WO2019109629A1 - 苯乙酮加氢制备α-苯乙醇的催化剂、制备方法及应用 - Google Patents

苯乙酮加氢制备α-苯乙醇的催化剂、制备方法及应用 Download PDF

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WO2019109629A1
WO2019109629A1 PCT/CN2018/093616 CN2018093616W WO2019109629A1 WO 2019109629 A1 WO2019109629 A1 WO 2019109629A1 CN 2018093616 W CN2018093616 W CN 2018093616W WO 2019109629 A1 WO2019109629 A1 WO 2019109629A1
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catalyst
earth metal
copper
silica sol
preparation
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French (fr)
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李作金
于海波
詹吉山
沙宇
初乃波
黎源
华卫琦
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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Priority to EP18886984.6A priority Critical patent/EP3721991A4/en
Priority to US16/763,865 priority patent/US11167280B2/en
Priority to JP2020530304A priority patent/JP7019813B2/ja
Publication of WO2019109629A1 publication Critical patent/WO2019109629A1/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0063—Granulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention belongs to the technical field of catalytic hydrogenation, and particularly relates to a catalyst for preparing ⁇ -phenylethanol by liquid phase hydrogenation of acetophenone, a preparation method thereof and application thereof.
  • Alpha-phenylethyl alcohol is an important chemical intermediate widely used in the pharmaceutical, fragrance manufacturing, cosmetics, food and fine chemicals industries.
  • the existing ⁇ -phenylethanol synthesis methods mainly include microbial fermentation and acetophenone reduction/catalytic hydrogenation.
  • the microbial fermentation method generally uses phenylalanine and fluorophenylalanine as raw materials to obtain ⁇ -phenylethanol by microbial fermentation.
  • the raw materials used in the microbial method are expensive and the production cost is high.
  • the industrial production of ⁇ -phenylethanol is usually carried out by the acetophenone hydrogenation method, which has the advantages of low production cost, low by-products, high product yield, high product purity, and the like, and is suitable for large-scale production of ⁇ -phenylethyl alcohol.
  • the acetophenone hydrogenation catalyst mainly includes platinum-palladium precious metal catalyst, nickel-based catalyst and copper-based catalyst.
  • the noble metal catalyst and nickel-based catalyst have high cost, easy to cause aromatic ring saturation and phenylethyl alcohol hydrogenolysis, and ⁇ -phenylethanol selectivity is poor.
  • the copper-based catalyst has the advantages of high activity, high selectivity, low cost, and the like for the hydrogenation reaction of acetophenone.
  • U.S. Patent 4,996,374 discloses a Pd-C catalyst, but its catalyst stability is poor, and the reaction temperature needs to be continuously increased when applied.
  • CN1315226A discloses a reduction-treated copper-based catalyst and a method for preparing ⁇ -phenylethyl alcohol, but it is required to adopt a liquid phase reduction method to improve the stability of the catalyst, and the process is complicated and high in cost.
  • CN1911883A discloses a method for preparing ⁇ -phenylethanol by using Raney nickel as a catalyst, but a large amount of aromatic ring hydrogenation product ⁇ -cyclohexylethanol appears in the acetophenone hydrogenation product, and ⁇ -phenylethanol selectivity Lower.
  • EP0714877B1 uses alkali metal and/or alkaline earth metal carbonate to modify the copper-silicon catalyst significantly inhibits the formation of by-product ethylbenzene, but its silicon source is added in the form of fumed silica or diatomaceous earth, which is not conducive to enhancing the active component. The interaction with the support is detrimental to the strength of the catalyst.
  • a part of the silicon source in the catalyst of WO2016198379 is added in the form of a silica sol during extrusion molding, and does not effectively disperse the active component copper. None of the above publications mentions the dispersion and stabilization of the active component by the auxiliary agent, as well as the mechanical stability and strength after use of the shaped catalyst.
  • the acetophenone hydrogenation process is prone to ⁇ -phenylethanol hydrogenolysis/dehydration side reaction to form ethylbenzene/styrene, the hydrogenation and dehydration reaction rates increase rapidly with the increase of reaction temperature.
  • the copper-based catalyst used for the liquid phase hydrogenation reaction is not only subjected to various internal or external forces in the processes of storage/loading/reduction/reaction, but also the actual use of the catalyst due to liquid immersion, swelling, and the like.
  • the strength is greatly reduced, which causes the catalyst to be easily broken and pulverized in the liquid phase hydrogenation system, which threatens the stable operation of the industrial device and affects the life of the catalyst.
  • the hydrogenation of acetophenone prepared by precipitation method to prepare ⁇ -phenylethyl alcohol-based catalyst generally has problems such as low dispersion of active component copper, strong acidity of the catalyst, weak interaction force between carrier and active component, etc., resulting in acetophenone.
  • the conversion rate is low, the amount of by-products such as ethylbenzene is large, the selectivity of phenylethyl alcohol is poor, and the catalyst strength is poor. Therefore, improving the dispersion of the active component copper and the mass transfer performance of the catalyst, inhibiting the acidity of the catalyst, and improving the liquid resistance of the catalyst are significant for preparing a high activity, high selectivity and high liquid resistance acetophenone hydrogenation catalyst.
  • the object of the present invention is to provide a preparation method of a catalyst for liquid phase hydrogenation of acetophenone to prepare ⁇ -phenylethanol and a catalyst obtained by the method.
  • the catalyst prepared by the method significantly inhibits side reactions such as hydrogenolysis, and has high catalyst activity.
  • the selectivity is good; at the same time, the catalyst has excellent liquid resistance, and has high strength after reduction and liquid phase hydrogenation reaction.
  • a method for preparing a hydrogenation catalyst comprising the steps of:
  • the step (1) is to uniformly mix deionized water, small molecule alcohol, Gemini surfactant and organic pore former and silica sol to form a small molecule alcohol, a Gemini surfactant and an organic pore former.
  • Silica sol aqueous dispersion.
  • the organic pore-forming agent is preferably selected from one or more of PMMA, microcrystalline cellulose, and methyl cellulose; and an organic pore-forming agent is added during the preparation process to reduce diffusion resistance in the raw material and the product. Effectively increases activity and selectivity.
  • the organic pore former has a particle diameter of ⁇ 100 ⁇ mm, more preferably 1 to 80 ⁇ m, further preferably 3 to 30 ⁇ m, such as 5, 10, 15, 20 or 25 ⁇ m; an organic pore former
  • the particle size is kept within a suitable range, which helps to further improve the diffusion and mass transfer of raw materials and products; the particle size is too large, which is not conducive to effectively improving the mass transfer performance, and the particle size is too small, which is not conducive to improving mass transfer. effect.
  • the organic pore former is used in an amount of from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, still more preferably from 2 to 5% by weight based on the total mass of the catalyst. Keeping the amount of organic pore-forming agent in the proper range helps to minimize the influence on the strength of the catalyst under the premise of achieving better mass transfer performance; the amount of organic pore-forming agent added is too small, which is not conducive to improvement. The effect of catalyst mass transfer performance; too much addition of pore former will affect the mechanical strength of the catalyst.
  • the total amount of silicon in the catalyst is introduced together by the silica sol and the silicon-containing basic precipitant, and preferably, the amount of silicon introduced from the silica sol accounts for 30-70 wt of the total amount of silicon in the catalyst. %, more preferably 35-65 wt%, further preferably 40-60 wt%, such as 50 wt%; it has been found that a highly dispersed silica sol and a silicon-containing basic precipitant are used as a composite silicon source, compared to the use of a single silicon source.
  • the catalyst not only has high activity but also good strength.
  • the silica sol is an alkaline silica sol having a pH of 8.0-10.0.
  • the small molecule alcohol means an alcohol having a molecular weight of not more than 400, such as a small molecule saturated monohydric alcohol having a molecular weight of not more than 400.
  • the mass ratio of the small molecule alcohol to deionized water is 1:20 to 1:10, such as 1:18, 1:15 or 1:12; further preferably, the step
  • the small molecule alcohol of (1) is one or more of methanol, ethanol, propanol and butanol.
  • Gemini surfactants used are well known in the art and are novel surfaces in which two or more conventional surfactant molecules are linked together at a hydrophilic group or near a hydrophilic group via a linking group.
  • Gemini surfactant has at least two hydrophobic hydrocarbon chains, two polar head groups and one linking group; the linking group can be long, short, rigid, flexible, polar, non-polar; Polar head groups are cationic, anionic or nonionic and can be classified into anionic, cationic, nonionic and zwitterionic Gemini surfactants; according to the bipolar head group and hydrophobic chain structure can be divided into symmetric Gemini surfactants and no Symmetric Gemini surfactant.
  • the Gemini surfactant of the step (1) is added in an amount of from 0.1% to 1% by mass based on the total mass of the deionized water and the small molecule organic alcohol.
  • the specific type of Gemini surfactant used in the present invention is not particularly limited.
  • the Gemini surfactant is a bromide having a structure of C mnm ; wherein m is preferably 12, 14 or 16, and n is preferably 2, 3, 6, 8 or 10.
  • the Gemini surfactants used may be obtained by a commercially available channel. For example, the structures available from Henan Road Purification Co., Ltd.
  • the addition of Gemini surfactant and small molecular alcohol to modify the silica sol improves the dispersibility of the silica sol, so that the active component copper has higher dispersibility and improves the activity of the catalyst;
  • the addition of Gemini surfactant can further cooperate with the organic pore former to promote the formation of mesoporous structure and improve the mass transfer performance of the catalyst.
  • a precipitating agent means a substance which can react with a metal cation in a mixed salt solution to form a corresponding precipitate.
  • Step (2) is to dispose a mixed salt solution and an aqueous alkaline precipitant solution, and jointly add the two to the aqueous silica sol dispersion, so as to form a mixed salt in the aqueous silica sol dispersion containing the pore-forming agent. precipitation. It has been found that pre-dispersing the pore former in the silica sol and then forming a precipitate therein facilitates better dispersion of the pore former in the precipitation.
  • the silicon-containing basic precipitating agent is a water-soluble silicate, preferably one or both of sodium silicate and potassium silicate; and the silicon-free alkaline precipitate
  • the agent is one or more of potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium hydrogencarbonate, urea, and ammonia.
  • each of the metal salts forming the mixed salt solution is a soluble salt of the corresponding metal.
  • the copper-containing compound salt is one or more of copper nitrate, copper chloride and copper acetate
  • the zinc-containing compound salt is zinc nitrate, zinc chloride and zinc acetate.
  • the rare earth metal compound salt is one or more of a nitrate, a chloride and an acetate
  • the alkaline earth metal compound salt is one or more of a nitrate, a chloride and an acetatekind.
  • Zn and Cu can form a "solid solution" during the preparation process, which can effectively promote the dispersion of the active component copper in the catalyst; the addition of the rare earth metal also serves to improve the dispersion of copper and the stability of the catalyst in the catalyst.
  • the rare earth metal is lanthanum and/or cerium; the addition of the alkaline earth metal significantly inhibits the acidity of the catalyst, can effectively inhibit the formation of ethylbenzene, and improve the reaction selectivity.
  • the alkaline earth metal is magnesium, calcium and strontium. One or two or more. It is understood by those skilled in the art that the amount of each metal component added is such that the corresponding oxide content of each metal component in the obtained catalyst reaches the target content.
  • the catalyst obtained contains 20-65 wt% of copper oxide, 15-50 wt% of silica, 2-25 wt% of zinc oxide, and 0.1-5 wt% of rare earth metal oxide, based on the total weight of the catalyst.
  • alkaline earth metal oxides 0.5 to 15% by weight; more preferably, 40 to 63% by weight of copper oxide, 20 to 45% by weight of silicon oxide, 5 to 20% by weight of zinc oxide, 0.2 to 3% by weight of rare earth metal oxide, and alkaline earth metal oxide 0.5 to 10% by weight; further preferably, 42 to 60% by weight of copper oxide, 22 to 40% by weight of silicon oxide, 10 to 18% by weight of zinc oxide, 0.5 to 2% by weight of rare earth metal oxide, and 1 to 5% by weight of alkaline earth metal oxide.
  • the pH of the reaction system during the reaction is controlled to be 5.0-9.0, such as 5.5-8.0, and then aged to obtain a slurry; preferably, the temperature of the reaction process and the aging process is controlled to be 60-90 ° C, for example 70 or 80 ° C.
  • the process in which the specific reaction forms a precipitate and the precipitation aging process are well known in the art. For example, the reaction process for forming a precipitate can be completed within 1-3 hours, and then can be aged for another 1-3 hours.
  • the step (3) is to filter and wash the slurry to obtain a filter cake; the filtration and washing processes can all adopt the filtration and washing processes commonly used in the art, and are all catalyst treatment processes commonly used in the art. .
  • drying, roasting and molding the filter cake are also catalyst treatment processes commonly used in the art; in one embodiment, the calcination temperature is 300-700 ° C, such as 400, 500 or 600 ° C; the calcination time is 4-12h, such as 6, 8 or 10h; the forming may be tablet forming or the like.
  • the present invention also provides a catalyst produced according to the above production method.
  • the catalyst composition comprises: 20-65 wt% of copper oxide, 15-50 wt% of silica, 2-25 wt% of zinc oxide, 0.1-5 wt of rare earth metal oxide, based on the total weight of the catalyst.
  • alkaline earth metal oxide 0.5-15wt% more preferably, including copper oxide 40-63wt%, silica 20-45wt%, zinc oxide 5-20wt%, rare earth metal oxide 0.2-3wt%, and alkaline earth metal Oxide 0.5-10% by weight; further preferably, including copper oxide 42-60 wt%, such as 50 wt%, silica 22-40 wt%, such as 30 wt%, zinc oxide 10-18 wt%, such as 15 wt%, rare earth metal oxide 0.5 - 2 wt%, such as 1 wt% or 1.5 wt%, and alkaline earth metal oxide 1-5 wt%, such as 2 wt% or 3 wt%.
  • the invention also provides the use of the above catalyst in the liquid phase hydrogenation of acetophenone to prepare ⁇ -phenylethyl alcohol.
  • the catalyst needs to be subjected to reduction activation to have corresponding catalytic activity for hydrogenation of acetophenone to prepare ⁇ -phenylethyl alcohol.
  • the method for reducing activation of the catalyst of the present invention comprises: maintaining a mixed gas volume velocity of hydrogen and nitrogen of 300-1000 h -1 , preferably first raising the reactor temperature to 160-180 ° C, The catalyst adsorbed physical water is removed at a constant temperature for 1-2 hours, and then the catalyst is pretreated by introducing a mixture of the hydrogen and nitrogen containing a volume fraction of not more than 10 v% H 2 , such as (5 v% ⁇ 2 v%) H 2 .
  • the obtained reduced state catalyst is used for hydrogenation of acetophenone to prepare ⁇ -phenylethanol
  • the reaction pressure is 2.5-5 MPa (relative pressure), for example, 3-5 MPa (relative pressure)
  • the amount of catalyst is 0.2-0.6g HPA ⁇ g cat -1 ⁇ h -1 .
  • the catalyst prepared by the invention is used for the liquid phase hydrogenation of acetophenone to prepare ⁇ -phenylethanol, the catalyst active component is uniformly distributed, the copper dispersion is high, the catalyst pores are smooth, and the acidity is weak. Excellent activity, selectivity and mechanical strength.
  • the addition of the pore former can effectively improve the mass transfer performance of the catalyst, and is beneficial to improving the activity of the catalyst;
  • the liquid phase hydrogenation catalyst with high activity and good mechanical strength can be obtained by using the composite silicon source;
  • the addition of Zn, rare earth and alkaline earth metal in the catalyst composition is beneficial to increase the dispersion of the active component Cu, inhibit the acidity of the catalyst, and improve the activity and selectivity of the catalyst.
  • the lateral pressure strength of the catalyst was measured by a particle strength tester, and the used catalyst was immersed and protected with ethylbenzene to prevent the catalyst from being oxidized. The lateral pressure strength of the catalyst after 40 reaction was measured, and the average value was taken.
  • the content of copper ions in the hydrogenation liquid was determined by inductively coupled plasma emission spectrometry (ICP).
  • the pH of the system was adjusted to >7.5 using a 10 wt% sodium carbonate solution, and aged at 75 ° C for 3 h, then filtered, washed and the filter cake was dried at 110 ° C for 12 h and calcined at 350 ° C for 8 h. Thereafter, 1.5 wt% of the powder mass of graphite was mixed and pressed into a 3*3 mm cylinder (diameter 3 mm, height 3 mm) catalyst to obtain a catalyst A of about 200 g.
  • the catalyst contained 55% of copper oxide, 30% of silicon oxide, 10% of zinc oxide, 1% of cerium oxide, and 4% of magnesium oxide.
  • Catalyst reduction Catalyst A was charged in a fixed bed hydrogenation reactor with a catalyst loading of 100 ml. The catalyst is reduced under the mixture of nitrogen and hydrogen before use. The volume velocity of the mixed gas is maintained at 300 h -1 during the reduction process. The temperature of the reactor is first raised to 160 ° C for 2 h to remove the physical water adsorbed by the catalyst, and then the volume is introduced. The mixture of hydrogen and nitrogen with a fraction of 5v%H 2 is pre-reduced for 1h, then gradually increase the proportion of hydrogen in the mixture of hydrogen and nitrogen to 10v%, 20v%, 50v%, 100v%, and control the hot spot temperature of the catalyst bed in the process. Not more than 220 ° C, and finally heated to 220 ° C in a pure hydrogen atmosphere for 3 h.
  • the hydrogenation feedstock composition is 15 wt% acetophenone in ethylbenzene solution at a pressure of 2.5 MPa, a temperature of 70 ° C, a H 2 /ketone molar ratio of 5:1, and a catalyst throughput of 0.3 g HPA /g cat /h. reaction.
  • the hydrogenation liquid was taken every 24 hours and the copper ion content in the hydrogenation liquid was measured.
  • the catalyst was removed from the reactor and the catalyst was sieved with a stainless steel sample sieve having a pore size of 2 mm, and the ratio of the mass of the catalyst particles having a particle size of ⁇ 1 mm to the total mass of the catalyst was calculated as the catalyst breakage rate.
  • the side pressure strength of the catalyst after the reaction was measured using a particle strength tester.
  • the results of the hydrogenation reaction and the average copper ion content in the hydrogenation liquid are shown in Table 1.
  • the catalyst comparison before and after the reaction is shown in Table 2.
  • the pH of the system was adjusted to >7.5 using a 10 wt% sodium carbonate solution, and aged at 80 ° C for 3 h, then filtered, washed and the filter cake was dried at 100 ° C for 24 h and calcined at 400 ° C for 12 h. Thereafter, 1.0 wt% of the powder mass of graphite was mixed and pressed into a 3*3 mm cylinder (diameter 3 mm, height 3 mm) catalyst to obtain a catalyst B of about 200 g.
  • the catalyst contained 60% copper oxide, 23% silicon oxide, 12% zinc oxide, 0.5% cerium oxide, and 4.5% calcium oxide, based on the oxide.
  • Example 1 The rest of the conditions are referred to in Example 1.
  • the reactor was charged with 200 g of water, 10 g of propanol, 10.0 g of methylcellulose having a particle size of 5-20 ⁇ m, and 1.0 g of a Gemini surfactant (purchased from Henan Road Purification Co., Ltd.) having a structure of C 14-8-14 . Uniform, then 116.7 g of a 30 wt% strength silica sol was added and stirred well.
  • the pH of the system was adjusted to >7.3 using a 10 wt% sodium carbonate solution, aged at 85 ° C for 3 h, then filtered, washed and the filter cake was dried at 120 ° C for 12 h and calcined at 550 ° C for 8 h. Thereafter, 1.2 wt% of the powder mass of graphite was mixed and pressed into a 3*3 mm cylinder (diameter 3 mm, height 3 mm) catalyst to obtain a catalyst C of about 200 g.
  • the catalyst contained 50% of copper oxide, 35% of silicon oxide, 12% of zinc oxide, 1% of cerium oxide, and 2% of cerium oxide.
  • Example 1 The rest of the conditions are referred to in Example 1.
  • the pH of the system was adjusted to >7.2 using a 10 wt% sodium carbonate solution, and aged at 70 ° C for 3 h, then filtered, washed, and the filter cake was dried at 100 ° C for 12 h and baked at 450 ° C for 6 h. Thereafter, 1.0 wt% of the powder mass of graphite was mixed and pressed into a 3*3 mm cylinder (diameter 3 mm, height 3 mm) catalyst to obtain a catalyst D of about 200 g.
  • the catalyst contained 45% of copper oxide, 35% of silicon oxide, 15% of zinc oxide, 2% of cerium oxide, and 3% of calcium oxide.
  • Example 1 The rest of the conditions are referred to in Example 1.
  • the two solutions were heated to 85 ° C.
  • the two solutions were simultaneously dropped into the reaction vessel, and the temperature in the autoclave was controlled at 85 ° C, the pH of the system was 7.0, and the reaction time was 1 h.
  • the pH of the system was adjusted to >7.5 using a 10 wt% sodium carbonate solution, and aged at 90 ° C for 3 h, then filtered, washed and the filter cake was dried at 110 ° C for 12 h and calcined at 650 ° C for 4 h.
  • the catalyst contained 40% copper oxide, 38% silicon oxide, 18% zinc oxide, 1.5% cerium oxide, and 2.5% calcium oxide, based on the oxide.
  • Example 1 The rest of the conditions are referred to in Example 1.
  • the two solutions were heated to 65 °C.
  • the two solutions were simultaneously dropped into the reaction vessel, and the temperature in the reactor was controlled to be 65 ° C, the pH of the system was 6.8, and the reaction time was 1 h.
  • the pH of the system was adjusted to >7.5 using a 10 wt% sodium carbonate solution, and aged at 70 ° C for 3 h, then filtered, washed and the filter cake was dried at 110 ° C for 24 h and calcined at 450 ° C for 8 h.
  • the catalyst contained 52% of copper oxide, 32% of silicon oxide, 10% of zinc oxide, 1% of cerium oxide, and 5% by weight of cerium oxide.
  • Example 1 The rest of the conditions are referred to in Example 1.
  • Example 7 is substantially the same as Example 1, except that the Gemini surfactant used is a Gemini surfactant ethylene bis(hexadecyldimethylammonium bromide) having a structure of C 16-2-16 ( Purchased from Henan Road Purification Company).
  • the Gemini surfactant used is a Gemini surfactant ethylene bis(hexadecyldimethylammonium bromide) having a structure of C 16-2-16 ( Purchased from Henan Road Purification Company).
  • Example 8 is substantially the same as Example 2, except that the Gemini surfactant used is a Gemini surfactant propylene bis(dodecyldimethylammonium bromide) having a structure of C 12-3-12 (purchased) From Henan Road Purification Company).
  • the Gemini surfactant used is a Gemini surfactant propylene bis(dodecyldimethylammonium bromide) having a structure of C 12-3-12 (purchased) From Henan Road Purification Company).
  • Example 9 is substantially the same as Example 3 except that the Gemini surfactant used is a Gemini surfactant ethylene bis(tetradecyldimethylammonium bromide) having a structure of C 14-2-14 (purchased) From Henan Road Purification Company).
  • the Gemini surfactant used is a Gemini surfactant ethylene bis(tetradecyldimethylammonium bromide) having a structure of C 14-2-14 (purchased) From Henan Road Purification Company).
  • Example 10 is substantially the same as Example 4, except that the Gemini surfactant used is a Gemini surfactant propylene bis(dodecyldimethylammonium bromide) of the formula C 12-3-12 (purchased) From Henan Road Purification Company).
  • the Gemini surfactant used is a Gemini surfactant propylene bis(dodecyldimethylammonium bromide) of the formula C 12-3-12 (purchased) From Henan Road Purification Company).
  • Example 11 is substantially the same as Example 5, except that the Gemini surfactant used is a Gemini surfactant ethylene bis(tetradecyldimethylammonium bromide) of the formula C 14-2-14 (purchased) From Henan Road Purification Company).
  • the Gemini surfactant used is a Gemini surfactant ethylene bis(tetradecyldimethylammonium bromide) of the formula C 14-2-14 (purchased) From Henan Road Purification Company).
  • Example 12 is substantially the same as Example 6, except that the Gemini surfactant used is a Gemini surfactant propylene bis(dodecyldimethylammonium bromide) of the formula C 12-3-12 (purchased) From Henan Road Purification Company).
  • the Gemini surfactant used is a Gemini surfactant propylene bis(dodecyldimethylammonium bromide) of the formula C 12-3-12 (purchased) From Henan Road Purification Company).
  • Example 1 The rest of the conditions are referred to in Example 1.
  • Example 1 The rest of the conditions are referred to in Example 1.
  • the catalyst preparation process was carried out without adding a small molecule alcohol and a Gemini surfactant, and the rest of the same procedure as in Example 1 was carried out to obtain about 200 g of the catalyst I.
  • Example 1 The rest of the conditions are referred to in Example 1.
  • the organic pore former PMMA was not added during the catalyst preparation, and the same as in Example 1, the catalyst J was prepared to obtain about 200 g.
  • Example 1 The rest of the conditions are referred to in Example 1.
  • the hydrogenation reaction results of the catalysts of Examples 1-6 and the average copper ion content in the hydrogenation liquid are shown in Table 1.
  • the catalyst comparison before and after the reaction is shown in Table 2.
  • the experimental results of the catalysts prepared in Examples 7-12 were all the same as the corresponding experimental results of Examples 1-6, respectively, wherein the conversion of acetophenone was above 98.1%, and the selectivity of ⁇ -phenylethanol was 99.3%.
  • the detection results of the average copper ion content in the hydrogenation liquid are all “undetected”; the lateral pressure strength of the catalyst before the reaction is all above 188 N/piece, and the lateral pressure strength of the catalyst after the reaction reaches 48.5 N/piece or more.
  • the catalysts are all intact, free of chalking and crushing.
  • the catalyst A to the catalyst F have high activity and can effectively suppress side reactions such as hydrogenolysis to ethylbenzene and dehydration to styrene, and the catalysts of Comparative Examples 1 to 4 are not only low in activity but also in poor selectivity.

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Abstract

一种苯乙酮液相加氢制备α-苯乙醇的催化剂的制备方法，包括：向反应釜中加入水、小分子醇、Gemini表面活性剂和有机造孔剂，然后加入硅溶胶，并搅拌均匀，配成硅溶胶水分散液；配置含铜、锌、稀土金属、碱土金属的化合物盐的混合盐溶液和碱性沉淀剂，并将两者共同加入到硅溶胶水分散液中，经沉淀反应、老化、过滤、洗涤、干燥、焙烧和成型得到催化剂。采用硅溶胶和硅酸盐作为复合硅源，沉淀过程之前加入有机造孔剂，并采用Zn、稀土及碱土金属对催化剂进行改性，用于苯乙酮液相加氢制备α-苯乙醇时不仅活性高、选择性好，而且有效提高了催化剂的抗液性，催化剂的强度高、稳定性好。

Description

苯乙酮加氢制备α-苯乙醇的催化剂、制备方法及应用 技术领域
本发明属于催化加氢技术领域，具体涉及一种苯乙酮液相加氢制备α-苯乙醇的催化剂、其制备方法以及应用。
背景技术
α-苯乙醇是一种重要的化工中间体，广泛应用于医药、香料制造业、化妆品、食品和精细化工等工业中。现有的α-苯乙醇合成方法主要有微生物发酵法和苯乙酮还原/催化加氢法等。
微生物发酵法一般以苯丙氨酸、氟苯丙氨酸为原料，通过微生物发酵转化制取α-苯乙醇。微生物法所采用的原料价格昂贵，生产成本高。目前工业上生产α-苯乙醇通常采用苯乙酮加氢法，该方法具有生产成本低、副产物少、产品收率高、产品纯度高等优点，适于大规模生成α-苯乙醇。
苯乙酮加氢催化剂主要有铂钯贵金属催化剂、镍基催化剂和铜基催化剂等，贵金属催化剂和镍基催化剂成本高、易造成芳环饱和及苯乙醇氢解，α-苯乙醇选择性较差。与贵金属催化剂、镍系催化剂相比，铜系催化剂用于苯乙酮加氢反应具有活性和选择性高、成本低等优势。
苯乙酮加氢制α-苯乙醇的催化剂在许多专利中都有报道。CN1557545A采用浸渍法制备了Ni-Sn-B/SiO 2催化剂，低温焙烧后采用KBH4为还原剂进行还原，其催化反应时，苯乙醇最高选择性达97.5％，但其活性组分Ni与载体SiO 2相互作用力弱、易流失。
US4996374公开了一种Pd-C催化剂，但其催化剂稳定性较差，套用时需不断提高反应温度。CN1315226A公开了一种还原处理的铜基催化剂及用其制备α－苯乙醇的方法，但其需要采用液相还原的方法以提高催化剂的稳定性，工艺复杂、成本高。CN1911883A公开了一种以雷尼镍为催化剂制备α-苯乙醇的方法，但其苯乙酮加氢产物中出现 了较多的芳环加氢产物α-环己基乙醇，α-苯乙醇选择性较低。
EP0714877B1采用碱金属和/或碱土金属碳酸盐对铜硅催化剂改性显著抑制了副产物乙苯的生成，但其硅源以气相二氧化硅或硅藻土的形式加入不利于增强活性组分和载体的相互作用，对催化剂强度不利。
WO2016198379催化剂中部分硅源以硅溶胶的形式在挤条成型时加入，不能有效起到对活性组分铜的分散作用。上述公开报道均未提及助剂对活性组分的分散、稳定作用，以及成型催化剂使用时的机械稳定性和使用后的强度。
由于苯乙酮加氢过程极易发生α-苯乙醇氢解/脱水副反应生成乙苯/苯乙烯，氢解和脱水反应速率均随反应温度升高迅速增长。为提高苯乙酮加氢过程选择性通常选择在较低的温度下进行液相加氢反应。因此要求苯乙酮加氢催化剂具有良好的抗液性能、较弱的酸性和良好的低温活性。
现有技术中，用于液相加氢反应的铜系催化剂不仅受到储存/装填/还原/反应等过程各种内部或外部力的作用，还会由于液体浸泡、溶胀等原因使催化剂的实际使用强度大幅下降，导致催化剂在液相加氢体系容易破碎、粉化，威胁工业装置稳定运行，影响催化剂寿命。
目前，采用沉淀法制备的苯乙酮加氢制备α-苯乙醇铜系催化剂通常存在活性组分铜分散度低、催化剂酸性强、载体和活性组分相互作用力弱等问题，导致苯乙酮转化率低、乙苯等副产物生成量大、苯乙醇选择性差、催化剂强度差。因此改善活性组分铜的分散度及催化剂的传质性能、抑制催化剂酸性、提高催化剂抗液性能对于制备高活性、高选择性及高抗液性能的苯乙酮加氢催化剂意义重大。
发明内容
本发明的目的在于提供一种苯乙酮液相加氢制备α-苯乙醇的催化剂的制备方法以及制得的催化剂，采用该方法制备的催化剂显著抑制了氢解等副反应，催化剂活性高、选择性好；同时催化剂具有优异的抗液能力，历经还原、液相加氢反应后强度高。
为实现上述目的的一个方面，本发明采用如下技术方案：
一种加氢催化剂的制备方法，包括以下步骤：
(1)向反应釜中加入去离子水、小分子醇、Gemini表面活性剂和有机造孔剂，然后加入硅溶胶，并搅拌均匀，配成含小分子醇、Gemini表面活性剂和有机造孔剂的硅溶胶水分散液；
(2)将含铜化合物盐、含锌化合物盐、含稀土金属化合物盐和含碱土金属化合物盐溶解于水中，配置成混合盐溶液；将含硅碱性沉淀剂和不含硅碱性沉淀剂溶于水配置成碱性沉淀剂水溶液；将混合盐溶液与碱性沉淀剂水溶液共同加入所述硅溶胶水分散液中进行反应，控制反应过程中反应体系pH为5.0-9.0，然后老化，得到浆料；
(3)将所述浆料进行过滤、洗涤，得到滤饼；
(4)将所述滤饼进行干燥、焙烧、成型，得到催化剂。
本发明中，步骤(1)为将去离子水、小分子醇、Gemini表面活性剂和有机造孔剂和硅溶胶混合均匀，配成含小分子醇、Gemini表面活性剂和有机造孔剂的硅溶胶水分散液。其中，所述有机造孔剂优选选自PMMA、微晶纤维素、甲基纤维素中的一种或多种；在制备过程中加入有机造孔剂，减小了原料和产物内扩散阻力，有效提高了活性和选择性。
根据本发明的制备方法，优选地，所述有机造孔剂的粒径＜100μmm，更优选1-80μm，进一步优选3-30μm，比如5、10、15、20或25μm；将有机造孔剂的粒径保持在合适的范围内，有助于进一步改善原料和产物扩散传质效果；粒径太大，不利于起到有效改善传质性能的作用，粒径太小，不利于改善传质作用。
根据本发明的制备方法，优选地，所述有机造孔剂的用量占所述催化剂总重的0.5～20wt％，更优选1-10wt％，进一步优选2-5wt％。将有机造孔剂添加量保持在合适的范围内，有助于在取得较好的传质性能的前提下尽量减少对催化剂强度的影响；有机造孔剂添加量太少，不利于起到改善催化剂传质性能的作用；造孔剂的添加量太多则会较多的影响催化剂机械强度。
在本发明中，所述催化剂中的总硅量由所述硅溶胶和含硅碱性沉 淀剂共同引入，优选地，由所述硅溶胶引入的硅量占催化剂中总硅量的30-70wt％，更优选35-65wt％，进一步优选40-60wt％，比如50wt％；研究发现，将高分散的硅溶胶与含硅碱性沉淀剂作复合硅源，与使用单一硅源相比，制备的催化剂不仅活性高，而且强度好。优选地，所述硅溶胶为碱性硅溶胶，pH值为8.0-10.0。
在本发明中，所述小分子醇是指分子量不大于400的醇，比如分子量不大于400的小分子饱和一元醇。根据本发明的制备方法，优选地，所述小分子醇与去离子水质量比为1:20至1:10，比如1:18、1:15或1:12；进一步优选地，所述步骤(1)的小分子醇为甲醇、乙醇、丙醇和丁醇中的一种或多种。
在本发明中，所用Gemini表面活性剂为本领域所熟知，它是通过联接基将2个或2个以上的传统表面活性剂分子在亲水基或接近亲水基处连接在一起的新型表面活性剂。Gemini表面活性剂至少有两个疏水碳氢链、两个极性头基和一个联接基团；联接基团可长、可短、可刚性、可柔性、可极性、可非极性；根据极性头基为阳离子、阴离子或非离子可分为阴离子型、阳离子型、非离子型和两性离子Gemini表面活性剂；根据两极性头基和疏水链结构可分为对称Gemini表面活性剂和不对称Gemini表面活性剂。根据本发明的制备方法，优选地，所述步骤(1)的Gemini表面活性剂，添加量为去离子水和小分子有机醇总质量的0.1％-1％。本发明所用的Gemini表面活性剂具体种类并无特别限制，在一些优选实施方式中，所述Gemini表面活性剂是结构为C m-n-m的溴化物；其中m优选为12、14或16，n优选为2、3、6、8或10。所用Gemini表面活性剂均可采用市售渠道获得的相应试剂，例如可购自河南道纯化工公司的结构为C 16-6-16、C 12-10-12、C 14-8-14、C 12-8-12、C 14-10-14的Gemini表面活性剂，或比如结构为C 16-2-16、C 12-3-12、C 14-2-14、C 12-3-12的Gemini表面活性剂等。
研究发现，本发明中，加入Gemini表面活性剂和小分子醇对硅溶胶进行改性，提高了硅溶胶的分散性，使得活性组分铜具有更高的分散性，提高了催化剂活性；同时，Gemini表面活性剂的添加还可以进一步与有机造孔剂配合促进介孔结构的形成，改善催化剂的传质性 能。
本发明中，沉淀剂是指可以与混合盐溶液中的金属阳离子反应形成相应沉淀的物质。步骤(2)为配置混合盐溶液和碱性沉淀剂水溶液，并将两者共同加入所述硅溶胶水分散液中，以便在含有机造孔剂的硅溶胶水分散液使混合盐形成相应的沉淀。研究发现，将造孔剂预先分散在硅溶胶中，然后再在里面形成沉淀，有利于造孔剂在沉淀中的更优分散。
根据本发明的制备方法，优选地，所述含硅碱性沉淀剂为水溶性硅酸盐，优选为硅酸钠、硅酸钾中的一种或两种；所述不含硅碱性沉淀剂为碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化钠、氢氧化钾、碳酸铵、碳酸氢铵、尿素和氨水中的一种或多种。
本领域技术人员理解，在本发明中，形成混合盐溶液的各金属盐均为相应金属的可溶性盐。根据本发明的制备方法，优选地，所述含铜化合物盐为硝酸铜、氯化铜和乙酸铜的一种或多种；所述含锌化合物盐为硝酸锌、氯化锌和乙酸锌的一种或多种；所述稀土金属化合物盐为硝酸盐、氯化物和乙酸盐的一种或多种；所述碱土金属化合物盐为硝酸盐、氯化物和乙酸盐的一种或多种。
在本发明中，制备过程中Zn与Cu可形成“固溶体”，可有效促进催化剂中活性组分铜的分散；稀土金属的加入也起到了提高催化剂中铜的分散度和催化剂稳定性的作用，优选地，所述稀土金属为镧和/或铈；碱土金属的加入显著抑制了催化剂酸性，可有效抑制乙苯的生成，提高反应选择性，优选地，所述碱土金属为镁、钙和钡的一种或两种或多种。本领域技术人员理解，各金属组分的加入量为使制得的催化剂中各金属组分对应的氧化物含量达到目标含量所对应的量即可。优选的一些实施方案中，制得的催化剂中，以催化剂总重计，含有氧化铜20-65wt％，氧化硅15-50wt％，氧化锌2-25wt％，稀土金属氧化物0.1-5wt％，和碱土金属氧化物0.5-15wt％；更优选地，含有氧化铜40-63wt％，氧化硅20-45wt％，氧化锌5-20wt％，稀土金属氧化物0.2-3wt％，和碱土金属氧化物0.5-10wt％；进一步优选地，含有氧化铜42-60wt％，氧化硅22-40wt％，氧化锌10-18wt％，稀土金属氧化 物0.5-2wt％，和碱土金属氧化物1-5wt％。
步骤(2)中，控制反应过程中反应体系pH为5.0-9.0，比如5.5-8.0，然后老化，得到浆料；优选地，所述反应过程和老化过程的温度控制为60-90℃，比如70或80℃。具体的反应形成沉淀的过程以及沉淀老化过程为本领域熟知，例如可以在1-3h内完成形成沉淀的反应过程，然后可以再老化1-3h。
在本发明中，步骤(3)为将所述浆料进行过滤、洗涤，得到滤饼；该过滤、洗涤过程均可采用本领域常用的过滤、洗涤过程，均为本领域常用的催化剂处理过程。步骤(4)中，对滤饼进行干燥、焙烧、成型也是本领域常用的催化剂处理过程；在一种实施方式中，焙烧温度为300-700℃，比如400、500或600℃；焙烧时间为4-12h，比如6、8或10h；所述成型可以是压片成型等。
为实现上述目的的一个方面，本发明还提供了根据上述制备方法制得的催化剂。
根据本发明的制备方法，优选地，按催化剂总重计，所述催化剂组成包括：氧化铜20-65wt％，氧化硅15-50wt％，氧化锌2-25wt％，稀土金属氧化物0.1-5wt％，和碱土金属氧化物0.5-15wt％；更优选地，包括氧化铜40-63wt％，氧化硅20-45wt％，氧化锌5-20wt％，稀土金属氧化物0.2-3wt％，和碱土金属氧化物0.5-10wt％；进一步优选地，包括氧化铜42-60wt％，比如50wt％，氧化硅22-40wt％，比如30wt％，氧化锌10-18wt％，比如15wt％，稀土金属氧化物0.5-2wt％，比如1wt％或1.5wt％，和碱土金属氧化物1-5wt％，比如2wt％或3wt％。
本发明还提供了上述催化剂在苯乙酮液相加氢制备α-苯乙醇中的应用。
本领域技术人员理解，所述的催化剂需要进行还原活化后才具备相应的催化活性，用于苯乙酮加氢制备α-苯乙醇。
在一种优选实施方式中，本发明所述的催化剂的还原活化的方法包括：保持氢气和氮气的混合气体体积空速300-1000h -1，优选首先将反应器温度升至160-180℃，恒温1-2h脱除催化剂吸附的物理水，然 后通入含体积分数不超过10v％H 2，比如(5v％±2v％)H 2的所述氢气和氮气的混合气对所述催化剂进行预还原至少0.5h，比如1h、1.5h或2h之后逐步提高氢气和氮气混合气中氢气的比例，例如逐步提升至10v％、20v％、50v％、100v％，控制该过程催化剂床层热点温度不超过220℃，最后升温至200-220℃在纯氢气氛下还原2-5h，比如3或4h，得到活化的催化剂。
在一种优选实施方式中，得到的还原态的催化剂用于苯乙酮加氢制备α-苯乙醇时，反应压力为2.5-5MPa(相对压力)，例如3-5MPa(相对压力)，反应温度为70-140℃，例如120-140℃，H 2/HPA(苯乙酮)摩尔比2-20:1，比如5:1、10:1或15:1，催化剂用量为0.2-0.6g HPA·g cat -1·h -1。
与现有技术相比，本发明制备得到的催化剂用于苯乙酮液相加氢制备α-苯乙醇的过程中，催化剂活性组分分布均匀、铜分散度高、催化剂孔道通畅、酸性弱、具有优异的活性、选择性及机械强度。
另外，本发明所述方法制备的催化剂，造孔剂的添加可有效改善催化剂传质性能，有利于提高催化剂活性；采用复合硅源可得到具有高活性和良好机械强度的液相加氢催化剂；催化剂组成中Zn、稀土、碱土金属的添加有利于提高活性组分Cu的分散度、抑制催化剂酸性，提高催化剂活性和选择性。
具体实施方式
下面结合实施例对本发明方法加以详细描述，但不局限于实施例。
催化剂的侧压强度采用颗粒强度测试仪测定，使用后的催化剂用乙苯浸泡保护，以防催化剂被氧化，测定40粒反应后催化剂侧压强度，取其平均值。
加氢液中铜离子含量采用电感耦合等离子发射光谱仪(ICP)测定。
如未特别说明，以下所用试剂均为分析纯，均为市售产品。
实施例1
反应釜内加入200g水、10g甲醇、4.0g粒径在10-30μm的PMMA、2.0g结构为C 16-6-16的Gemini表面活性剂(购自河南道纯化工公司)混合均匀，然后加入120.0g 30wt％浓度的pH值为9的碱性硅溶胶并搅拌均匀。将332.2g硝酸铜、73.1g硝酸锌、21.3g硝酸镧、12.7g硝酸镁溶于1.5kg水中配成混合盐水溶液，将113.5g硅酸钠和142.5g碳酸钠溶于水中配成沉淀剂溶液，分别将两种溶液加热至70℃。采用共沉淀的方法，将两种溶液同时滴入反应釜内，控制沉淀过程釜内温度70℃、体系pH为7.0、反应时间为1h。两种溶液滴加完毕后使用10wt％碳酸钠溶液将体系pH值调至＞7.5，在75℃下老化3h，然后过滤、洗涤并将滤饼在110℃干燥12h，并于350℃焙烧8h，之后混入1.5wt％粉料质量的石墨并压成3*3mm圆柱体(直径3mm、高度3mm)催化剂，即得催化剂A约200g。以氧化物计，该催化剂含氧化铜55％，氧化硅30％，氧化锌10％，氧化镧1％，氧化镁4％。
催化剂还原：将催化剂A装于固定床加氢反应器中，催化剂装填量100ml。催化剂使用前在氮气和氢气混合气下进行还原，还原过程中保持混合气体体积空速300h -1，首先将反应器温度升至160℃恒温2h脱除催化剂吸附的物理水，然后通入含体积分数5v％H 2的氢气和氮气的混合气进行预还原1h，之后逐步提高氢气和氮气混合气中氢气的比例至10v％、20v％、50v％、100v％，控制该过程催化剂床层热点温度不超过220℃，最后升温至220℃在纯氢气氛下还原3h。
加氢原料组成为15wt％苯乙酮的乙苯溶液，在压力2.5Mpa，温度70℃，H 2/酮摩尔比5:1，催化剂处理量为0.3g HPA/g cat/h的条件下进行反应。每间隔24h取加氢液并测定加氢液中铜离子含量。反应100h后将催化剂从反应器拆卸出并用孔径2mm的不锈钢分样筛对催化剂进行筛分，并计算粒径＜1mm的催化剂颗粒质量占催化剂总质量的比例，以此作为催化剂破损率。采用颗粒强度测试仪测定反应后催化剂侧压强度。加氢反应结果及加氢液中平均铜离子含量见表1。反应前后催化剂对比见表2。
实施例2
反应釜内加入200g水、15g乙醇、6.0g粒径在5-30μm的微晶纤维素、0.5g结构为C 12-10-12的Gemini表面活性剂(购自河南道纯化工公司)，然后加入61.3g 30wt％浓度的硅溶胶，搅拌均匀。将362.4g硝酸铜、87.7g硝酸锌、22.7g硝酸铈、4.21g硝酸钙溶于1.45kg水中配成混合盐水溶液，将130.5g硅酸钠和149.0g碳酸钠溶于水中配成沉淀剂溶液，分别将两种溶液加热至75℃。采用共沉淀的方法，将两种溶液同时滴入反应釜内，控制沉淀过程釜内温度75℃、体系pH为7.2、反应时间为1h。两种溶液滴加完毕后使用10wt％碳酸钠溶液将体系pH值调至＞7.5，在80℃下老化3h，然后过滤、洗涤并将滤饼在100℃干燥24h，并于400℃焙烧12h，之后混入1.0wt％粉料质量的石墨并压成3*3mm圆柱体(直径3mm、高度3mm)催化剂，即得催化剂B约200g。以氧化物计，该催化剂含氧化铜60％，氧化硅23％，氧化锌12％，氧化铈0.5％，氧化钙4.5％。
其余条件参照实施例1。
实施例3
反应釜内加入200g水、10g丙醇、10.0g粒径在5-20μm的甲基纤维素、1.0g结构为C 14-8-14的Gemini表面活性剂(购自河南道纯化工公司)混合均匀，然后加入116.7g 30wt％浓度的硅溶胶并搅拌均匀。将302g硝酸铜、87.7g硝酸锌、5.0g硝酸铈、6.8g硝酸钡溶于1.37kg水中配成混合盐水溶液，将198.7g硅酸钠和93.6g碳酸钠溶于水中配成沉淀剂溶液，分别将两种溶液加热至80℃。采用共沉淀的方法，将两种溶液同时滴入反应釜内，控制沉淀过程釜内温度80℃、体系pH为8.0、反应时间为1h。两种溶液滴加完毕后使用10wt％碳酸钠溶液将体系pH值调至＞7.3，在85℃下老化3h，然后过滤、洗涤并将滤饼在120℃干燥12h，并于550℃焙烧8h，之后混入1.2wt％粉料质量的石墨并压成3*3mm圆柱体(直径3mm、高度3mm)催化剂，即得催化剂C约200g。以氧化物计，该催化剂含氧化铜50％，氧化硅35％， 氧化锌12％，氧化铈1％，氧化钡2％。
其余条件参照实施例1。
实施例4
反应釜内加入200g水、20g丁醇、6.0g粒径在3-20μm的微晶纤维素、0.2g结构式为C 12-8-12的Gemini表面活性剂(购自河南道纯化工公司)混合均匀，然后加入105g 30wt％浓度的硅溶胶并搅拌均匀。将271.8g硝酸铜、109.7g硝酸锌、10.6g硝酸镧、25.3g硝酸钙溶于1.39kg水中配成混合盐水溶液，将182.1g硅酸钠和105.6g碳酸钠溶于水中配成沉淀剂溶液，分别将两种溶液加热至60℃。采用共沉淀的方法，将两种溶液同时滴入反应釜内，控制沉淀过程釜内温度60℃、体系pH为6.5、反应时间为1h。两种溶液滴加完毕后使用10wt％碳酸钠溶液将体系pH值调至＞7.2，在70℃下老化3h，然后过滤、洗涤并将滤饼在100℃干燥12h，并于450℃焙烧6h，之后混入1.0wt％粉料质量的石墨并压成3*3mm圆柱体(直径3mm、高度3mm)催化剂，即得催化剂D约200g。以氧化物计，该催化剂含氧化铜45％，氧化硅35％，氧化锌15％，氧化镧2％，氧化钙3％。
其余条件参照实施例1。
实施例5
反应釜内加入200g水、20g乙醇、10.0g粒径在10-30μm的PMMA、1.5g结构式为C 14-10-14的Gemini表面活性剂(购自河南道纯化工公司)混合均匀，然后加入177.3g 30wt％浓度的硅溶胶，搅拌均匀。将24.6g硝酸铜、131.6g硝酸锌、7.97g硝酸镧、31.8g硝酸镁溶于1.65kg水中配成混合盐水溶液，将107.8g硅酸钠和128.7g碳酸钠溶于水中配成沉淀剂溶液，分别将两种溶液加热至85℃。采用共沉淀的方法，将两种溶液同时滴入反应釜内，控制沉淀过程釜内温度85℃、体系pH为7.0、反应时间为1h。两种溶液滴加完毕后使用10wt％碳酸钠溶液将体系pH值调至＞7.5，在90℃下老化3h，然后过滤、洗涤并将滤饼在110℃干燥12h，并于650℃焙烧4h，之后混入1.2wt％粉料质量 的石墨并压成3*3mm圆柱体(直径3mm、高度3mm)催化剂，即得催化剂E约200g。以氧化物计，该催化剂含氧化铜40％，氧化硅38％，氧化锌18％，氧化镧1.5％，氧化钙2.5％。
其余条件参照实施例1。
实施例6
反应釜内加入200g水、15g甲醇、4.0g粒径在3-30μm的甲基纤维素、0.8g结构式为C 12-8-12的Gemini表面活性剂(购自河南道纯化工公司)混合均匀，然后加入117.3g 30wt％浓度的硅溶胶，搅拌均匀。将314.1g硝酸铜、73.1g硝酸锌、5.0g硝酸铈、17.0g硝酸钡溶于1.5kg水中配成混合盐水溶液，将136.2g硅酸钠和121.2g碳酸钠溶于水中配成沉淀剂溶液，分别将两种溶液加热至65℃。采用共沉淀的方法，将两种溶液同时滴入反应釜内，控制沉淀过程釜内温度65℃、体系pH为6.8、反应时间为1h。两种溶液滴加完毕后使用10wt％碳酸钠溶液将体系pH值调至＞7.5，在70℃下老化3h，然后过滤、洗涤并将滤饼在110℃干燥24h，并于450℃焙烧8h，之后混入1.5wt％粉料质量的石墨并压成3*3mm圆柱体(直径3mm、高度3mm)催化剂，即得催化剂F约200g。以氧化物计，该催化剂含氧化铜52％，氧化硅32％，氧化锌10％，氧化铈1％，氧化钡5％。
其余条件参照实施例1中。
实施例7-12
其中实施例7与实施例1基本相同，不同仅在于所用Gemini表面活性剂是结构为C 16-2-16的Gemini表面活性剂乙撑基双(十六烷基二甲基溴化铵)(购自河南道纯化工公司)。
实施例8与实施例2基本相同，不同仅在于所用Gemini表面活性剂是结构为C 12-3-12的Gemini表面活性剂丙撑基双(十二烷基二甲基溴化铵)(购自河南道纯化工公司)。
实施例9与实施例3基本相同，不同仅在于所用Gemini表面活性剂是结构为C 14-2-14的Gemini表面活性剂乙撑基双(十四烷基二甲基溴化铵)(购自河南道纯化工公司)。
实施例10与实施例4基本相同，不同仅在于所用Gemini表面活性剂是结构式为C 12-3-12的Gemini表面活性剂丙撑基双(十二烷基二甲基溴化铵)(购自河南道纯化工公司)。
实施例11与实施例5基本相同，不同仅在于所用Gemini表面活性剂是结构式为C 14-2-14的Gemini表面活性剂乙撑基双(十四烷基二甲基溴化铵)(购自河南道纯化工公司)。
实施例12与实施例6基本相同，不同仅在于所用Gemini表面活性剂是结构式为C 12-3-12的Gemini表面活性剂丙撑基双(十二烷基二甲基溴化铵)(购自河南道纯化工公司)。
对比例1
反应釜内加入200g水，并加入60g气相二氧化硅，搅拌均匀。将332.2g硝酸铜溶于1.5kg水中配成混合盐水溶液，配置10wt％碳酸钠水溶液为沉淀剂，分别将两种溶液加热至65℃。采用共沉淀的方法，将两种溶液同时滴入反应釜内，控制沉淀过程釜内温度65℃、体系pH为7.0、反应时间为1h。溶液滴加完毕后在70℃下老化3h，然后过滤、洗涤并将滤饼在110℃干燥24h，并于450℃焙烧8h，之后混入1.2wt％粉料质量的石墨并压成3*3mm圆柱体(直径3mm、高度3mm)催化剂，即得催化剂G约170g。
其余条件参照实施例1。
对比例2
将332.2g硝酸铜、292.4g硝酸锌溶于1.65kg水中配成混合盐水溶液，将碳酸钠溶于水中配成10wt％的碳酸钠溶液，分别将两种溶液加热至65℃。采用共沉淀的方法，将两种溶液同时滴入反应釜内，控制沉淀过程釜内温度65℃、沉淀pH为7.0，沉淀结束后在70℃下老化3h，向过滤、洗涤后的滤饼中加入10.0g氧化铝并在110℃干燥12h、 350℃焙烧4h，之后混入1.5wt％粉料质量的石墨并压片成型得到3*3mm圆柱体(直径3mm、高度3mm)催化剂，即得催化剂H约190g。
其余条件参照实施例1。
对比例3
催化剂制备过程不加入小分子醇和Gemini表面活性剂，其余同实施例1，制备得到催化剂I约200g。
其余条件参照实施例1。
对比例4
催化剂制备过程不加入有机造孔剂PMMA，其余同实施例1，制备得到催化剂J约200g。
其余条件参照实施例1。
实施例1-6催化剂的加氢反应结果及加氢液中平均铜离子含量见表1，反应前后催化剂对比见表2。实施例7-12制得的催化剂的实验结果均依次分别与实施例1-6的相应实验结果基本相同，其中苯乙酮转化率均在98.1％以上，α-苯乙醇选择性均达到99.3％以上，加氢液中平均铜离子含量的检测结果均为“未检出”；反应前催化剂侧压强度均在188N/颗以上，反应后催化剂侧压强度均达到48.5N/颗以上，反应后催化剂均为完整状态，无粉化和破碎。
表1 加氢反应结果及加氢液中平均铜离子含量
Figure PCTCN2018093616-appb-000001
Figure PCTCN2018093616-appb-000002
注：“未检出”表示加氢液中平均铜离子含量＜0.1μg/g
表2 反应前后催化剂对比
Figure PCTCN2018093616-appb-000003
*N/颗是催化剂强度单位即使1颗催化剂破碎所施加的力
由表1、表2可知，使用催化剂A至催化剂F，以及催化剂I和催化剂J时，加氢液中未检测到铜，反应后催化剂完整且侧压强度在30N/粒以上；而对比例1和对比例2所述催化剂，反应后催化剂破碎严重、侧压强度低，催化剂H出现粉化以致无法测其侧压强度，ICP分析显示加氢液中铜含量较高，说明催化剂有明显流失。并且，催化剂A至催化剂F活性高且能够有效抑制氢解生成乙苯和脱水生成苯乙 烯等副反应，而对比例1至对比例4所述催化剂不仅活性低而且选择性差。

Claims (12)

  1. 一种加氢催化剂的制备方法，包括以下步骤：
    (1)向反应釜中加入水、小分子醇、Gemini表面活性剂、有机造孔剂，然后加入硅溶胶，并搅拌均匀，配成含小分子醇、Gemini表面活性剂和有机造孔剂的硅溶胶水分散液；
    (2)将含铜化合物盐、含锌化合物盐、含稀土金属化合物盐和含碱土金属化合物盐溶解于水中，配置成混合盐溶液；将含硅碱性沉淀剂和不含硅碱性沉淀剂溶于水配置成碱性沉淀剂水溶液；将混合盐溶液与碱性沉淀剂水溶液共同加入所述硅溶胶水分散液中进行反应，控制反应过程中反应体系pH为5.0-9.0，然后老化，得到浆料；
    (3)将所述浆料进行过滤、洗涤，得到滤饼；
    (4)将所述滤饼进行干燥、焙烧、成型，得到催化剂。
  2. 根据权利要求1所述的制备方法，其特征在于，所述催化剂中的总硅量由所述硅溶胶和含硅碱性沉淀剂共同引入，由所述硅溶胶引入的硅量占催化剂中总硅量的30-70wt％，优选35-65wt％，更优选40-60wt％；
    优选地，所述硅溶胶为碱性硅溶胶，pH值为8.0-10.0。
  3. 根据权利要求1或2所述的制备方法，其特征在于，所述含硅碱性沉淀剂为水溶性硅酸盐，优选为硅酸钠、硅酸钾中的一种或两种；
    所述不含硅碱性沉淀剂为碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化钠、氢氧化钾、碳酸铵、碳酸氢铵、尿素和氨水中的一种或多种。
  4. 根据权利要求1-3中任一项所述的制备方法，其特征在于，所述有机造孔剂的粒径＜100μmm，优选1-80μm，更优选3-30μm；
    优选地，所述有机造孔剂选自PMMA、微晶纤维素、甲基纤维素中的一种或多种。
  5. 根据权利要求1-4中任一项所述的制备方法，其特征在于，所述有机造孔剂的用量占所述催化剂总重的0.5～20wt％，优选1-10wt％，更优选2-5wt％。
  6. 根据权利要求1-5中任一项所述的制备方法，其特征在于，步 骤(1)中，所述小分子醇与水质量比为1:20至1:10；优选地，所述步骤(1)的小分子醇为甲醇、乙醇、丙醇和丁醇中的一种或多种。
  7. 根据权利要求1-6中任一项所述的制备方法，其特征在于，所述步骤(1)的Gemini表面活性剂，添加量为水和小分子醇总质量的0.1％-1％；优选地，所述Gemini表面活性剂是结构为C m-n-m的溴化物；其中m为12、14或16，n为2、3、6、8或10。
  8. 根据权利要求1-7中任一项所述的制备方法，其特征在于，所述稀土金属为镧和/或铈；所述碱土金属为镁、钙和钡的一种或两种或多种；
    优选地，所述含铜化合物盐为硝酸铜、氯化铜和乙酸铜的一种或多种；所述含锌化合物盐为硝酸锌、氯化锌和乙酸锌的一种或多种；所述稀土金属化合物盐为硝酸盐、氯化物和乙酸盐的一种或多种；所述碱土金属化合物盐为硝酸盐、氯化物和乙酸盐的一种或多种。
  9. 根据权利要求1-8中任一项所述的制备方法，其特征在于，步骤(2)的反应过程和老化过程的温度为60-90℃；
    步骤(4)的焙烧温度为300-700℃，焙烧时间为4-12h。
  10. 采用权利要求1-9中任一项所述的制备方法制得的催化剂；优选的，制得的催化剂中，以催化剂总重计，含有氧化铜20-65wt％，氧化硅15-50wt％，氧化锌2-25wt％，稀土金属氧化物0.1-5wt％，和碱土金属氧化物0.5-15wt％；
    更优选地，含有氧化铜40-63wt％，氧化硅20-45wt％，氧化锌5-20wt％，稀土金属氧化物0.2-3wt％，和碱土金属氧化物0.5-10wt％；
    进一步优选地，含有氧化铜42-60wt％，氧化硅22-40wt％，氧化锌10-18wt％，稀土金属氧化物0.5-2wt％，和碱土金属氧化物1-5wt％。
  11. 采用权利要求1-9中任一项所述的制备方法制得的催化剂，在苯乙酮液相加氢制备α-苯乙醇中的应用。
  12. 根据权利要求11所述的应用，其特征在于，在催化苯乙酮加氢制备α-苯乙醇前，对所述催化剂进行还原活化；
    优选的，所述催化剂的还原活化包括如下步骤：保持氢气和氮气的混合气体体积空速300-1000h -1，通入含体积分数不超过10v％H 2的 所述氢气和氮气的混合气对所述催化剂进行预还原至少0.5h，之后逐步提高氢气和氮气混合气中氢气的比例，控制该过程催化剂床层热点温度不超过220℃，最后升温至200-220℃在纯氢气氛下还原2-5h，得到活化的催化剂；
    优选地，将得到的活化催化剂用于苯乙酮加氢制备α-苯乙醇反应的工艺条件包括：反应压力为2.5-5MPa，反应温度为70-140℃，H 2/HPA摩尔比2-20:1，催化剂用量为0.2-0.6g HPA·g cat -1·h -1。
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