium, preferably one or more of nano-terbium oxide, nano-cerium oxide, nano-yttrium oxide, and lutetium acetate; The conditions of the nitridation reaction are: potassium hydroxide is used as a catalyst, and the mass space velocity is 0.1 to 10 h -1 , the reaction temperature is 500-800°C, the reaction pressure is 1-3MPa; and / or The particle size of the nitride particles is 0.01-1.0 mm.

6. The method according to claim 4 or 5, characterized in that: In step S2, the cobalt source, molybdenum source, nickel source, and zinc source are one or more of oxides, acetates, and hydrochlorides of cobalt, molybdenum, nickel, and zinc, preferably one or more of cobalt oxide, nano-molybdenum oxide, nickel acetate, and nano-zinc oxide; The conditions of the hydrogenation reaction are: zinc acetate is used as a catalyst, and the mass space velocity is 0.1 to 10 h -1 , the reaction temperature is 200-800°C, the reaction pressure is 1-3MPa; and / or The particle size of the hydride particles is 0.02-1.0 mm.

7. The method according to any one of claims 4 to 6, characterized in that: In step S5, the coating thickness is 1 to 5 mm; The drying conditions are: drying at 50-70°C for 2-6 hours, and then drying at 110-130°C for 4-14 hours; The calcination conditions are: calcination at 450-1100°C for 4-10h; and / or The specific surface area of ​​the tungsten disulfide is 40 to 120 m 2 / g, pore volume is 0.4~0.7cm 3 / g.

8. The method according to any one of claims 4 to 7, characterized in that: In step S6, the palladium-containing compound is chloropalladic acid and / or ammonium chloropalladate; The conditions of the saturated impregnation are: liquid / solid ratio of 1.0-2.0 mL / g, immersion at 20-70° C. for 0.5-5 h; The drying conditions are: drying at 100-300°C for 1-20h; and / or The calcination conditions are: calcination at 500-630° C. for 1-20 hours.

9. Use of the catalyst according to claim 1 or 2 and / or the electrocatalytic electrode according to claim 3 in the selective hydrogenation of ketene to prepare saturated ketone; Preferably, the enone is one or more of pseudoionone, tetrahydrofarnesyl ketone, farnesyl acetone, 6,10-dimethyl-4,5,9-undecatrien-2-one, 6,10,14-trimethyl-4,5-pentadecadien-2-one, more preferably farnesyl acetone.

10. A method for preparing a saturated ketone by selective hydrogenation of ketene, comprising the step of preparing the corresponding saturated ketone by electrochemical method using water as a hydrogen source under the action of the catalyst according to claim 1 or 2 and / or the electrocatalytic electrode according to claim 3; Preferably, the enone is one or more of pseudoionone, tetrahydrofarnesyl ketone, farnesyl acetone, 6,10-dimethyl-4,5,9-undecatrien-2-one, 6,10,14-trimethyl-4,5-pentadecadien-2-one, more preferably farnesyl acetone.