WO2024066446A1 - Method for preparing cyclohexanone compound by photocatalysis of biomass phenolic compound - Google Patents

Method for preparing cyclohexanone compound by photocatalysis of biomass phenolic compound Download PDF

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WO2024066446A1
WO2024066446A1 PCT/CN2023/098197 CN2023098197W WO2024066446A1 WO 2024066446 A1 WO2024066446 A1 WO 2024066446A1 CN 2023098197 W CN2023098197 W CN 2023098197W WO 2024066446 A1 WO2024066446 A1 WO 2024066446A1
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photocatalyst
cyclohexanone
guaiacol
reactor
stirring
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PCT/CN2023/098197
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林丽利
赵淑芳
陈翔翔
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浙江工业大学
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring

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  • the invention relates to the technical field of high-value utilization of biomass, and in particular to a method for preparing cyclohexanone compounds by photocatalysis of biomass phenolic compounds.
  • cyclohexanone is mainly used in the production of chemical intermediates such as caprolactam and adipic acid, while caprolactam and adipic acid are important monomers in the production of nylon 6 and nylon 66.
  • the main processes for producing cyclohexanone are phenol oxygenation (accounting for about 3%), cyclohexene hydration (accounting for about 4%), cyclohexane liquid phase oxidation (accounting for more than 90%) and phenol one-step hydrogenation.
  • phenol oxygenation ascending for about 3%
  • cyclohexene hydration ascending for about 4%
  • cyclohexane liquid phase oxidation accounting for more than 90%
  • phenol one-step hydrogenation Using photocatalytic oxidation with molecular oxygen as the oxidant, the process of selective oxidation of organic matter to produce cyclohexanone can also be achieved at room temperature or lower temperatures.
  • Biomass energy is an important part of renewable energy, and the development and utilization of biomass energy is of great significance to the development of world energy.
  • Lignin is one of the main components of woody biomass and is an amorphous aromatic polymer widely found in plants. Lignin can be selectively degraded under high temperature and catalyst to obtain a mixture rich in biomass phenolic compounds.
  • the biomass phenolic compound guaiacol (2-methoxyphenol, Guaiacol) is the most representative lignin depolymerization product and a renewable aromatic compound with high utilization value.
  • the chemical structure of guaiacol includes two oxygen-containing phenolic hydroxyl groups (Csp 2 OH) and phenolic methoxyl groups (Csp 2 OCH 3 ). Among them, the chemical bond energy of the methoxyl group is the weakest (247kJ/mol), and the bond energy of the CO bond between the aromatic benzene ring and the phenolic hydroxyl group is the strongest (414kJ/mol).
  • guaiacol can be directed to dissociate, and selectively breaking some of its chemical bonds can produce a variety of high value-added chemicals, such as catechol, phenol, anisole, cyclohexane, etc.
  • high value-added chemicals such as catechol, phenol, anisole, cyclohexane, etc.
  • due to the CO bond Due to the serious competitive hydrogenation reaction with CC on the benzene ring, the highly selective hydrogenolysis of guaiacol is very challenging.
  • the traditional thermal catalytic reaction has the following problems: first, the reaction temperature is relatively high, and the reaction occurs at above 240°C, and sometimes even as high as 450°C to occur; second, the reaction almost entirely requires H2 atmosphere conditions to occur, and the pressure during the reaction is relatively high, and sometimes the reaction pressure is as high as 65 bar to occur; third, while producing cyclohexanone, the reaction also generates some by-products such as methanol, cyclohexanol, and cyclohexane, which face the difficulty of separation and utilization of the by-products.
  • the present invention provides a method for preparing cyclohexanone compounds with high selectivity through photocatalysis of biomass phenolic compounds, thereby achieving high selectivity of cyclohexanone compounds.
  • a method for preparing cyclohexanone compounds from biomass phenolic compounds by photocatalysis comprising: adding a biomass phenolic compound represented by formula I, a photocatalyst and an aqueous solvent into a reactor, and performing a selective hydrogenation reaction at 150-180° C. under inert gas protection and light irradiation conditions to obtain a cyclohexanone compound represented by formula II;
  • the photocatalyst is composed of a carrier and nanometer-scale bimetallic alloy particles loaded on the carrier, the bimetallic alloy particles are selected from RuPd, PtPd, RhPd, RuRh, RuPt or RhPt, and the carrier is TiO 2 , At least one of CdS, Cu 2 O, CuO, Bi 2 O 3 , NiO, Cr 2 O 3 , Fe 3 O 4 , MoO 3 , ZnO, and MoS 2 , wherein the total loading amount of the bimetallic alloy relative to the carrier in the photocatalyst is 4.0 wt%-20.0 wt%, and the mass ratio of the two metals is 1-10:1-10;
  • R 1 is -H or -OCH 3
  • R 2 is -H, -CH 3 , -C 2 H 5 , -C 3 H 7 or -OCH 3 .
  • the biomass phenolic compounds of the present invention can be obtained by refining phenol-containing bio-oil obtained by depolymerization of lignin.
  • the carrier of the photocatalyst is TiO 2
  • the bimetallic alloy is RuPd alloy.
  • the total loading amount of the bimetallic alloy particles in the photocatalyst relative to the carrier is 5-10 wt %, most preferably 5 wt %.
  • the mass ratio of the two metals is 0.5-3:0.5-3, more preferably 2-3:2-3, most preferably 1:1.
  • the photocatalyst is prepared by the following method: uniformly dispersing the carrier in deionized water to obtain a slurry; adding the above slurry dropwise to an aqueous solution containing metal ions under stirring, and continuing to stir for 0.5-6h after the addition is complete; adding a sodium citrate protective agent, adding a reducing agent aqueous solution dropwise, and continuing to stir for 0.5-6h after the addition is complete; then after washing and drying, reducing at 50-500°C in a hydrogen atmosphere for 0.5-6h, and cooling to obtain the photocatalyst.
  • the reducing agent is sodium borohydride
  • the ratio of its molar amount to the total molar amount of metal ions is 20-1:1.
  • the ratio of the molar amount of sodium citrate to the total molar amount of metal ions is 20-1:1.
  • the aqueous solvent is water or a methanol aqueous solution with a volume concentration of 50-5%.
  • the aqueous solvent contains methanol, it is beneficial to increase the yield of cyclohexanone compounds.
  • the mass ratio of the biomass phenolic compound: the photocatalyst: the aqueous solvent is 100:1-25:500-5000, more preferably 100:20:5000.
  • the illumination is performed by visible light, ultraviolet light or infrared light.
  • xenon lamp illumination is selected.
  • the reaction is carried out under stirring at a stirring rate of 100-1200 r/min.
  • the reaction temperature of the selective hydrogenation reaction is 150°C.
  • the reaction time of the selective hydrogenation reaction is 0.5-20 h, more preferably 3-12 h, further preferably 3-6 h.
  • the present invention takes a sample and filters it, the filter cake is a catalyst, the catalyst is washed with water or ethanol and dried and can be recovered and reused, ethyl acetate is added to the filtrate for extraction, and after sufficient extraction, the upper organic phase is taken for gas chromatography analysis to calculate the conversion rate of biomass phenolic compounds and the selectivity of cyclohexanone compounds.
  • the preparation method of cyclohexanone compounds of the present invention takes guaiacol as a hydrogenation substrate and water as a solvent to prepare cyclohexanone as an example, and the reaction equation is as follows:
  • the present invention has the following beneficial effects: the method for preparing cyclohexanone compounds of the present invention reacts in a water-containing solvent under the conditions of photocatalysis and illumination, and uses hydrogen or H + generated by photocatalytic decomposition of water as a reducing agent to selectively hydrogenate biomass phenolic compounds to prepare cyclohexanone compounds.
  • This process is a water-phase photoreaction body that does not require additional hydrogen and reacts at medium-low temperature and normal pressure.
  • the system has mild reaction conditions, uses water as a solvent, is green and pollution-free, has a high conversion rate of biomass phenolic compounds, and has good selectivity for cyclohexanone compounds.
  • Figure 1 is a HR-TEM image of Ru 5 @TiO 2 , Pd 5 @TiO 2 , and Ru 2.5 Pd 2.5 @TiO 2 catalysts prepared in an embodiment of the present invention.
  • the particle size of RuPd metal in the RuPd@TiO 2 catalyst is 5-10 nm, and the size distribution is relatively uniform.
  • Figure 2 is an EDS-mapping diagram of the Ru 2.5 Pd 2.5 @TiO 2 catalyst prepared in an embodiment of the present invention. As can be seen from the figure, the distribution of the elements Ru and Pd on the metal particles in the Ru 2.5 Pd 2.5 @TiO 2 catalyst is consistent.
  • Figure 3 is an XPS graph of Ru 5 @TiO 2 , Pd 5 @TiO 2 , and Ru 2.5 Pd 2.5 @TiO 2 catalysts prepared in the examples of the present invention.
  • the Pd 3d peak of RuPd@TiO 2 is shifted toward the high binding energy direction
  • the Ru 5 @TiO 2 catalyst compared with the Ru 5 @TiO 2 catalyst, the Ru 3d peak is shifted toward the low binding energy direction.
  • the metal RuPd in RuPd@TiO 2 is an alloy, and Pd transfers electrons to Ru.
  • FIG. 4 is a gas chromatography analysis result of the organic phase obtained in Example 1 of the present invention.
  • guaiacol 0.5 g of guaiacol (0.004 mol), 0.1 g of the Ru 2.5 Pd 2.5 @TiO 2 photocatalyst prepared above, and 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, magnetic stirring was performed at 150°C, the stirring speed was 1000 rpm, and the reaction time was 3 h. Then, a sample was taken and filtered, and the filter cake was used as the catalyst, which could be recycled. 15 mL of ethyl acetate was added to the filtrate, and after sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 0%.
  • the method for preparing cyclohexanone defined in the present invention has higher conversion rate of guaiacol and selectivity of cyclohexanone than those in the comparative example.

Abstract

A method for preparing a cyclohexanone compound by photocatalysis of a biomass phenolic compound, the method comprising: adding a biomass phenolic compound represented by formula I, a photocatalyst, and an aqueous solvent into a reactor, and carrying out a selective hydrogenation reaction at 150-180 °C in an inert gas atmosphere under illumination conditions to obtain a cyclohexanone compound represented by formula II. The method has mild reaction conditions, uses water as an environmentally friendly solvent, yields high conversion rates of biomass phenolic compounds, and has good selectivity for cyclohexanone compounds.

Description

一种由生物质酚类化合物光催化制备环己酮类化合物的方法A method for preparing cyclohexanone compounds by photocatalysis of biomass phenolic compounds 技术领域Technical Field
本发明涉及生物质高值化利用的技术领域，特别是涉及一种由生物质酚类化合物光催化制备环己酮类化合物的方法。The invention relates to the technical field of high-value utilization of biomass, and in particular to a method for preparing cyclohexanone compounds by photocatalysis of biomass phenolic compounds.
背景技术Background technique
环己酮作为一种重要的化工原料，主要用于生产己内酰胺、己二酸等化工中间体，而己内酰胺和己二酸是生产尼6和尼龙66的重要单体。As an important chemical raw material, cyclohexanone is mainly used in the production of chemical intermediates such as caprolactam and adipic acid, while caprolactam and adipic acid are important monomers in the production of nylon 6 and nylon 66.
目前生产环己酮的工艺主要有苯酚加氧法(占比约3％)，环己稀水合法(占比约4％)、环己烷液相氧化法(占比90％以上)和苯酚一步加氢法。利用光催化氧化法以分子氧为氧化剂，在室温或者较低温度下也可实现有机物选择性氧化制环己酮过程。At present, the main processes for producing cyclohexanone are phenol oxygenation (accounting for about 3%), cyclohexene hydration (accounting for about 4%), cyclohexane liquid phase oxidation (accounting for more than 90%) and phenol one-step hydrogenation. Using photocatalytic oxidation with molecular oxygen as the oxidant, the process of selective oxidation of organic matter to produce cyclohexanone can also be achieved at room temperature or lower temperatures.
生物质能源是可再生能源的一个重要组成部分，开发利用生物质能源对世界能源的发展具有重要意义。木质素是木质生物质的主要成分之一，广泛存在于植物体中的无定形的芳香性高聚物。木质素在高温以及催化剂的作用下可以选择性的降解，得到富含生物质酚类化合物的混合物。Biomass energy is an important part of renewable energy, and the development and utilization of biomass energy is of great significance to the development of world energy. Lignin is one of the main components of woody biomass and is an amorphous aromatic polymer widely found in plants. Lignin can be selectively degraded under high temperature and catalyst to obtain a mixture rich in biomass phenolic compounds.
生物质酚类化合物愈创木酚(2-甲氧基苯酚，Guaiacol)作为最具代表性的木质素解聚产物，是一种可再生的芳香族化合物，具有很高的利用价值。愈创木酚的化学结构包括两个含氧酚羟基(Csp2OH)和酚甲氧基(Csp2OCH3)基团。其中，甲氧基的C-O键的化学键能最弱(247kJ/mol)，芳烃苯环与酚羟基之间的C-O键的键能最强(414kJ/mol)。通过选择合适的反应条件和催化剂，可对愈创木酚进行定向解离，选择性地断裂其中的部分化学键可以制得多种高附加值化学品，比如邻苯二酚、苯酚、苯甲醚、环己烷等。然而，由于C-O键 和苯环上的C-C存在严重的加氢竞争反应，愈创木酚的高选择性氢解非常具有挑战性。The biomass phenolic compound guaiacol (2-methoxyphenol, Guaiacol) is the most representative lignin depolymerization product and a renewable aromatic compound with high utilization value. The chemical structure of guaiacol includes two oxygen-containing phenolic hydroxyl groups (Csp 2 OH) and phenolic methoxyl groups (Csp 2 OCH 3 ). Among them, the chemical bond energy of the methoxyl group is the weakest (247kJ/mol), and the bond energy of the CO bond between the aromatic benzene ring and the phenolic hydroxyl group is the strongest (414kJ/mol). By selecting appropriate reaction conditions and catalysts, guaiacol can be directed to dissociate, and selectively breaking some of its chemical bonds can produce a variety of high value-added chemicals, such as catechol, phenol, anisole, cyclohexane, etc. However, due to the CO bond Due to the serious competitive hydrogenation reaction with CC on the benzene ring, the highly selective hydrogenolysis of guaiacol is very challenging.
现有技术中，关于将木质素降解的生物质酚类化合物愈创木酚进行选择性高值化利用的研究，传统热催化反应存在以下几方面问题：一是反应温度较高，反应均发生在240℃以上，有时候甚至高达450℃才能发生反应；二是该反应几乎全部需要在H2气氛条件下才能发生，而且反应时的压力较大，有时候反应压力甚至高达65bar才能发生反应；三是该反应在生产环己酮的同时，还会生成部分甲醇、环己醇、环己烷等副产物，副产物面临分离与利用的难题。In the prior art, regarding the selective high-value utilization of guaiacol, a phenolic compound in biomass degraded from lignin, the traditional thermal catalytic reaction has the following problems: first, the reaction temperature is relatively high, and the reaction occurs at above 240°C, and sometimes even as high as 450°C to occur; second, the reaction almost entirely requires H2 atmosphere conditions to occur, and the pressure during the reaction is relatively high, and sometimes the reaction pressure is as high as 65 bar to occur; third, while producing cyclohexanone, the reaction also generates some by-products such as methanol, cyclohexanol, and cyclohexane, which face the difficulty of separation and utilization of the by-products.
当前生物质酚类化合物类化合物的转化研究主要集中在将其制备为苯酚、环己醇类及环烷烃类化合物，而很少有将其高效选择性地以制备环己酮的报道。Current research on the conversion of biomass phenolic compounds mainly focuses on their preparation into phenol, cyclohexanol and cycloalkane compounds, while there are few reports on their efficient and selective preparation of cyclohexanone.
发明内容Summary of the invention
针对传统热催化方法活化生物质酚类化合物愈创木酚存在反应温度高、愈创木酚转化率低、副产物多、环己酮选择性低的问题，本发明提供了一种通过生物质酚类化合物光催化高选择性地制备环己酮类化合物的方法，实现环己酮类化合物的高选择性。In view of the problems of high reaction temperature, low guaiacol conversion rate, many by-products and low cyclohexanone selectivity in the activation of biomass phenolic compound guaiacol by traditional thermal catalytic method, the present invention provides a method for preparing cyclohexanone compounds with high selectivity through photocatalysis of biomass phenolic compounds, thereby achieving high selectivity of cyclohexanone compounds.
本发明采用的技术方案如下：The technical solution adopted by the present invention is as follows:
一种由生物质酚类化合物光催化制备环己酮类化合物的方法，所述方法包括：在反应器中加入式I所示的生物质酚类化合物、光催化剂和含水溶剂，在惰性气体保护和光照条件下于150-180℃进行选择性加氢反应，得到式II所示的环己酮类化合物；A method for preparing cyclohexanone compounds from biomass phenolic compounds by photocatalysis, the method comprising: adding a biomass phenolic compound represented by formula I, a photocatalyst and an aqueous solvent into a reactor, and performing a selective hydrogenation reaction at 150-180° C. under inert gas protection and light irradiation conditions to obtain a cyclohexanone compound represented by formula II;
所述的光催化剂由载体和负载在载体上的纳米级双金属合金颗粒组成，所述双金属选自RuPd、PtPd、RhPd、RuRh、RuPt或RhPt，所述的载体为TiO2、 CdS、Cu2O、CuO、Bi2O3、NiO、Cr2O3、Fe3O4、MoO3、ZnO、MoS2中的至少一种，所述的光催化剂中双金属合金相对于载体的总负载量为4.0wt％-20.0wt％，两种金属的质量比为1-10:1-10；
The photocatalyst is composed of a carrier and nanometer-scale bimetallic alloy particles loaded on the carrier, the bimetallic alloy particles are selected from RuPd, PtPd, RhPd, RuRh, RuPt or RhPt, and the carrier is TiO 2 , At least one of CdS, Cu 2 O, CuO, Bi 2 O 3 , NiO, Cr 2 O 3 , Fe 3 O 4 , MoO 3 , ZnO, and MoS 2 , wherein the total loading amount of the bimetallic alloy relative to the carrier in the photocatalyst is 4.0 wt%-20.0 wt%, and the mass ratio of the two metals is 1-10:1-10;
其中，R1为-H或-OCH3；R2为-H、-CH3、-C2H5、-C3H7或-OCH3。Wherein, R 1 is -H or -OCH 3 ; R 2 is -H, -CH 3 , -C 2 H 5 , -C 3 H 7 or -OCH 3 .
本发明所述的生物质酚类化合物可由木质素解聚获得的含酚生物油精炼而得。The biomass phenolic compounds of the present invention can be obtained by refining phenol-containing bio-oil obtained by depolymerization of lignin.
作为优选，所述光催化剂的载体为TiO2，所述双金属合金为RuPd合金。Preferably, the carrier of the photocatalyst is TiO 2 , and the bimetallic alloy is RuPd alloy.
作为优选，所述光催化剂中双金属合金颗粒相对于载体的总负载量为5-10wt％，最优选5wt％。Preferably, the total loading amount of the bimetallic alloy particles in the photocatalyst relative to the carrier is 5-10 wt %, most preferably 5 wt %.
作为优选，所述光催化剂中，两种金属的质量比为0.5-3:0.5-3，更优选2-3:2-3，最优选1:1。Preferably, in the photocatalyst, the mass ratio of the two metals is 0.5-3:0.5-3, more preferably 2-3:2-3, most preferably 1:1.
作为优选，所述的光催化剂通过如下方法制备：使载体均匀分散于去离子水中，得到浆液；将上述浆液在搅拌下逐滴加入到含有金属离子的水溶液中，滴加完毕后继续搅拌0.5-6h；加入柠檬酸钠保护剂后，逐滴加入还原剂水溶液，滴加完毕后继续搅拌0.5-6h；然后经洗涤、干燥后，在氢气气氛下于50-500℃还原0.5-6h，降温后得到所述光催化剂。作为进一步的优选，所述还原剂为硼氢化钠，其摩尔量与金属离子的总摩尔量之比为20-1：1。作为进一步的优选，所述柠檬酸钠的摩尔量与金属离子的总摩尔量之比为20-1：1。该光催化剂的制备方法中，载体和金属离子按照两种金属所需的负载量进行投料。 Preferably, the photocatalyst is prepared by the following method: uniformly dispersing the carrier in deionized water to obtain a slurry; adding the above slurry dropwise to an aqueous solution containing metal ions under stirring, and continuing to stir for 0.5-6h after the addition is complete; adding a sodium citrate protective agent, adding a reducing agent aqueous solution dropwise, and continuing to stir for 0.5-6h after the addition is complete; then after washing and drying, reducing at 50-500°C in a hydrogen atmosphere for 0.5-6h, and cooling to obtain the photocatalyst. As a further preference, the reducing agent is sodium borohydride, and the ratio of its molar amount to the total molar amount of metal ions is 20-1:1. As a further preference, the ratio of the molar amount of sodium citrate to the total molar amount of metal ions is 20-1:1. In the preparation method of the photocatalyst, the carrier and the metal ions are fed according to the required loading amount of the two metals.
作为优选，所述含水溶剂为水或体积浓度为50-5％的甲醇水溶液。当含水溶剂中含有甲醇时，有利于提高环己酮类化合物的收率。Preferably, the aqueous solvent is water or a methanol aqueous solution with a volume concentration of 50-5%. When the aqueous solvent contains methanol, it is beneficial to increase the yield of cyclohexanone compounds.
作为优选，所述生物质酚类化合物：光催化剂：含水溶剂的质量比＝100：1-25：500-5000，更优选100:20:5000。Preferably, the mass ratio of the biomass phenolic compound: the photocatalyst: the aqueous solvent is 100:1-25:500-5000, more preferably 100:20:5000.
作为优选，所述光照采用可见光、紫外光或红外光照射，在本申请的具体实施方式中，选择氙灯照射。Preferably, the illumination is performed by visible light, ultraviolet light or infrared light. In a specific embodiment of the present application, xenon lamp illumination is selected.
作为优选，所述反应在搅拌下进行，搅拌速率为100-1200r/min。Preferably, the reaction is carried out under stirring at a stirring rate of 100-1200 r/min.
作为优选，所述选择性加氢反应的反应温度为150℃。Preferably, the reaction temperature of the selective hydrogenation reaction is 150°C.
作为优选，所述选择性加氢反应的反应时间为0.5-20h，更优选3-12h，更进一步优选3-6h。Preferably, the reaction time of the selective hydrogenation reaction is 0.5-20 h, more preferably 3-12 h, further preferably 3-6 h.
本发明在选择性加氢反应完毕后，取样过滤，滤饼为催化剂，催化剂用水或乙醇洗涤干燥后可回收套用，在滤液中加入乙酸乙酯进行萃取，充分萃取后取上层有机相进行气相色谱分析计算生物质酚类化合物的转化率和环己酮类化合物的选择性。After the selective hydrogenation reaction is completed, the present invention takes a sample and filters it, the filter cake is a catalyst, the catalyst is washed with water or ethanol and dried and can be recovered and reused, ethyl acetate is added to the filtrate for extraction, and after sufficient extraction, the upper organic phase is taken for gas chromatography analysis to calculate the conversion rate of biomass phenolic compounds and the selectivity of cyclohexanone compounds.
本发明所述环己酮类化合物的制备方法，以愈创木酚为加氢底物、水为溶剂制备环己酮为例，反应方程式如下：
The preparation method of cyclohexanone compounds of the present invention takes guaiacol as a hydrogenation substrate and water as a solvent to prepare cyclohexanone as an example, and the reaction equation is as follows:
与现有技术相比，本发明的有益效果在于：本发明所述环己酮类化合物的制备方法，在光催化剂和光照条件下在含水溶剂中发生反应，以光催化分解水产生的氢气或H+为还原剂，对生物质酚类化合物进行选择性加氢制备环己酮类化合物。该过程是一种无需额外通入氢气的、中低温常压反应的水相光反应体 系，具有温和的反应条件，水作溶剂绿色无污染，生物质酚类化合物的转化率高，对于环己酮类化合物的选择性好。Compared with the prior art, the present invention has the following beneficial effects: the method for preparing cyclohexanone compounds of the present invention reacts in a water-containing solvent under the conditions of photocatalysis and illumination, and uses hydrogen or H + generated by photocatalytic decomposition of water as a reducing agent to selectively hydrogenate biomass phenolic compounds to prepare cyclohexanone compounds. This process is a water-phase photoreaction body that does not require additional hydrogen and reacts at medium-low temperature and normal pressure. The system has mild reaction conditions, uses water as a solvent, is green and pollution-free, has a high conversion rate of biomass phenolic compounds, and has good selectivity for cyclohexanone compounds.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是本发明实施例制得的Ru5@TiO2、Pd5@TiO2、Ru2.5Pd2.5@TiO2催化剂的HR-TEM图。由图可见，RuPd@TiO2催化剂中RuPd金属的颗粒尺寸为5-10nm，尺寸分布较为均匀。Figure 1 is a HR-TEM image of Ru 5 @TiO 2 , Pd 5 @TiO 2 , and Ru 2.5 Pd 2.5 @TiO 2 catalysts prepared in an embodiment of the present invention. As can be seen from the image, the particle size of RuPd metal in the RuPd@TiO 2 catalyst is 5-10 nm, and the size distribution is relatively uniform.
图2是本发明实施例制得的Ru2.5Pd2.5@TiO2催化剂的EDS-mapping图。由图可知，Ru2.5Pd2.5@TiO2催化剂中元素Ru和Pd在金属颗粒上的分布一致。Figure 2 is an EDS-mapping diagram of the Ru 2.5 Pd 2.5 @TiO 2 catalyst prepared in an embodiment of the present invention. As can be seen from the figure, the distribution of the elements Ru and Pd on the metal particles in the Ru 2.5 Pd 2.5 @TiO 2 catalyst is consistent.
图3是本发明实施例制得的Ru5@TiO2、Pd5@TiO2、Ru2.5Pd2.5@TiO2催化剂的XPS图。由图可见，RuPd@TiO2相比于Pd5@TiO2催化剂，Pd 3d峰向高结合能方向偏移，相比于Ru5@TiO2催化剂，Ru 3d峰向低结合能方向偏移，由此可知RuPd@TiO2中金属RuPd为合金，Pd向Ru传递电子。Figure 3 is an XPS graph of Ru 5 @TiO 2 , Pd 5 @TiO 2 , and Ru 2.5 Pd 2.5 @TiO 2 catalysts prepared in the examples of the present invention. As can be seen from the figure, compared with the Pd 5 @TiO 2 catalyst, the Pd 3d peak of RuPd@TiO 2 is shifted toward the high binding energy direction, and compared with the Ru 5 @TiO 2 catalyst, the Ru 3d peak is shifted toward the low binding energy direction. It can be seen that the metal RuPd in RuPd@TiO 2 is an alloy, and Pd transfers electrons to Ru.
图4是本发明实施例1得到的有机相的气相色谱分析结果。FIG. 4 is a gas chromatography analysis result of the organic phase obtained in Example 1 of the present invention.
具体实施方式Detailed ways
下面结合具体实施例对本发明的技术方案作进一步说明，但本发明的保护范围不限于此：The technical solution of the present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto:
金属总负载量为5％，Ru/Pd比为1：1的双金属Ru2.5Pd2.5合金负载TiO2光催化剂(Ru2.5Pd2.5@TiO2)的制备方法如下：The preparation method of the bimetallic Ru 2.5 Pd 2.5 alloy-loaded TiO 2 photocatalyst (Ru 2.5 Pd 2.5 @TiO 2 ) with a total metal loading of 5% and a Ru/Pd ratio of 1:1 is as follows:
称取1.0g的TiO2粉末，加入50mL的去离子水，在搅拌下分散2h。称取RuCl3(以Ru计：25mg Ru)、PdCl2(以Pd计：25mg Pd)水溶液，加入25mL的去离子水，搅拌均匀后逐滴加入上述TiO2水溶液，滴加完毕后继续搅拌1h。 加入柠檬酸钠(柠檬酸钠/(Ru+Pd)＝3:1(mol/mol))保护剂后，逐滴加入10g/L的NaHB4溶液(NaHB4/(Ru+Pd)＝10:1(mol/mol))，滴加完毕后继续搅拌12h。用去离子水离心洗涤3次，乙醇洗2次，随后在60℃干燥过夜，最后在管式炉40mL/min的氢气气氛下200℃还原2h，降温后取出密封保存。Weigh 1.0 g of TiO 2 powder, add 50 mL of deionized water, and disperse under stirring for 2 h. Weigh RuCl 3 (in terms of Ru: 25 mg Ru) and PdCl 2 (in terms of Pd: 25 mg Pd) aqueous solutions, add 25 mL of deionized water, stir evenly, then add the above TiO 2 aqueous solution dropwise, and continue stirring for 1 h after the addition is complete. After adding sodium citrate (sodium citrate/(Ru+Pd)=3:1(mol/mol)) protective agent, add 10g/L NaHB 4 solution (NaHB 4 /(Ru+Pd)=10:1(mol/mol)) dropwise, and continue stirring for 12h after the addition is complete. Wash with deionized water by centrifugation for 3 times, wash with ethanol for 2 times, then dry at 60°C overnight, and finally reduce at 200°C for 2h in a tubular furnace under a hydrogen atmosphere of 40mL/min, take out and seal for storage after cooling.
实施例和对比例中使用的其它催化剂AxBy@C的制备过程采用上述制备方法进行，只是改变不同载体、金属组分、负载量及质量比，其中A和B代表不同的金属，x和y分别代表A和B两种金属相对于载体的负载量为x％和y％，C代表载体，并且各载体的来源如下表所示。The preparation process of other catalysts AxBy @ C used in the embodiments and comparative examples is carried out by the above-mentioned preparation method, except that different carriers, metal components, loading amounts and mass ratios are changed, wherein A and B represent different metals, x and y represent the loading amounts of A and B metals relative to the carrier as x% and y%, respectively, C represents the carrier, and the sources of each carrier are shown in the following table.
表1
Table 1
实施例1 Example 1
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g上述制备的Ru2.5Pd2.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300W PLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为45.7％，环己酮的收率为42.7％、选择性为93.5％。气相色谱分析结果如下图4所示。0.5g of guaiacol (0.004mol), 0.1g of the Ru 2.5 Pd 2.5 @TiO 2 photocatalyst prepared above, 25mL H 2 O, and nitrogen replaced the air in the reactor 5 times. Then, magnetic stirring was carried out at 150°C with a stirring speed of 1000 rpm, and irradiated with a 300W PLS-SXE300 xenon lamp for 3h, and then a sample was taken and filtered. The filter cake was a catalyst and could be recycled. 15mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation. The conversion rate of guaiacol was 45.7%, the yield of cyclohexanone was 42.7%, and the selectivity was 93.5%. The gas chromatography analysis results are shown in Figure 4 below.
实施例2Example 2
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g上述制备的Ru2.5Pd2.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射1h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为28.8％，环己酮的收率为20.4％、选择性为70.8％。0.5 g of guaiacol (0.004 mol), 0.1 g of the Ru 2.5 Pd 2.5 @TiO 2 photocatalyst prepared above, and 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, the reactor was magnetically stirred at 150°C at a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 1 hour, and then a sample was taken and filtered. The filter cake was the catalyst and could be recycled. 15 mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 28.8%, the yield of cyclohexanone was 20.4%, and the selectivity was 70.8%.
实施例3Example 3
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g上述制备的Ru2.5Pd2.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射6h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为52.0％，环己酮的收率为45.4％、选择性为87.3％。0.5 g of guaiacol (0.004 mol), 0.1 g of the Ru 2.5 Pd 2.5 @TiO 2 photocatalyst prepared above, and 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, the reactor was magnetically stirred at 150°C at a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 6 hours. Then, the sample was filtered, and the filter cake was the catalyst, which could be recycled. 15 mL of ethyl acetate was added to the filtrate, and after sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 52.0%, the yield of cyclohexanone was 45.4%, and the selectivity was 87.3%.
实施例4 Example 4
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g上述制备的Ru2.5Pd2.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射12h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为53.5％，环己酮的收率为45.1％、选择性为84.3％。0.5 g of guaiacol (0.004 mol), 0.1 g of the Ru 2.5 Pd 2.5 @TiO 2 photocatalyst prepared above, and 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, the reactor was magnetically stirred at 150°C at a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 12 h, and then a sample was taken and filtered. The filter cake was the catalyst and could be recycled. 15 mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 53.5%, the yield of cyclohexanone was 45.1%, and the selectivity was 84.3%.
实施例5Example 5
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g上述制备的Ru2.5Pd2.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在25℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为3.2％，环己酮的收率为1.0％、选择性为30.6％。0.5 g of guaiacol (0.004 mol), 0.1 g of the Ru 2.5 Pd 2.5 @TiO 2 photocatalyst prepared above, and 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, the reactor was magnetically stirred at 25°C at a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3 hours. Then, the sample was filtered, and the filter cake was used as the catalyst, which could be recycled. 15 mL of ethyl acetate was added to the filtrate, and after sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 3.2%, the yield of cyclohexanone was 1.0%, and the selectivity was 30.6%.
实施例6Example 6
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g上述制备的Ru2.5Pd2.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在75℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为10.3％，环己酮的收率为6.7％、选择性为64.9％。0.5 g of guaiacol (0.004 mol), 0.1 g of the Ru 2.5 Pd 2.5 @TiO 2 photocatalyst prepared above, and 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, the reactor was magnetically stirred at 75°C at a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3 hours. Then, the sample was filtered, and the filter cake was the catalyst, which could be recycled. 15 mL of ethyl acetate was added to the filtrate, and after sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 10.3%, the yield of cyclohexanone was 6.7%, and the selectivity was 64.9%.
实施例7Example 7
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g上述制备的Ru2.5Pd2.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在180℃ 下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为60.4％，环己酮的收率为47.3％、选择性为78.3％。0.5 g of guaiacol (0.004 mol), 0.1 g of the Ru 2.5 Pd 2.5 @TiO 2 photocatalyst prepared above, 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen 5 times. The mixture was stirred magnetically at a speed of 1000 rpm and irradiated with a 300WPLS-SXE300 xenon lamp for 3 h. The mixture was then sampled and filtered. The filter cake was a catalyst and could be recycled. 15 mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation results showed that the conversion rate of guaiacol was 60.4%, the yield of cyclohexanone was 47.3%, and the selectivity was 78.3%.
实施例8Example 8
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g上述制备的Ru2.5Pd2.5@TiO2光催化剂，25mL H2O，5mL CH3OH，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为67.3％，环己酮的收率为58.6％、选择性为87.0％。0.5 g of guaiacol (0.004 mol), 0.1 g of the Ru 2.5 Pd 2.5 @TiO 2 photocatalyst prepared above, 25 mL of H 2 O, and 5 mL of CH 3 OH were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, the reactor was magnetically stirred at 150°C at a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3 h. Then, the reactor was sampled and filtered. The filter cake was the catalyst and could be recycled. 15 mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculations showed that the conversion rate of guaiacol was 67.3%, the yield of cyclohexanone was 58.6%, and the selectivity was 87.0%.
实施例9Example 9
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g金属总负载量为1.0％的Ru0.5Pd0.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为8.0％，环己酮的收率为6.4％、选择性为80.6％。0.5 g of guaiacol (0.004 mol), 0.1 g of Ru 0.5 Pd 0.5 @TiO 2 photocatalyst with a total metal loading of 1.0%, 25 mL of H 2 O, and nitrogen replaced the air in the reactor 5 times. Then, magnetic stirring was carried out at 150°C with a stirring speed of 1000 rpm, and irradiation was performed with a 300WPLS-SXE300 xenon lamp for 3 hours. Then, a sample was taken and filtered, and the filter cake was used as a catalyst and could be recycled. 15 mL of ethyl acetate was added to the filtrate, and after sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 8.0%, the yield of cyclohexanone was 6.4%, and the selectivity was 80.6%.
实施例10Example 10
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g金属总负载量为3.0％的Ru1.5Pd1.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL 乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为22.5％，环己酮的收率为19.5％、选择性为86.5％。0.5 g guaiacol (0.004 mol), 0.1 g Ru 1.5 Pd 1.5 @TiO 2 photocatalyst with a total metal loading of 3.0%, 25 mL H 2 O, and nitrogen replaced the air in the reactor 5 times. Then, magnetic stirring was carried out at 150°C with a stirring speed of 1000 rpm, and irradiation was performed with a 300WPLS-SXE300 xenon lamp for 3 h. Then, a sample was taken and filtered. The filter cake was the catalyst and could be recycled. 15 mL of Ethyl acetate, after sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the results showed that the conversion rate of guaiacol was 22.5%, the yield of cyclohexanone was 19.5%, and the selectivity was 86.5%.
实施例11Embodiment 11
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g金属总负载量为7.0％的Ru3.5Pd3.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为47.8％，环己酮的收率为44.4％、选择性为92.8％。0.5g of guaiacol (0.004mol), 0.1g of Ru 3.5 Pd 3.5 @TiO 2 photocatalyst with a total metal loading of 7.0%, 25mL H 2 O, and nitrogen replaced the air in the reactor 5 times. Then, magnetic stirring was carried out at 150°C with a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3h, and then a sample was taken and filtered. The filter cake was a catalyst and could be recycled. 15mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation results showed that the conversion rate of guaiacol was 47.8%, the yield of cyclohexanone was 44.4%, and the selectivity was 92.8%.
实施例12Example 12
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g金属总负载量为10.0％的Ru5Pd5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为50.5％，环己酮的收率为46.6％、选择性为92.3％。0.5 g of guaiacol (0.004 mol), 0.1 g of Ru 5 Pd 5 @TiO 2 photocatalyst with a total metal loading of 10.0%, and 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, the reactor was magnetically stirred at 150°C with a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3 hours. Then, the sample was filtered, and the filter cake was used as the catalyst, which could be recycled. 15 mL of ethyl acetate was added to the filtrate, and after sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 50.5%, the yield of cyclohexanone was 46.6%, and the selectivity was 92.3%.
实施例13Example 13
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Ru0.5Pd4.5@TiO2光催化剂(金属总负载量为5.0％，Ru/Pd比1：9)，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为17.7％，环己酮的收率为13.1％、选择性为73.8％。 0.5g guaiacol (0.004mol), 0.1g Ru 0.5 Pd 4.5 @TiO 2 photocatalyst (total metal loading of 5.0%, Ru/Pd ratio 1:9), 25mL H 2 O, and nitrogen replaced the air in the reactor 5 times. Then, magnetic stirring was carried out at 150°C with a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3h, and then the sample was filtered. The filter cake was the catalyst and could be recycled. 15mL ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 17.7%, the yield of cyclohexanone was 13.1%, and the selectivity was 73.8%.
实施例14Embodiment 14
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Ru4.5Pd0.5@TiO2光催化剂(金属总负载量为5.0％，Ru/Pd比9：1)，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为28.8％，环己酮的收率为20.0％、选择性为69.3％。0.5g guaiacol (0.004mol), 0.1g Ru 4.5 Pd 0.5 @TiO 2 photocatalyst (total metal loading of 5.0%, Ru/Pd ratio 9:1), 25mL H 2 O, and nitrogen replaced the air in the reactor 5 times. Then, magnetic stirring was carried out at 150°C with a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3h, and then the sample was filtered. The filter cake was the catalyst and could be recycled. 15mL ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 28.8%, the yield of cyclohexanone was 20.0%, and the selectivity was 69.3%.
实施例15Embodiment 15
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Ru2Pd3@TiO2光催化剂(金属总负载量为5.0％，Ru/Pd比2：3)，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为40.0％，环己酮的收率为37.4％、选择性为93.4％。0.5g guaiacol (0.004mol), 0.1g Ru 2 Pd 3 @TiO 2 photocatalyst (total metal loading of 5.0%, Ru/Pd ratio 2:3), 25mL H 2 O, and nitrogen replaced the air in the reactor 5 times. Then, magnetic stirring was carried out at 150°C with a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3h, and then the sample was filtered. The filter cake was the catalyst and could be recycled. 15mL ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation results showed that the conversion rate of guaiacol was 40.0%, the yield of cyclohexanone was 37.4%, and the selectivity was 93.4%.
实施例16Example 16
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Ru3Pd2@TiO2光催化剂(金属总负载量为5.0％，Ru/Pd比3：2)，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为44.5％，环己酮的收率为39.4％、选择性为88.5％。0.5g guaiacol (0.004mol), 0.1g Ru 3 Pd 2 @TiO 2 photocatalyst (total metal loading of 5.0%, Ru/Pd ratio of 3:2), 25mL H 2 O, and nitrogen replaced the air in the reactor 5 times. Then, magnetic stirring was carried out at 150°C with a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3h, and then the sample was filtered. The filter cake was the catalyst and could be recycled. 15mL ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation results showed that the conversion rate of guaiacol was 44.5%, the yield of cyclohexanone was 39.4%, and the selectivity was 88.5%.
实施例17 Embodiment 17
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Ru2.5Pd2.5@C3N4光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为51.2％，环己酮的收率为46.6％、选择性为91.1％。0.5 g of guaiacol (0.004 mol), 0.1 g of Ru 2.5 Pd 2.5 @C 3 N 4 photocatalyst, 25 mL of H 2 O, and nitrogen were used to replace the air in the reactor for 5 times. Then, the reaction mixture was stirred magnetically at 150°C at a speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3 h. Then, the mixture was sampled and filtered. The filter cake was used as a catalyst and could be recycled. 15 mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculations showed that the conversion rate of guaiacol was 51.2%, the yield of cyclohexanone was 46.6%, and the selectivity was 91.1%.
实施例18Embodiment 18
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Ru2.5Pd2.5@Bi2O3光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为58.8％，环己酮的收率为54.7％、选择性为93.0％。0.5 g of guaiacol (0.004 mol), 0.1 g of Ru 2.5 Pd 2.5 @Bi 2 O 3 photocatalyst, 25 mL of H 2 O, and nitrogen were used to replace the air in the reactor for 5 times. Then, magnetic stirring was carried out at 150°C with a stirring speed of 1000 rpm, and irradiation was performed with a 300WPLS-SXE300 xenon lamp for 3 h. Then, a sample was taken and filtered. The filter cake was the catalyst and could be recycled. 15 mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation. The results showed that the conversion rate of guaiacol was 58.8%, the yield of cyclohexanone was 54.7%, and the selectivity was 93.0%.
实施例19Embodiment 19
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Ru2.5Pd2.5@MoO3光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为49.6％，环己酮的收率为43.6％、选择性为88.0％。0.5 g of guaiacol (0.004 mol), 0.1 g of Ru 2.5 Pd 2.5 @MoO 3 photocatalyst, 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, the reactor was magnetically stirred at 150°C with a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3 hours. Then, the sample was filtered, and the filter cake was used as the catalyst, which could be recycled. 15 mL of ethyl acetate was added to the filtrate, and after sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 49.6%, the yield of cyclohexanone was 43.6%, and the selectivity was 88.0%.
实施例20Embodiment 20
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Ru2.5Pd2.5@WO3光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌， 搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为50.8％，环己酮的收率为45.5％、选择性为89.6％。0.5 g guaiacol (0.004 mol), 0.1 g Ru 2.5 Pd 2.5 @WO 3 photocatalyst, 25 mL H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced with nitrogen 5 times. Then, the reactor was stirred magnetically at 150 °C. The stirring speed was 1000 rpm, and a 300WPLS-SXE300 xenon lamp was used for irradiation for 3 h. Then, a sample was taken for filtration. The filter cake was a catalyst and could be recovered for reuse. 15 mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation results showed that the conversion rate of guaiacol was 50.8%, the yield of cyclohexanone was 45.5%, and the selectivity was 89.6%.
实施例21Embodiment 21
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Ru2.5Pd2.5@Cu2O光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为50.5％，环己酮的收率为46.8％、选择性为92.6％。0.5 g of guaiacol (0.004 mol), 0.1 g of Ru 2.5 Pd 2.5 @Cu 2 O photocatalyst, 25 mL of H 2 O, and nitrogen were used to replace the air in the reactor for 5 times. Then, the reaction mixture was stirred magnetically at 150°C at a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3 h. Then, the mixture was sampled and filtered. The filter cake was the catalyst and could be recycled. 15 mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculations showed that the conversion rate of guaiacol was 50.5%, the yield of cyclohexanone was 46.8%, and the selectivity was 92.6%.
实施例22Embodiment 22
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Ru2.5Pd2.5@CdS光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为59.5％，环己酮的收率为55.8％、选择性为93.7％。0.5 g of guaiacol (0.004 mol), 0.1 g of Ru 2.5 Pd 2.5 @CdS photocatalyst, 25 mL of H 2 O, and nitrogen were used to replace the air in the reactor for 5 times. Then, the reaction mixture was stirred magnetically at 150°C at a speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3 h. Then, the mixture was sampled and filtered. The filter cake was used as a catalyst and could be recycled. 15 mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculations showed that the conversion rate of guaiacol was 59.5%, the yield of cyclohexanone was 55.8%, and the selectivity was 93.7%.
实施例23Embodiment 23
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Ru2.5Pt2.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后 取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为57.5％，环己酮的收率为50.5％、选择性为87.9％。0.5 g guaiacol (0.004 mol), 0.1 g Ru 2.5 Pt 2.5 @TiO 2 photocatalyst, 25 mL H 2 O, and nitrogen were used to replace the air in the reactor 5 times. Then, magnetic stirring was carried out at 150 ° C, the stirring speed was 1000 rpm, and irradiation was carried out with a 300WPLS-SXE300 xenon lamp for 3 h. Then, the sample was filtered, and the filter cake was used as the catalyst, which could be recycled. 15 mL of ethyl acetate was added to the filtrate, and after sufficient extraction, The upper organic phase was analyzed by gas chromatography and the results showed that the conversion rate of guaiacol was 57.5%, the yield of cyclohexanone was 50.5%, and the selectivity was 87.9%.
实施例24Embodiment 24
在光催化反应器中加入0.376g苯酚(0.004mol)、0.1g Ru2.5Pd2.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：苯酚的转化率为63.5％，环己酮的收率为60.2％、选择性为94.8％。0.376g phenol (0.004mol), 0.1g Ru 2.5 Pd 2.5 @TiO 2 photocatalyst, 25mL H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, magnetic stirring was carried out at 150°C with a stirring speed of 1000 rpm, and irradiation was performed with a 300WPLS-SXE300 xenon lamp for 3h, and then sampling and filtration were performed. The filter cake was the catalyst and could be recycled. 15mL ethyl acetate was added to the filtrate, and after sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of phenol was 63.5%, the yield of cyclohexanone was 60.2%, and the selectivity was 94.8%.
实施例25Embodiment 25
在光催化反应器中加入0.55g 4-甲基愈创木酚(0.004mol)、0.1g Ru2.5Pd2.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：4-甲基愈创木酚的转化率为42.0％，4-甲基环己酮的收率为37.9％、选择性为90.2％。0.55g 4-methylguaiacol (0.004mol), 0.1g Ru 2.5 Pd 2.5 @TiO 2 photocatalyst, 25mL H 2 O, and nitrogen replaced the air in the reactor 5 times. Then, magnetic stirring was carried out at 150°C with a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3h, and then a sample was taken and filtered. The filter cake was a catalyst and could be recycled. 15mL ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of 4-methylguaiacol was 42.0%, the yield of 4-methylcyclohexanone was 37.9%, and the selectivity was 90.2%.
对比实施例1Comparative Example 1
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Ru5@TiO2光催化剂(金属Ru负载量为5.0％)，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为7.1％，环己酮的收率为2.0％、选择性为28.4％。 0.5 g of guaiacol (0.004 mol), 0.1 g of Ru 5 @TiO 2 photocatalyst (metal Ru loading of 5.0%), and 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, the reaction was stirred magnetically at 150°C at a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3 hours, and then the sample was filtered. The filter cake was the catalyst and could be recycled. 15 mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 7.1%, the yield of cyclohexanone was 2.0%, and the selectivity was 28.4%.
对比实施例2Comparative Example 2
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g Pd5@TiO2光催化剂(金属Pd负载量为5.0％)，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为5.0％，环己酮的收率为2.4％、选择性为47.0％。0.5 g of guaiacol (0.004 mol), 0.1 g of Pd 5 @TiO 2 photocatalyst (metal Pd loading of 5.0%), and 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, the reaction was stirred magnetically at 150°C at a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3 hours, and then the sample was filtered. The filter cake was the catalyst and could be recycled. 15 mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation results showed that the conversion rate of guaiacol was 5.0%, the yield of cyclohexanone was 2.4%, and the selectivity was 47.0%.
对比实施例3Comparative Example 3
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.05g Ru5@TiO2和0.05gPd5@TiO2物理混合光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，同时用300WPLS-SXE300氙灯照射3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为11.5％，环己酮的收率为4.4％、选择性为38.0％。0.5g of guaiacol (0.004mol), 0.05g of Ru 5 @TiO 2 and 0.05g of Pd 5 @TiO 2 physical mixed photocatalyst, 25mL of H 2 O, and nitrogen replaced the air in the reactor 5 times. Then, magnetic stirring was carried out at 150°C with a stirring speed of 1000 rpm, and irradiated with a 300WPLS-SXE300 xenon lamp for 3h, and then a sample was taken and filtered. The filter cake was a catalyst and could be recycled. 15mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 11.5%, the yield of cyclohexanone was 4.4%, and the selectivity was 38.0%.
对比实施例4Comparative Example 4
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g上述制备的Ru2.5Pd2.5@TiO2光催化剂，25mL H2O，氮气置换反应釜中空气5次。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，反应时间3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为0％。0.5 g of guaiacol (0.004 mol), 0.1 g of the Ru 2.5 Pd 2.5 @TiO 2 photocatalyst prepared above, and 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, magnetic stirring was performed at 150°C, the stirring speed was 1000 rpm, and the reaction time was 3 h. Then, a sample was taken and filtered, and the filter cake was used as the catalyst, which could be recycled. 15 mL of ethyl acetate was added to the filtrate, and after sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 0%.
对比实施例5Comparative Example 5
在光催化反应器中加入0.5g愈创木酚(0.004mol)、0.1g上述制备的Ru2.5Pd2.5@TiO2光催化剂，25mL H2O，氢气置换反应釜中空气5次，氢气分压 0.4MPa。然后在150℃下磁力搅拌，搅拌速度为1000转/分钟，反应时间3h，然后取样过滤，滤饼为催化剂，可回收套用，在滤液中加入15mL乙酸乙酯，充分萃取后取上层有机相进行气相色谱分析计算得到：愈创木酚的转化率为46.1％，环己酮的收率为19.2％、选择性为41.7％。0.5 g of guaiacol (0.004 mol), 0.1 g of the Ru 2.5 Pd 2.5 @TiO 2 photocatalyst prepared above, and 25 mL of H 2 O were added to the photocatalytic reactor. The air in the reactor was replaced by hydrogen 5 times. The hydrogen partial pressure was 0.4MPa. Then, magnetic stirring was performed at 150°C, the stirring speed was 1000 rpm, the reaction time was 3h, and then sampling and filtration were performed. The filter cake was a catalyst and could be recycled. 15mL of ethyl acetate was added to the filtrate. After sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation. The conversion rate of guaiacol was 46.1%, the yield of cyclohexanone was 19.2%, and the selectivity was 41.7%.
从上述实施例可以得知，本发明限定的环己酮制备方法，其愈创木酚的转化率、环己酮的选择性均比对比实施例高。 It can be seen from the above examples that the method for preparing cyclohexanone defined in the present invention has higher conversion rate of guaiacol and selectivity of cyclohexanone than those in the comparative example.

Claims (10)

  1. 一种由生物质酚类化合物光催化制备环己酮类化合物的方法，其特征在于所述方法包括：在反应器中加入式I所示的生物质酚类化合物、光催化剂和含水溶剂，在惰性气体保护和光照条件下于150-180℃进行选择性加氢反应，得到式II所示的环己酮类化合物；A method for preparing cyclohexanone compounds from biomass phenolic compounds by photocatalysis, characterized in that the method comprises: adding a biomass phenolic compound represented by formula I, a photocatalyst and an aqueous solvent into a reactor, and performing a selective hydrogenation reaction at 150-180° C. under inert gas protection and light irradiation conditions to obtain a cyclohexanone compound represented by formula II;
    所述的光催化剂由载体和负载在载体上的纳米级双金属合金颗粒组成，所述双金属选自RuPd、PtPd、RhPd、RuRh、RuPt或RhPt，所述的载体为TiO2、CdS、Cu2O、CuO、Bi2O3、NiO、Cr2O3、Fe3O4、MoO3、ZnO、MoS2中的至少一种，所述的光催化剂中双金属合金相对于载体的总负载量为4.0wt％-20.0wt％，两种金属的质量比为1-10:1-10；
    The photocatalyst is composed of a carrier and nanometer-scale bimetallic alloy particles loaded on the carrier, the bimetallic is selected from RuPd, PtPd, RhPd, RuRh, RuPt or RhPt, the carrier is at least one of TiO 2 , CdS, Cu 2 O, CuO, Bi 2 O 3 , NiO, Cr 2 O 3 , Fe 3 O 4 , MoO 3 , ZnO and MoS 2 , the total loading amount of the bimetallic alloy in the photocatalyst relative to the carrier is 4.0wt%-20.0wt%, and the mass ratio of the two metals is 1-10:1-10;
    其中，R1为-H或-OCH3；R2为-H、-CH3、-C2H5、-C3H7或-OCH3。Wherein, R 1 is -H or -OCH 3 ; R 2 is -H, -CH 3 , -C 2 H 5 , -C 3 H 7 or -OCH 3 .
  2. 如权利要求1所述的方法，其特征在于：所述光催化剂中双金属合金颗粒相对于载体的总负载量为5-10wt％，最优选5wt％。The method according to claim 1 is characterized in that the total loading amount of the bimetallic alloy particles in the photocatalyst relative to the carrier is 5-10wt%, most preferably 5wt%.
  3. 如权利要求1所述的方法，其特征在于：所述光催化剂中，两种金属的质量比为0.5-3:0.5-3，更优选2-3:2-3，最优选1:1。The method according to claim 1, characterized in that: in the photocatalyst, the mass ratio of the two metals is 0.5-3:0.5-3, more preferably 2-3:2-3, and most preferably 1:1.
  4. 如权利要求1-3中任一项所述的方法，其特征在于：所述的光催化剂通过如下方法制备：使载体均匀分散于去离子水中，得到浆液；将上述浆液在搅 拌下逐滴加入到含有金属离子的水溶液中，滴加完毕后继续搅拌0.5-6h；加入柠檬酸钠保护剂后，逐滴加入还原剂水溶液，滴加完毕后继续搅拌0.5-6h；然后经洗涤、干燥后，在氢气气氛下于50-500℃还原0.5-6h，降温后得到所述光催化剂。The method according to any one of claims 1 to 3, characterized in that: the photocatalyst is prepared by the following method: uniformly dispersing the carrier in deionized water to obtain a slurry; stirring the slurry The mixture is added dropwise into an aqueous solution containing metal ions while stirring, and stirring is continued for 0.5-6 hours after the addition is completed; after adding the sodium citrate protective agent, the reducing agent aqueous solution is added dropwise, and stirring is continued for 0.5-6 hours after the addition is completed; after washing and drying, the mixture is reduced at 50-500°C in a hydrogen atmosphere for 0.5-6 hours, and the photocatalyst is obtained after cooling.
  5. 如权利要求1所述的方法，其特征在于：所述含水溶剂为水或体积浓度为50-5％的甲醇水溶液。The method according to claim 1, characterized in that the aqueous solvent is water or a methanol aqueous solution with a volume concentration of 50-5%.
  6. 如权利要求1所述的方法，其特征在于：所述生物质酚类化合物：光催化剂：含水溶剂的质量比＝100：1-25：500-5000，更优选100:20:5000。The method according to claim 1, characterized in that the mass ratio of the biomass phenolic compound: the photocatalyst: the aqueous solvent is 100:1-25:500-5000, more preferably 100:20:5000.
  7. 如权利要求1所述的方法，其特征在于：所述光照采用可见光、紫外光或红外光照射，如氙灯照射。The method according to claim 1, characterized in that the illumination is irradiated by visible light, ultraviolet light or infrared light, such as xenon lamp irradiation.
  8. 如权利要求1所述的方法，其特征在于：所述反应在搅拌下进行，搅拌速率为100-1200r/min。The method according to claim 1, characterized in that the reaction is carried out under stirring at a stirring rate of 100-1200 r/min.
  9. 如权利要求1所述的方法，其特征在于：所述选择性加氢反应的反应温度为150℃。The method according to claim 1, characterized in that the reaction temperature of the selective hydrogenation reaction is 150°C.
  10. 如权利要求1所述的方法，其特征在于：所述选择性加氢反应的反应时间为0.5-20h，更优选3-12h，更进一步优选3-6h。 The method according to claim 1, characterized in that the reaction time of the selective hydrogenation reaction is 0.5-20 h, more preferably 3-12 h, and further preferably 3-6 h.
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