WO2020186421A1 - 一种配位型磷钨酸锆催化剂及其在催化氢化糠醛中的应用 - Google Patents

一种配位型磷钨酸锆催化剂及其在催化氢化糠醛中的应用 Download PDF

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WO2020186421A1
WO2020186421A1 PCT/CN2019/078471 CN2019078471W WO2020186421A1 WO 2020186421 A1 WO2020186421 A1 WO 2020186421A1 CN 2019078471 W CN2019078471 W CN 2019078471W WO 2020186421 A1 WO2020186421 A1 WO 2020186421A1
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furfural
catalyst
furfuryl alcohol
zirconium phosphotungstate
coordination type
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PCT/CN2019/078471
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English (en)
French (fr)
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王海军
徐广志
刘晨
胡爱云
夏咏梅
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江南大学
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Priority to PCT/CN2019/078471 priority Critical patent/WO2020186421A1/zh
Priority to US16/971,775 priority patent/US11938465B2/en
Publication of WO2020186421A1 publication Critical patent/WO2020186421A1/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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • 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
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J37/06—Washing
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C07D307/44—Furfuryl alcohol

Definitions

  • the invention relates to a coordination type zirconium phosphotungstate catalyst and its application in the catalytic hydrogenation of furfural, belonging to the field of heterogeneous catalysis.
  • Biomass is not only a renewable resource, but also the most widely distributed, quantity and type of energy on the earth, so it has attracted great attention from many researchers.
  • biomass Through the basic material platform of biomass, more and more high-value-added compounds are produced using these basic substances as raw materials. Therefore, the development of new production technologies, production routes, and the production of high-value-added compounds are important for actual production and modern industry. Development has a profound impact.
  • Furfural as the basic platform substance of biomass, is a five-carbon compound derived from some agricultural products such as wheat and corncob. It has abundant reserves and has a wide range of uses. Furfural can be used as a basic raw material to synthesize many high value-added compounds. Among them, furfuryl alcohol is a high value-added compound. Furfural can be used in the production of resins, fuels, synthetic fibers, rubber, plastics, and pesticides in a wide range of industries.
  • CN107445923A discloses a process for preparing furfuryl alcohol by hydrogenation of furfural, which uses copper-supported polyglutamic acid/N-methylolacrylamide as a catalyst and hydrogen as a hydrogen source.
  • CN107963998A discloses a method for preparing furfuryl alcohol by transfer hydrogenation of furfural formic acid. Pd/C and CuO are used as a composite catalyst, formic acid is a hydrogen donor, and a reaction at 170°C for 3 hours can be achieved to obtain a better catalytic effect.
  • Phosphotungstic acid has acidity and redox properties. It is a multifunctional new catalyst with high catalytic activity and good stability. It can be used in homogeneous and heterogeneous reactions. It is mainly used as a catalyst for organic synthesis reactions. , Biochemical reagents and chromatographic analysis reagents. As a catalyst, phosphotungstic acid has the advantages of high reaction activity, green pollution-free, can be recycled for many times, and less activity loss.
  • the present invention provides a coordination type zirconium phosphotungstate catalyst with high-efficiency catalytic ability, which can catalyze the conversion of furfural
  • the yield of furfuryl alcohol can reach 98.64% after reacting at 120°C for 1 hour, which can achieve high catalytic activity under mild reaction conditions, and is easy to recycle and reuse.
  • the present invention first provides a preparation method of the coordination type zirconium phosphotungstate catalyst.
  • the method includes the following steps: separately dissolving phosphotungstic acid and ZrCl 4 in DMF, and after ultrasonic treatment, within 5-30 minutes Add the phosphotungstic acid solution dropwise to the ZrCl 4 solution. After uniformly mixing, add triethylamine, and then react at room temperature for 3 to 6 hours. The aging time is greater than 4 hours. Wash with DMF, methanol, and anhydrous ether for 1 to 3, respectively. Next, vacuum drying is carried out at 70-100°C, and the drying time is longer than 8 hours to obtain the coordination type zirconium phosphotungstate catalyst.
  • the time of the ultrasonic treatment is 5-30 min, and the frequency of the ultrasonic is 40-60 kHz.
  • the molar ratio of the phosphotungstic acid to ZrCl 4 is 3:1 to 1:3.
  • the concentration of phosphotungstic acid is (0.05-0.15) mol/L, and the concentration of ZrCl 4 is (0.05-0.15) mol/L.
  • the addition amount of the triethylamine is 1 to 3 mL/mmol phosphotungstic acid.
  • the present invention also provides the coordination type zirconium phosphotungstate catalyst prepared by the above preparation method.
  • the present invention provides a method for catalyzing the hydrogenation of furfural to prepare furfuryl alcohol.
  • the coordination type zirconium phosphotungstate prepared by the above method is used as a catalyst, and furfural is used as a substrate.
  • Zirconium acid/mmol furfural is added to the catalyst and reacted at 110-150°C for 0.5-4h, wherein isopropanol is used as the hydrogen source, and the added amount is 5-10mL/mmol furfural.
  • the reaction temperature is preferably 120°C.
  • the reaction time is preferably 1 h.
  • the added amount of isopropanol is 5 mL/mmol furfural.
  • the added amount of coordination type zirconium phosphotungstate is preferably 0.2 g/mmol furfural.
  • the present invention also provides the application of the above-mentioned method for catalyzing the hydrogenation of furfural to prepare furfuryl alcohol in the preparation of resins, fuels, synthetic fibers, rubber, plastics, and pesticides.
  • the present invention has the following advantages and effects:
  • the catalyst used in the present invention is coordinated zirconium phosphotungstate, which not only has a good catalytic effect on the conversion of furfural to furfuryl alcohol, but also has mild reaction conditions.
  • the solid furfuryl alcohol yield is 98.64 after reacting at 120°C for 1 hour. %, greatly reducing the energy consumption required in the prior art.
  • the raw material phosphotungstic acid used in the catalyst of the present invention has a special structure, which can provide a good microenvironment for the reaction, thereby improving the yield and selectivity of furfuryl alcohol;
  • the active part of the catalyst used in the present invention is metal Zirconium, which has good properties, realizes the efficient conversion of furfural to furfuryl alcohol under relatively mild reaction conditions.
  • the coordination type zirconium phosphotungstate catalyst of the present invention is a heterogeneous type. After the reaction, the catalyst can be recovered and used in the next reaction through simple filtration, and it still has a good catalytic effect after multiple cycles. Reflects the policy of green chemistry.
  • Fig. 1 is an XRD pattern of the coordination zirconium phosphotungstate catalyst prepared in Example 1.
  • Example 2 is the SEM (a) and TEM (b) photos of the coordination type zirconium phosphotungstate catalyst prepared in Example 1.
  • Figure 3 shows the yield of furfuryl alcohol in the hydrogenation of furfural catalyzed by different types of metal zirconium phosphotungstate catalysts in Example 4.
  • Figure 4 shows the yield of furfuryl alcohol in the hydrogenation of furfural by the coordination type zirconium phosphotungstate catalyst in Example 5 at different temperatures.
  • Figure 5 shows the furfuryl alcohol yield of the coordination type zirconium phosphotungstate catalyst in Example 6 for catalyzing the hydrogenation of furfural at different times.
  • Figure 6 shows the yield of furfuryl alcohol in the catalytic hydrogenation of furfural with the coordination type zirconium phosphotungstate catalyst in Example 7 under different catalyst dosages.
  • Figure 7 shows the yield of furfuryl alcohol in the hydrogenation of furfural by the coordination type zirconium phosphotungstate catalyst in Example 8 under different reaction solvents.
  • GC Gas chromatography
  • Zr-PW zirconium phosphotungstate
  • Zirconium phosphotungstate can be prepared by grinding into powder.
  • the prepared zirconium phosphotungstate (Zr-PW) was characterized, and its XRD pattern and electron micrograph were shown in Figures 1 and 2, respectively. It can be seen that the catalyst prepared in the present invention has an irregular mesoporous structure.
  • Zr-PW zirconium phosphotungstate
  • Zirconium phosphotungstate can be prepared by grinding into powder.
  • Zr-PW zirconium phosphotungstate
  • Zr-PW zirconium phosphotungstate
  • its catalytic performance take the molar ratio of ZrCl 4 :PW (phosphotungstic acid) as 3:1, 2:1, 1:1, 1 respectively
  • ZrCl 4 :PW phosphotungstic acid
  • the two raw materials obtained above were each dissolved in 20ml of DMF, and ultrasonicated for 20min. After the above solution is uniformly mixed, add 3ml of triethylamine solution dropwise, then react at room temperature for 4h, aging for 4h, wash three times with DMF, methanol, and anhydrous ether, and dry it in vacuum drying at 80°C for 12h.
  • Zirconium phosphotungstate catalyst can be prepared by grinding into powder.
  • the prepared zirconium phosphotungstate catalyst was used as a catalyst for catalyzing furfural:
  • step (2) Weigh 1mmol furfural and add it to the system of step (1), put the polytetrafluoroethylene lining into the stainless steel reactor, heat it to 150°C under magnetic stirring, react for 3h, the reaction is over, wait until the reactor is cooled to After room temperature, the solid and liquid are separated by a centrifuge, and the liquid phase is to be sampled;
  • step (3) Use a sampler to pipette 0.2 ⁇ L of the reaction solution in step (2), and use a gas chromatograph to determine the yield of furfuryl alcohol.
  • zirconium phosphotungstate prepared when the molar ratio of ZrCl 4 :PW (phosphotungstic acid) is 2:1 is preferred as a catalyst for subsequent research.
  • the ZrCl 4 was replaced with AlCl 3 to prepare the corresponding catalyst aluminum phosphotungstate (Al-PW); in addition, phosphotungstic acid and ZrCl 4 were used separately as the reaction raw materials according to the method of Example 1.
  • the catalyst phosphotungstic acid and ZrCl 4 are prepared .
  • the phosphotungstic acid was replaced with phosphomolybdic acid (PM), respectively, and ZrCl 4 and AlCl 3 were reacted to prepare the corresponding catalysts: zirconium phosphomolybdate (Zr-PM) and aluminum phosphomolybdate (Al -PM), in addition, the catalyst phosphomolybdic acid was prepared separately using phosphomolybdic acid according to the method of Example 1.
  • the catalyst Zr-PW prepared in Example 1 and the catalyst prepared in Example 4 Al-PW, phosphotungstic acid, ZrCl 4 , zirconium phosphomolybdate Zr-PM, aluminum phosphomolybdate Al-PM or phosphomolybdic acid PM As a catalyst for catalyzing furfural:
  • step (2) Weigh 1mmol of furfural and add it to the system of step (1), put the polytetrafluoroethylene lining into the stainless steel reactor, heat it to 120°C under magnetic stirring, react for 1h, the reaction is over, and the reactor is cooled to After room temperature, the solid and liquid are separated by a centrifuge, and the liquid phase is to be sampled;
  • step (3) Pipette 0.2 ⁇ L of the reaction solution in step (2) with a sampler, and measure the yield of furfuryl alcohol with a gas chromatograph.
  • step (2) Weigh 1 mmol furfural and add it to the reaction system of step (1), put the polytetrafluoroethylene lining into the stainless steel reactor, and heat to 110°C ⁇ 150°C under magnetic stirring, react for 1h, and wait until the end of the reaction. After the reactor is cooled to room temperature, the solid and liquid are separated by a centrifuge, and the liquid phase is to be sampled;
  • step (3) Use a sampler to pipette 0.2 ⁇ L of the reaction solution in step (2), and use a gas chromatograph to determine the yield of furfuryl alcohol.
  • step (2) Weigh 1 mmol furfural and add it to the reaction system of step (1), put the polytetrafluoroethylene lining into the stainless steel reaction kettle, heat it to 120°C under magnetic stirring, react for 0.5 to 4 hours, and wait for the reaction kettle to complete After cooling to room temperature, separate the solid and liquid with a centrifuge, and take the liquid phase as the sample to be tested;
  • step (3) Use a sampler to pipette 0.2 ⁇ L of the reaction solution in step (2), and use a gas chromatograph to determine the yield of furfuryl alcohol.
  • step (2) Weigh 1mmol furfural into the reaction system of step (1), put the polytetrafluoroethylene lining into the stainless steel reactor, heat to 120°C under magnetic stirring, and react for 1 hour. After the reaction, the reactor is cooled to room temperature After that, use a centrifuge to separate the solid and liquid, and take the liquid as the sample to be tested;
  • step (3) Use a sampler to pipette 0.2 ⁇ L of the reaction solution in step (2), and use a gas chromatograph to determine the yield of furfuryl alcohol.
  • step (2) Weigh 1mmol of furfural and add it to the reaction system of step (1), put the polytetrafluoroethylene lining into the stainless steel reactor, heat to 120°C under magnetic stirring, react for 1h, the reaction is over, wait until the reactor is cooled to After room temperature, separate the solid and liquid with a centrifuge, and take the liquid as the sample to be tested;
  • step (3) Use a sampler to pipette 0.2 ⁇ L of the reaction solution in step (2), and use a gas chromatograph to determine the yield of furfuryl alcohol.
  • step (2) Weigh 1mmol of furfural and add it to the reaction system of step (1), put the polytetrafluoroethylene lining into the stainless steel reactor, heat to 120°C under magnetic stirring, react for 1h, the reaction is over, wait until the reactor is cooled to After room temperature, separate the solid and liquid with a centrifuge, and take the liquid phase as the sample to be tested;
  • step (3) Use a sampler to pipette 0.2 ⁇ L of the reaction solution in step (2), and use a gas chromatograph to determine the yield of furfuryl alcohol.
  • the filtered catalyst is washed and dried, and then put into the above-mentioned catalytic reaction for recycling.

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Abstract

本发明公开了一种配位型磷钨酸锆催化剂及其在催化氢化糠醛中的应用，属于非均相催化领域。本发明制备得到的磷钨酸锆催化剂不仅对糠醛转化为糠醇具有良好的催化效果，而且反应条件温和，能够在120℃下反应1h即可实线糠醇的收率为98.64％，且催化剂的用量较少，大大减少了现有技术中所需的能耗。此外，本发明制备得到的磷钨酸锆易于分离，对催化氢化糠醛到糠醇的反应具有很好的稳定性，是一种新型、高效、绿色的催化剂。

Description

一种配位型磷钨酸锆催化剂及其在催化氢化糠醛中的应用 技术领域
本发明涉及一种配位型磷钨酸锆催化剂及其在催化氢化糠醛中的应用，属于非均相催化领域。
背景技术
随着社会快速发展，化石能源的供不应求，资源的过度开采以及浪费，所以寻找新型、绿色、可再生的能源收到了广泛的关注。生物质不仅是一种可再生的资源，而且在地球上分布最广泛、数量和种类最多的能源，所以引起很多研究者极大的关注。通过生物质的基本的物质平台，以这些基本物质为原料生产高附加值的化合物越来越多，所以开发新的生产技术、生产路线，以及生产高附加值得化合物对实际的生产和现代化工业的发展具有深远的影响。
糠醛作为生物质的基本平台物质，是一种五碳化合物，衍生于一些小麦、玉米芯等农产品中，其储量丰富，具有很广泛的用途。糠醛可以作为基本的原料合成很多高附加值得化合物，其中糠醇就是一种高附加值的化合物，糠醇可以用于生产树脂、燃料、合成纤维、橡胶、塑料、农药等广泛的工业行业中。
但目前工业上仍以高温和高氢气压力下氢化糠醛到糠醇的生产路线，使用的是石油所衍生传统化石能源，而且反应条件比较苛刻，给能源和经济方面都带来了很大的负担。近年来，不断有以配位型催化剂的出现催化糠醛为原料合成糠醇的报道出现，但这些报道中制备方法的反应条件仍比较苛刻，很多都需要在高于120℃的反应温度或需要在氢气下进行，或者在反应温度低于120℃下反应时间较长等问题。例如，CN107445923A公开了一种利用糠醛加氢制备糠醇的工艺，其利用铜负载多聚谷氨酸/N-羟甲基丙烯酰胺作为催化剂，以氢气作为氢气源。CN107963998A公开了糠醛甲酸转移加氢制备糠醇的方法，以Pd/C与CuO为复合催化剂，甲酸为氢供体，需要在170℃反应3h才能取得较好的催化效果。
因此，需要寻找一种新的催化剂，以解决现有技术中催化糠醛加氢转化为糠醇时反应条件苛刻以及贵金属的使用等问题，比如：H 2的使用、较高的反应温度或Pd的使用。
磷钨酸具有酸性和氧化还原性，是一种多功能的新型催化剂，具有很高的催化活性，稳定性好，可作均相及非均相反应，其主要用于作为有机合成反应的催化剂、生化试剂及色谱分析试剂。磷钨酸作为催化剂具有反应活性高、绿色无污染和可以循环多次使用，活性损失少等优点。
发明内容
[技术问题]
现有技术中催化糠醛加氢转化为糠醇时反应条件苛刻以及贵金属的使用等问题。
[技术方案]
为了解决现有技术中催化糠醛加氢转化为糠醇时反应条件苛刻以及贵金属的使用等问题，本发明提供了一种具有高效的催化能力的配位型磷钨酸锆催化剂，其在催化糠醛转化为糠醇的过程中，糠醇的收率在120℃下反应1h即可达到98.64％，能够在温和的反应条件下实线较高的催化活性，而且易于回收再利用。
具体的，本发明首先提供了所述配位型磷钨酸锆催化剂的制备方法，所述方法包括以下步骤：将磷钨酸和ZrCl 4分别溶于DMF中，超声处理后，在5～30min内向ZrCl 4溶液内逐滴加入磷钨酸溶液，待均匀混合后，加入三乙胺，然后在室温下反应3～6h，老化时间大于4h，分别用DMF、甲醇、无水乙醚洗涤1～3次，在70～100℃进行真空干燥，干燥时间大于8h，即得配位型磷钨酸锆催化剂。
在本发明的一种实施方式中，所述超声处理的时间为5～30min，所述超声的频率为40～60kHz。
在本发明的一种实施方式中，所述磷钨酸和ZrCl 4的摩尔比为3:1～1:3。
在本发明的一种实施方式中，磷钨酸的浓度为(0.05～0.15)mol/L，ZrCl 4的浓度为(0.05～0.15)mol/L。
在本发明的一种实施方式中，所述三乙胺的添加量为1～3mL/mmol磷钨酸。
其次，本发明还提供了上述制备方法制备得到的配位型磷钨酸锆催化剂。
再者，本发明提供了一种催化糠醛加氢制备糠醇的方法，以上述方法制备得到的配位型磷钨酸锆为催化剂，以糠醛为底物，按照0.1～0.3g配位型磷钨酸锆/mmol糠醛加入催化剂，于110～150℃反应0.5～4h，其中，以异丙醇为氢源，其加入量为5～10mL/mmol糠醛。
在本发明的一种实施方式中，反应温度优选为120℃。
在本发明的一种实施方式中，反应时间优选为1h。
在本发明的一种实施方式中，异丙醇的加入量为5mL/mmol糠醛。
在本发明的一种实施方式中，配位型磷钨酸锆的加入量优选为0.2g/mmol糠醛。
最后，本发明还提供了上述一种催化糠醛加氢制备糠醇的方法在制备树脂、燃料、合成纤维、橡胶、塑料、农药中的应用。
本发明相对于现有技术，具有以下的优点和效果：
(1)本发明使用的催化剂为配位型磷钨酸锆，不仅对糠醛转化为糠醇具有良好的催化效 果，而且反应条件温和，在120℃下反应1h即可实线糠醇的收率为98.64％，大大减少了现有技术中所需的能耗。
(2)本发明的催化剂所选用的原料磷钨酸具有特殊的结构，能为反应提供一个良好的微环境，从而提高了糠醇的产率与选择性；本发明使用的催化剂的活性部位为金属锆，它具备良好的性质，在较为温和的反应条件下实现了糠醛到糠醇的高效转化。
(3)本发明的配位型磷钨酸锆催化剂为非均相型，反应结束后通过简单的过滤可将催化剂回收并用于下一次反应中，而且多次循环后仍具有良好的催化效果，体现了绿色化学的方针。
附图说明
图1为实施例1制备得到的配位型磷钨酸锆催化剂的XRD图。
图2为实施例1制备得到的配位型磷钨酸锆催化剂的SEM(a)和TEM(b)照片。
图3为实施例4中不同类型金属磷钨酸锆催化剂催化氢化糠醛反应的糠醇产率。
图4为实施例5中配位型磷钨酸锆催化剂在不同温度下催化氢化糠醛反应的糠醇产率。
图5为实施例6中配位型磷钨酸锆催化剂在不同时间下催化氢化糠醛反应的糠醇产率。
图6为实施例7中配位型磷钨酸锆催化剂在不同催化剂用量下催化氢化糠醛反应的糠醇产率。
图7为实施例8中配位型磷钨酸锆催化剂在不同反应溶剂下催化氢化糠醛反应的糠醇产率。
具体实施方式
气相色谱(GC)测定糠醛的方法：用糠醛(FF)和糠醇(FA)峰面积的比例进行计算出，其中萘作为参比样。
转化率的计算公式：
Figure PCTCN2019078471-appb-000001
产率的计算公式：
Figure PCTCN2019078471-appb-000002
下面结合实施例对本发明作进一步的描述，但本发明的实施方式不限于此。
实施例1
(1)原料的预处理：将含有结晶水的磷钨酸进行100℃真空干燥10h，然后将其在研钵中磨成粉末状。
(2)磷钨酸锆(Zr-PW)的制备：取2.88g的步骤(1)预处理过的磷钨酸溶于DMF中， 磷钨酸的浓度为0.05mol/L，并在超声波中处理20min，然后取0.466g的ZrCl 4溶于DMF中，ZrCl 4的浓度为0.1mol/L，并在超声波中处理20min。将超声处理的ZrCl 4溶液置于圆底烧瓶中，在30min之内逐滴加入超声处理的磷钨酸溶液。待上述溶液均匀混合后，逐滴加入3ml三乙胺溶液，然后在室温下反应4h，老化4h，分别用DMF、甲醇、无水乙醚洗三次，在80℃的真空干燥中干燥12h，将其研磨成粉末即可制备得到磷钨酸锆(Zr-PW)。
对制备得到的磷钨酸锆(Zr-PW)进行表征，其XRD图和电镜图分别如图1和2所示，可见，本发明制备得到的催化剂为一种不规则的介孔结构。
实施例2
(1)原料的预处理：将含有结晶水的磷钨酸进行100℃真空干燥10h，然后将其在研钵中磨成粉末状。
(2)磷钨酸锆(Zr-PW)的制备：取2.88g的步骤(1)预处理过的磷钨酸溶于DMF中，磷钨酸的浓度为0.10mol/L，并在超声波中处理15min，然后取0.466g的ZrCl 4溶于DMF中，ZrCl 4的浓度为0.10mol/L，并在超声波中处理20min。将超声处理的ZrCl 4溶液置于圆底烧瓶中，在20min之内逐滴加入超声处理的磷钨酸溶液。待上述溶液均匀混合后，逐滴加入3ml三乙胺溶液，然后在室温下反应3h，老化5h，分别用DMF、甲醇、无水乙醚洗三次，在100℃的真空干燥中干燥10h，将其研磨成粉末即可制备得到磷钨酸锆(Zr-PW)。
实施例3
(1)原料的预处理：将含有结晶水的磷钨酸进行100℃真空干燥10h，然后将其在研钵中磨成粉末状。
(2)不同配比磷钨酸锆(Zr-PW)的制备及其催化性能：分别取ZrCl 4:PW(磷钨酸)的摩尔比为3:1、2:1、1:1、1:2、1:3的配比进行合成磷钨酸锆，将上述取得两种原料各自溶于20ml的DMF中，并将其超声处理20min。待上述溶液均匀混合后，逐滴加入3ml三乙胺溶液，然后在室温下反应4h，老化4h，分别用DMF、甲醇、无水乙醚洗三次，在80℃的真空干燥中干燥12h，将其研磨成粉末即可制备得到磷钨酸锆催化剂。
将制备得到的磷钨酸锆催化剂分别作为催化糠醛的催化剂：
(1)分别称取200mg上述催化剂于20mL聚四氟乙烯内衬中，加入定量的萘(此处的萘作为参比样，下同)和5mL的异丙醇；
(2)称取1mmol糠醛加入到步骤(1)的体系中，将聚四氟乙烯内衬放入不锈钢反应釜，在磁力搅拌下加热至150℃，反应3h，反应结束，待反应釜冷却至室温后，用离心机将固液分离，待取液相测样；
(3)用进样器移取0.2μL步骤(2)中反应液，用气相色谱仪测定糠醇的产率。
表1 不同配比的磷钨酸锆催化剂的催化性能
比例 3:1 2:1 1:1 1:2 1:3
C FF 100 92.3 90.03 100 99.14
Y FA 35 58.37 40.24 39.86 42.22
可见，优选当ZrCl 4:PW(磷钨酸)的摩尔比为2:1时制备得到的磷钨酸锆作为催化剂，进行后续的研究。
实施例4
按照实施例1的方法，将ZrCl 4换成AlCl 3，制备得到对应的催化剂磷钨酸铝(Al-PW)；此外，分别按照实施例1的方法单独用磷钨酸、ZrCl 4作为反应原料制备得到催化剂磷钨酸、ZrCl 4。
按照实施例1的方法，将磷钨酸换成磷钼酸(PM)，分别与ZrCl 4和AlCl 3，反应制备得到对应的催化剂磷钼酸锆(Zr-PM)和磷钼酸铝(Al-PM)，此外，分别按照实施例1的方法单独用磷钼酸制备得到催化剂磷钼酸。
将实施例1制备得到的催化剂Zr-PW和实施例4制备得到的催化剂Al-PW、磷钨酸、ZrCl 4、磷钼酸锆Zr-PM、磷钼酸铝Al-PM或磷钼酸PM分别作为催化糠醛的催化剂：
(1)分别称取200mg上述催化剂(Zr-PW、Al-PW、磷钨酸、ZrCl 4、Zr-PM、Al-PM或PM)于20mL聚四氟乙烯内衬中，加入定量的萘(此处的萘作为参比样，下同)和5mL的异丙醇；
(2)称取1mmol糠醛加入到步骤(1)的体系中，将聚四氟乙烯内衬放入不锈钢反应釜，在磁力搅拌下加热至120℃，反应1h，反应结束，待反应釜冷却至室温后，用离心机将固液分离，待取液相测样；
(3)用用进样器移取0.2μL步骤(2)中反应液，用气相色谱仪测定糠醇的产率。
经测定，结果如图3所示，以Zr-PM、PM、PW、ZrCl 4、Al-PW、Al-PM或Zr-PW为原料所制得的催化剂催化氢化糠醛，糠醇的产率分别为31.56％、0.32％、0.81％、3.26％、5.11％、0％、98.64％，可见，只有磷钨酸锆催化剂Zr-PW对糠醛制备糠醇有良好的催化性能。
实施例5
(1)称取200mg实施例1制备得到的配位型磷钨酸锆于20mL聚四氟乙烯内衬中，加入定量的萘和5mL的异丙醇；
(2)称取1mmol糠醛加入步骤(1)的反应体系中，将聚四氟乙烯内衬放入不锈钢反应 釜，在磁力搅拌下分别加热至110℃～150℃，反应1h，反应结束，待反应釜冷却至室温后，用离心机将固液分离，待取液相测样；
(3)用进样器移取0.2μL步骤(2)中反应液，用气相色谱仪测定糠醇的产率。
经测定，结果如图4所示，当反应温度分别为110℃、120℃、130℃、140℃、150℃时，糠醇的产率分别为46.24％、98.64％、92.89％、92.86％、80.41％。可见，本发明制备得到的配位型磷钨酸锆催化剂在120℃、反应1h即可实现较高的糠醇产率。
实施例6
(1)称取200mg实施例1制备得到的配位型磷钨酸锆催化剂于20mL聚四氟乙烯内衬中，加入定量的萘和5mL异丙醇；
(2)称取1mmol糠醛加入步骤(1)的反应体系中，将聚四氟乙烯内衬放入不锈钢反应釜，在磁力搅拌下加热至120℃，反应0.5～4h，反应结束，待反应釜冷却至室温后，用离心机将固液分离，取其液相作为待测样；
(3)用进样器移取0.2μL步骤(2)中反应液，用气相色谱仪测定糠醇的产率。
经测定，结果如图5所示，当反应时间分别为0.5h、1h、2h、3h、4h时，糠醇的产率分别为52.82％、98.64％、96.72％、92.67％、91.38％。可见，随着反应的时间增加，糠醇的产率逐渐升高，之后有所降低。
实施例7
(1)分别称取100mg、150mg、200mg、250mg或300mg实施例1制备得到的配位型磷钨酸锆催化剂于20mL聚四氟乙烯内衬中，加入定量的萘和20mL异丙醇；
(2)称取1mmol糠醛加入步骤(1)的反应体系中，将聚四氟乙烯内衬放入不锈钢反应釜，在磁力搅拌下加热至120℃，反应1h，反应结束待反应釜冷却至室温后，用离心机将固液分离，取液体为待测样；
(3)用进样器移取0.2μL步骤(2)中反应液，用气相色谱仪测定糠醇的产率。
经测定，结果如图6所示，当催化剂的用量分别为100mg、150mg、200mg、250mg、300mg时，糠醇的产率分别为87.76％、92.61％、98.64％、93.52％、93.52％。
实施例8
(1)称取200mg实施例1制备得到的配位型磷钨酸锆催化剂于20mL聚四氟乙烯内衬中，加入定量的萘，分别加入溶剂甲醇、乙醇、正戊醇、正丁醇、2-丁醇、叔丁醇；
(2)称取1mmol糠醛加入步骤(1)的反应体系中，将聚四氟乙烯内衬放入不锈钢反应釜，在磁力搅拌下加热至120℃，反应1h，反应结束，待反应釜冷却至室温后，用离心机将 固液分离，取液体为待测样；
(3)用进样器移取0.2μL步骤(2)中反应液，用气相色谱仪测定糠醇的产率。
经测定，结果如图7所示，当反应溶剂为甲醇、乙醇、正戊醇、正丁醇、2-丁醇、叔丁醇时，糠醇的产率分别为0％，21.08％，23.75％，33.75％，31.35％，0％。
实施例9
(1)称取200mg实施例1制备得到的配位型磷钨酸锆催化剂于20mL聚四氟乙烯内衬中，加入定量的萘和5mL异丙醇；
(2)称取1mmol糠醛加入步骤(1)的反应体系中，将聚四氟乙烯内衬放入不锈钢反应釜，在磁力搅拌下加热至120℃，反应1h，反应结束，待反应釜冷却至室温后，用离心机将固液分离，取其液相作为待测样；
(3)用进样器移取0.2μL步骤(2)中反应液，用气相色谱仪测定糠醇的产率。
反应结束后，通过过滤的催化剂，洗净烘干，再投入到上述催化反应中，循环使用。
经实验计算，配位型磷钨酸锆循环使用6次后，糠醇的产率仍高达82.44％。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (11)

  1. 一种配位型磷钨酸锆催化剂的制备方法，其特征在于，包括以下步骤：将磷钨酸和ZrCl 4分别溶于DMF中得到磷钨酸溶液、ZrCl 4溶液，超声处理后，在5～30min内向ZrCl 4溶液内逐滴加入磷钨酸溶液，待均匀混合后，加入三乙胺，然后在室温下反应3～6h，老化时间大于4h，分别用DMF、甲醇、无水乙醚洗涤1～3次，在70～100℃进行真空干燥，干燥时间大于8h，即得配位型磷钨酸锆催化剂。
  2. 根据权利要求1所述的一种配位型磷钨酸锆催化剂的制备方法，其特征在于，所述磷钨酸和ZrCl 4的摩尔比为3:1～1:3。
  3. 根据权利要求1或2所述的一种配位型磷钨酸锆催化剂的制备方法，其特征在于，所述磷钨酸溶液的浓度为(0.05～0.15)mol/L，所述ZrCl 4溶液的浓度为(0.05～0.15)mol/L。
  4. 根据权利要求1～3任一所述的一种配位型磷钨酸锆催化剂的制备方法，其特征在于，所述超声处理的时间为5～30min。
  5. 权利要求1～4任一所述的一种配位型磷钨酸锆催化剂的制备方法制备得到的配位型磷钨酸锆催化剂。
  6. 一种催化糠醛加氢制备糠醇的方法，其特征在于，所述方法以权利要求5所述的配位型磷钨酸锆为催化剂，以糠醛为底物，按照0.1～0.3g配位型磷钨酸锆/mmol糠醛加入催化剂，于110～150℃反应0.5～4h。
  7. 根据权利要求6所述的一种催化糠醛加氢制备糠醇的方法，其特征在于，以异丙醇为氢源，其加入量为5～10mL/mmol糠醛。
  8. 根据权利要求7所述的一种催化糠醛加氢制备糠醇的方法，其特征在于，所述异丙醇的加入量为5mL/mmol糠醛。
  9. 根据权利要求6～8任一所述的一种催化糠醛加氢制备糠醇的方法，其特征在于，反应温度为120℃。
  10. 根据权利要求6～9任一所述的一种催化糠醛加氢制备糠醇的方法，其特征在于，反应时间为1h。
  11. 权利要求6～10任一所述的一种催化糠醛加氢制备糠醇的方法在制备树脂、燃料、合成纤维、橡胶、塑料或农药中的应用
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