WO2019214247A1 - 一种高效催化糠醛转化制备环戊酮的方法和催化剂及其制备方法 - Google Patents

一种高效催化糠醛转化制备环戊酮的方法和催化剂及其制备方法 Download PDF

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WO2019214247A1
WO2019214247A1 PCT/CN2018/122982 CN2018122982W WO2019214247A1 WO 2019214247 A1 WO2019214247 A1 WO 2019214247A1 CN 2018122982 W CN2018122982 W CN 2018122982W WO 2019214247 A1 WO2019214247 A1 WO 2019214247A1
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catalyst
precursor
hydrotalcite
reaction
furfural
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French (fr)
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何静
朱彦儒
安哲
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北京化工大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J23/80—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 zinc, cadmium or mercury
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    • 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
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    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • B01J23/42—Platinum
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    • 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
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B01J27/236—Hydroxy carbonates
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    • 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
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/04—Mixing
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    • 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
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
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    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B01J35/73—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline having a two-dimensional layered crystalline structure, e.g. layered double hydroxide [LDH]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated

Definitions

  • the invention belongs to the technical field of biomass catalysis, and particularly relates to a catalyst for efficiently converting valeraldehyde to cyclopentanone and a preparation method thereof, and a method for efficiently converting furfural to prepare cyclopentanone.
  • Furfural can be produced by acid-catalyzed dehydration of renewable biomass resource pentose, which is one of the important biomass platform molecules and can be converted into high value-added biofuels and fine chemicals.
  • Cyclopentanone is a multifunctional fine chemical and an important intermediate in many chemical synthesis. It can be used in synthetic drugs, fungicides, rubber chemicals, and fragrance and fragrance chemicals.
  • the industry uses oil route production, and cyclopentanone is mainly prepared by liquid phase oxidation of cyclopentene by nitrous oxide or gas phase cyclization of 1,6-hexanediol or adipic acid.
  • the preparation of cyclopentanone from renewable biomass or platform molecules is in line with the current development trend of green and clean chemical processes.
  • work has reported the route of furfural to prepare cyclopentanone, which may replace unsustainable fossil fuels as raw materials.
  • Furfural is the product of acid-catalyzed dehydration of pentose sugars in the aqueous phase.
  • the process of separating furfural from the formed aqueous solution increases its production cost. Therefore, the use of aqueous furfural as a raw material for the preparation of chemicals and fuels is very beneficial.
  • Hronec et al. reported a new method for the re-hydrogenation of furfural and sterol rearrangement in water to cyclopentanone. They found that some metal catalysts (such as Pt/C, Pd-Cu/C and Ni-based catalysts) exhibited good conversion of furfural or sterol to cyclopentanone.
  • Ni-Cu/SBA-15, Cu-Co, ZnAl oxide-supported Cu, Ru/MIL-101 and other catalytic systems have been developed for the preparation of cyclopentanone in aqueous furfural.
  • the object of the present invention is to provide a catalyst for efficiently converting furfural to cyclopentanone and a preparation method thereof, and a method for efficiently converting furfural to cyclopentanone, and a method for preparing cyclopentanone by mildly and efficiently catalyzing the conversion of furfural.
  • the first aspect of the present invention provides a catalyst for efficiently converting furfural to produce cyclopentanone, which is composed of uniformly dispersed metal active center nanoparticles and an oxide obtained by calcining hydrotalcite, and the metal active center is a single atom Pt /Cu is the Pt atom in situ displacement loading on the Cu surface.
  • the content of Cu in the metal active center in the catalyst is 5 to 30 wt%
  • the content of Pt is 0.01 to 3 wt%
  • the particle diameter of the metal active center PtCu is 2 to 20 nm.
  • the metal active center Cu is contained in an amount of 8 to 20% by weight, the Pt content is 0.05 to 1% by weight, and the metal active center single atom Pt/Cu has a particle diameter ranging from 2 to 10 nm.
  • a second aspect of the present invention provides a method for preparing a catalyst for efficiently converting a furfural to produce cyclopentanone, which comprises: preparing a Cu-containing catalyst precursor by using hydrotalcite as a precursor, reducing in a H 2 atmosphere, and then The Pt 2+ is reacted with the Cu-containing catalyst precursor, washed and dried to obtain a catalyst containing a metal active center PtCu.
  • the preparation of the Cu-containing catalyst precursor is carried out by using hydrotalcite as a precursor system: the hydrotalcite precursor containing Cu ions is reduced in a H 2 atmosphere, the reduction temperature is controlled at 400 ° C to 650 ° C, and the reduction time is controlled at 5 min. At 6 h, a Cu-containing catalyst precursor was obtained.
  • the divalent cation of the hydrotalcite layer containing the Cu ion-containing hydrotalcite precursor is selected from Zn 2+ or / and Mg 2+
  • the trivalent cation is selected from Al 3+
  • the metal active center ion entering the interlayer is Cu 2+ .
  • the molar ratio of the divalent cation Zn 2+ or / and Mg 2+ of the hydrotalcite layer to the metal active center ion Cu 2+ entering the interlayer is (0-10): 1, and the hydrotalcite layer is bivalent.
  • the hydrotalcite precursor further contains tetravalent cations entering the laminate, and the tetravalent cations are selected from Zr 4+ , Zr 4+ and
  • the molar ratio of the valent cation Al 3+ is (0.1-1):1, such as 0.5:1.
  • the preparation method of the catalyst comprises: a Cu-containing catalyst precursor, the hydrotalcite precursor is reduced in a H 2 atmosphere, the reduction temperature is controlled at 400 ° C to 650 ° C, and the reduction time is controlled at 5 min to 6 h to obtain a Cu-containing catalyst precursor.
  • the third aspect of the present invention provides a method for efficiently converting furfural to produce cyclopentanone, which comprises using the above catalyst or the catalyst prepared by the above preparation method to catalyze furfural reaction, and the reaction conditions include: reaction temperature is 120-250 ° C The reaction pressure is 0.1 to 5 MPa. The reaction time is 0.5 to 24 hours, and the reaction solvent is ultrapure water.
  • the present invention uses a monoatomic Pt/Cu catalyst to catalyze the preparation of cyclopentanone from furfural by replacing the air in the reaction vessel with hydrogen and charging it with an appropriate pressure.
  • the mass fraction of the substrate furfural is 1 to 20 wt%, using a Cu-containing catalyst, the reaction temperature is 120 to 250 ° C, the reaction pressure is 0.1 to 5 MPa, the reaction time is 0.5 to 24 h, and the reaction solvent is ultrapure water.
  • the PtCu-containing catalyst is composed of oxides obtained by uniformly dispersing metal active center nanoparticles and hydrotalcite, and the metal active center is a single atom of Pt/Cu; preferably, the catalyst metal active center Cu is 5 to 30 wt%.
  • the content of Pt is 0.01 to 3 wt%, and the particle diameter of the active metal is in the range of 2 to 20 nm.
  • the preparation of the monoatomic Pt/Cu catalyst comprises: using a bimetallic composite hydroxide, also known as hydrotalcite as a precursor, and selecting a Zn 2+ or Mg 2+ as a divalent cation of the hydrotalcite laminate, trivalent
  • the cation selects Al 3+
  • the metal active center ion entering the interlayer is Cu 2+
  • the molar ratio of the divalent cation of the hydrotalcite layer to the metal active center ion is (0-10): 1, the hydrotalcite layer is bivalent.
  • the reduction time is controlled from 5 min to 6 h, the Cu-containing catalyst can be obtained, and a small amount of Pt 2+ is reacted with the Cu catalyst, and after reduction in the H 2 atmosphere, a monoatomic Pt/Cu catalyst can be obtained. Further tetravalent cations in the hydrotalcite enter the interlayer and Zr 4+ is selected.
  • the catalyst of the present invention consists of a uniformly dispersed metal nanoparticle PtCu alloy and a supported zinc aluminum composite oxide.
  • the metal active center element of the catalyst is controlled by the proportion and composition of the metal cation of the hydrotalcite laminate.
  • the Cu-based catalyst containing Cu was prepared by in-situ reduction, and the PtCu supported catalyst was obtained by loading Pt.
  • the high-dispersion supported monoatomic Pt/Cu catalyst with adjustable loading and composition was prepared by using the metal ion ratio and composition of the hydrotalcite laminate to catalyze the conversion of furfural to cyclopentanone.
  • the yield of cyclopentanone reached 99%. .
  • the reaction conditions are mild and the energy consumption is low.
  • the reaction was carried out at 160 ° C, an initial pressure of 0.1 MPa, and the furfural was completely converted at 10 h.
  • the reaction is easy to operate and can occur in a sealed reaction vessel.
  • Step A Cu(NO 3 ) 2 ⁇ 3H 2 O (14 mmol), Zn(NO 3 ) 2 ⁇ 6H 2 O (42 mmol), Al(NO 3 ) 3 ⁇ 9H 2 O (12 mmol), and ZrO (NO) 3 ) 2 ⁇ 6H 2 O (6 mmol) was dissolved in 200 mL of deionized water into solution A, and NaOH (0.156 mol) and Na 2 CO 3 (0.024 mol) were dissolved in solution B in 200 mL of deionized water. Solutions A and B were then simultaneously added dropwise to a four-necked flask containing 200 mL of deionized water at a constant pH (10.0).
  • Step B The CuZnAlZr-LDHs synthesized in the step (A) are placed in a tube furnace under H 2 (40 mL min -1 ), and the temperature is raised from room temperature to 450 ° C for 2 h, and the heating rate is 2 ° C min -1 .
  • Cu-Zn(Al)(Zr)O was obtained. 1 g of the reduced Cu-Zn(Al)(Zr)O was directly sealed with 5 mL of deionized water except peroxygen, poured into a round bottom flask, and a Pt 2+ solution was added dropwise under vigorous stirring and N 2 protection. After that, the replacement reaction was carried out for 2 h under vigorous stirring at 100 ° C under reflux. The centrifuged separated sludge was washed three times with deionized water and dried under vacuum at 40 ° C for 24 h. obtain.
  • a Pt/Cu-Zn(Al)(Zr)O catalyst was prepared, and the actual loading of Pt was 0.1%, the actual loading of Cu was 11%, and the metal center particle diameter ranged from 2 to 20 nm.
  • the mixture is cooled to room temperature, and the liquid in the reaction vessel is centrifuged to quantitatively analyze the product.
  • the conversion of furfural to the Pt/Cu-Zn(Al)(Zr)O catalyst was determined to be 100%, and the selectivity to cyclopentanone was 99%.
  • Step A Cu(NO 3 ) 2 ⁇ 3H 2 O (10 mmol), Zn(NO 3 ) 2 ⁇ 6H 2 O (46 mmol), Al(NO 3 ) 3 ⁇ 9H 2 O (12 mmol), and ZrO (NO) 3 ) 2 ⁇ 6H 2 O (6 mmol) was dissolved in 200 mL of deionized water into solution A, and NaOH (0.156 mol) and Na 2 CO 3 (0.024 mol) were dissolved in solution B in 200 mL of deionized water. Solutions A and B were then simultaneously added dropwise to a four-necked flask containing 200 mL of deionized water at a constant pH (10.0).
  • Step B The CuZnAlZr-LDHs synthesized in the step (A) are placed in a tube furnace under H 2 (40 mL min -1 ), and the temperature is raised from room temperature to 450 ° C for 2 h, and the heating rate is 2 ° C min -1 .
  • Cu-Zn(Al)(Zr)O was obtained. 1 g of the reduced Cu-Zn(Al)(Zr)O was directly sealed with 5 mL of deionized water except peroxygen, poured into a round bottom flask, and a Pt 2+ solution was added dropwise under vigorous stirring and N 2 protection. After that, the replacement reaction was carried out for 2 h under vigorous stirring at 100 ° C under reflux. The centrifuged separated sludge was washed three times with deionized water and dried under vacuum at 40 ° C for 24 h. obtain.
  • a Pt/Cu-Zn(Al)(Zr)O catalyst was prepared, and the actual loading of Pt was 0.1%, the actual loading of Cu was 8%, and the metal center particle diameter ranged from 2 to 20 nm.
  • the mixture is cooled to room temperature, and the liquid in the reaction vessel is centrifuged to quantitatively analyze the product.
  • the conversion of furfural to the Pt/Cu-Zn(Al)(Zr)O catalyst was determined to be 100%, and the cyclopentanone selectivity was 92%.
  • Step A Cu(NO 3 ) 2 ⁇ 3H 2 O (20 mmol), Zn(NO 3 ) 2 ⁇ 6H 2 O (36 mmol), Al(NO 3 ) 3 ⁇ 9H 2 O (12 mmol), and ZrO (NO) 3 ) 2 ⁇ 6H 2 O (6 mmol) was dissolved in 200 mL of deionized water into solution A, and NaOH (0.156 mol) and Na 2 CO 3 (0.024 mol) were dissolved in solution B in 200 mL of deionized water. Solutions A and B were then simultaneously added dropwise to a four-necked flask containing 200 mL of deionized water at a constant pH (10.0).
  • Step B The CuZnAlZr-LDHs synthesized in the step (A) are placed in a tube furnace under H 2 (40 mL min -1 ), and the temperature is raised from room temperature to 450 ° C for 2 h, and the heating rate is 2 ° C min -1 .
  • Cu-Zn(Al)(Zr)O was obtained. 1 g of the reduced Cu-Zn(Al)(Zr)O was directly sealed with 5 mL of deionized water except peroxygen, poured into a round bottom flask, and a Pt 2+ solution was added dropwise under vigorous stirring and N 2 protection. After that, the replacement reaction was carried out for 2 h under vigorous stirring at 100 ° C under reflux. The centrifuged separated sludge was washed three times with deionized water and dried under vacuum at 40 ° C for 24 h. obtain.
  • a Pt/Cu-Zn(Al)(Zr)O catalyst was prepared, and the actual loading of Pt was 0.1%, the actual loading of Cu was 17%, and the metal center particle diameter ranged from 2 to 20 nm.
  • the mixture is cooled to room temperature, and the liquid in the reaction vessel is centrifuged to quantitatively analyze the product.
  • the conversion of furfural to the Pt/Cu-Zn(Al)(Zr)O catalyst was determined to be 100%, and the cyclopentanone selectivity was 90%.
  • Step A Cu(NO 3 ) 2 ⁇ 3H 2 O (14 mmol), Zn(NO 3 ) 2 ⁇ 6H 2 O (42 mmol), Al(NO 3 ) 3 ⁇ 9H 2 O (12 mmol), and ZrO (NO) 3 ) 2 ⁇ 6H 2 O (6 mmol) was dissolved in 200 mL of deionized water into solution A, and NaOH (0.156 mol) and Na 2 CO 3 (0.024 mol) were dissolved in solution B in 200 mL of deionized water. Solutions A and B were then simultaneously added dropwise to a four-necked flask containing 200 mL of deionized water at a constant pH (10.0).
  • Step B The CuZnAlZr-LDHs synthesized in the step (A) are placed in a tube furnace under H 2 (40 mL min -1 ), and the temperature is raised from room temperature to 450 ° C for 2 h, and the heating rate is 2 ° C min -1 . .
  • a Cu-Zn(Al)(Zr)O catalyst was prepared, and the actual loading of Cu was 11%, and the metal center particle diameter ranged from 2 to 20 nm.
  • the furfural hydroconversion was catalyzed by the Cu-Zn(Al)(Zr)O catalyst obtained in Comparative Example 1.
  • the autoclave lining was added with furfural 0.5g, 0.03g catalyst, and ultra-pure water 10mL.
  • the autoclave was installed, H 2 was charged from the inlet, the air in the autoclave was replaced 5 times, and then filled with 0.1 MPa of H 2 , sealed.
  • the autoclave is heated to a preset temperature.
  • the pressure at 160 ° C is about 0.5 MPa, the timing starts, the reaction is 10 h, and the process is continuously supplemented with H 2 to 0.5 MPa.
  • the mixture is cooled to room temperature, and the liquid in the reaction vessel is centrifuged to quantitatively analyze the product.
  • the conversion of furfural to the Cu-Zn(Al)(Zr)O catalyst was determined to be 24%, and the cyclopentanone selectivity was 9%.
  • the Pt/Cu catalyst has a good performance of hydrogenation of furfural to cyclopentanone.

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Abstract

一种高效催化糠醛转化制备环戊酮的方法和催化剂及其制备方法，属于生物质催化转化领域。该催化剂由均分散的金属活性中心纳米颗粒和水滑石煅烧所得的氧化物组成，其金属活性中心为单原子Pt/Cu；以水滑石为前体制得含Cu催化剂前体，H 2气氛中还原后，再利用少量Pt 2+与含Cu催化剂前体反应，得到单原子Pt/Cu催化剂，采用该催化剂催化糠醛水相加氢制环戊酮，反应温度为120～250℃，反应压力为0.1～5MPa，反应时间为0.5～24h，反应溶剂为超纯水。该催化剂便宜高效，催化糠醛水相加氢制环戊酮，反应在160℃、0.1MPa初始压力，10h时可将糠醛完全转化，环戊酮产率达到99％。

Description

一种高效催化糠醛转化制备环戊酮的方法和催化剂及其制备方法 技术领域
本发明属于生物质催化技术领域，具体涉及一种高效催化糠醛转化制备环戊酮的催化剂及其制备方法，以及一种高效催化糠醛转化制备环戊酮的方法。
背景技术
糠醛可由可再生生物质资源戊糖通过酸催化脱水生产，是重要的生物质平台分子之一，可以转化为高附加值化的生物燃料和精细化学品。糠醛的催化加氢是一系列重要的反应，可以得到糠醇，四氢糠醇，2-甲基呋喃和环戊酮等产物。由于糠醛的加氢过程中，涉及C＝O、C＝C键的加氢，C-C、C-O键的断裂等多种基元反应，因此高选择性的获得所需目标产物具有很大挑战。
环戊酮是一种多功能的精细化工品和多种化工合成中重要的中间体。它可以用于合成药物，杀真菌剂，橡胶化学品以及香料和香料化学品。目前工业中均采用石油路线生产，环戊酮主要通过氧化亚氮液相氧化环戊烯或气相环化1,6-己二醇或己二酸来制备。相比而言，从可再生生物质或平台分子出发制备环戊酮符合当前绿色、清洁化工过程的发展趋势，具有重要意义。最近，有工作报道了糠醛制备环戊酮的路线，有可能作为原料取代不可持续的化石燃料。
糠醛是在水相中戊糖的酸催化脱水的产物。从形成的水溶液中分离糠醛的过程增加了其生产成本。因此，使用糠醛水溶液作为制备化学品和燃料的原料是非常有益的。最近，Hronec等人报道了在水中糠醛和糠醇重排反应再加氢制环戊酮的新方法。他们发现一些金属催化剂(例如Pt/C，Pd-Cu/C和Ni基催化剂)表现出良好的糠醛或糠醇选择性转化为环戊酮的性能。在其他报道中，陆续发展了Ni-Cu/SBA-15,Cu-Co，ZnAl氧化物负载Cu，Ru/MIL-101等催化体系用于糠醛水相制备环戊酮。
尽管在这一领域已经做了一些开创性的工作，但该研究尚处于起步阶段。由于气体在水中的溶解度低以及多相界面之间的传输阻力，气-液-固相多相催化反应经常遇到催化效率低的问题。在温和条件下高效催化转化糠醛制环戊酮仍然是一个挑战。
发明内容
本发明的目的在于提供一种高效催化糠醛转化制备环戊酮的催化剂及其制备方法，以及一种高效催化糠醛转化制备环戊酮的方法，可以温和高效催化糠醛转化制备环戊酮的方法。
本发明的第一方面提供了一种高效催化糠醛转化制备环戊酮的催化剂，该催化剂由均分散的金属活性中心纳米颗粒和水滑石煅烧所得的氧化物组成，其金属活性中心为单原子Pt/Cu即Pt原子原位置换负载在Cu表面。
优选情况下，催化剂中金属活性中心的Cu的含量为5～30wt％，Pt的含量为0.01～3wt％，金属活性中心PtCu的粒径范围为2～20nm。
进一步优选地，金属活性中心Cu的含量为8～20wt％，Pt的含量为0.05～1wt％，金属活性中心单原子Pt/Cu的粒径范围为2～10nm。
本发明的第二方面提供了上述高效催化糠醛转化制备环戊酮的催化剂的制备方法，该制备方法包括：以水滑石为前体制得含Cu催化剂前体，H 2气氛中还原后，然后再利用Pt 2+与含Cu催化剂前体反应，洗涤干燥，得到含金属活性中心PtCu的催化剂。
优选地，以水滑石为前体制得含Cu催化剂前体的制备：将含Cu离子的水滑石前体在H 2气氛中还原，还原温度控制在400℃～650℃，还原时间控制在5min～6h，得到含Cu催化剂前体。
本发明中，上述含Cu离子的水滑石前体的水滑石层板二价阳离子选择Zn 2+或/和Mg 2+，三价阳离子选择Al 3+，进入层板间的金属活性中心离子为Cu 2+。
本发明中，水滑石层板二价阳离子Zn 2+或/和Mg 2+与进入层板间的金属活性中心离子Cu 2+摩尔比为(0～10)：1，水滑石层板二价阳Zn 2+或/和Mg 2+离子不为0，水滑石层板所有二价金属阳离子Zn 2+、Mg 2+及Cu 2+与水滑石层板所有三价金属阳离子摩尔比＝(2～5)：1。
进一步优选地，以水滑石为前体制得含Cu催化剂前体的制备过程中，水滑石前体中还含有进入层板内的四价阳离子，四价阳离子选择Zr 4+，Zr 4+与三价阳离子Al 3+的摩尔比为(0.1-1):1，如0.5:1。
催化剂的制备方法包括：含Cu催化剂前体，将水滑石前体在H 2气氛中还原，还原温度控制在400℃～650℃，还原时间控制在5min～6h，得到含Cu催化剂前体，采用除氧的去离子水将其液封；在搅拌及N 2保护的条件下，向含Cu催化剂前体的液封液中滴加Pt 2+溶液，90-120℃下置换反应1-3h，分离、洗涤、干燥，得到单原子Pt/Cu催化剂。
本发明的第三方面提供了一种高效催化糠醛转化制备环戊酮的方法，采用上述的催化剂或上述的制备方法制得的催化剂，催化糠醛反应，反应条件包括：反应温度为120～250℃，反应压力为0.1～5MPa.反应时间为0.5～24h，反应溶剂为超纯水。
按照本发明的一种优选实施方式，本发明采用含单原子Pt/Cu催化剂催化糠醛制备环戊酮的方法：采用氢气置换反应釜中空气并充入适当压力，加入底物糠醛的质量分数为1～20wt％，采用含Cu催化剂，反应温度为120～250℃，反应压力为0.1～5MPa，反应时间为0.5～24h，反应溶剂为超纯水。
本发明中，含PtCu催化剂为由均分散的金属活性中心纳米颗粒和水滑石煅烧所得的氧化物组成，金属活性中心为单原子Pt/Cu；优选催化剂金属活性中心Cu的含量为5～30wt％，Pt的含量为0.01～3wt％，活性金属中心粒径范围2～20nm。
优选情况下，含单原子Pt/Cu催化剂的制备包括：以双金属复合氢氧化物又称为水滑石为前体制得，水滑石层板二价阳离子选择Zn 2+或Mg 2+，三价阳离子选择Al 3+，进入层板间的金属活性中心离子为Cu 2+，其中水滑石层板二价阳离子与金属活性中心离子摩尔比为(0～10)：1，水滑石层板二价阳离子不为0，水滑石层板所有二价金属阳离子，水滑石层板所有三价金属阳离子摩尔比＝(2～5)：1，将水滑石前体在H 2气氛中还原，还原温度控制在400℃～550℃，还原时间控制在5min～6h，即可得到含Cu催化剂，再利用少量Pt 2+与Cu催化剂反应，H 2气氛中还原后，即可获得单原子Pt/Cu催化剂。进一步水滑石中还有四价阳离子进入层板间，选择Zr 4+。
本发明具有如下优点：
1.本发明催化剂由均分散的金属纳米颗粒PtCu合金，载体锌铝复合氧化物组成。该催化剂由水滑石前体还原制的，所选用的水滑石层板二价阳离子铜和锌、三价阳离子铝，其摩尔比为M 2+/M 3+＝2～5，Cu 2+、Zn 2+与Al 3+摩尔比为(0～10)。利用水滑石层板金属阳离子比例和组成可调，控制了催化剂的金属活性中心元素。含Cu水滑石经原位还原制备了均分散的Cu基催化剂，再负载Pt获得PtCu负载型催化剂。利用水滑石层板金属离子比例和组成可调控的特点，制备负载量和组成可调的高分散负载型单原子Pt/Cu催化剂，催化糠醛转化制环戊酮，环戊酮产率达到99％。
2.反应条件温和，能耗低。反应在160℃、0.1MPa初始压力，10h时可将糠醛完全转化。
3.反应操作简便，密封反应釜中即可发生。
具体实施方式
下面结合实施例对本发明做进一步说明，但本发明并不限于以下实施例。
实施例1
步骤A：将Cu(NO 3) 2·3H 2O(14mmol)，Zn(NO 3) 2·6H 2O(42mmol)，Al(NO 3) 3·9H 2O(12mmol)，和ZrO(NO 3) 2·6H 2O(6mmol)用200mL去离子水溶解为溶液A，NaOH(0.156mol)和Na 2CO 3(0.024mol)用200mL去离子水中溶解为溶液B。然后在恒定的pH(10.0)下，将溶液A和B同时逐滴滴加到含有200mL去离子水的四口烧瓶中。在65℃晶化12h后，将固体过滤，用去离子水多次洗涤直至滤液呈中性，之后在80℃干燥过夜，得到CuZnAlZr-LDHs样品。
步骤B：对装有步骤(A)中合成的CuZnAlZr-LDHs在管式炉中，H 2下(40mL min -1)，由室温升温至450℃并保持2h，升温速率为2℃ min -1，获得Cu-Zn(Al)(Zr)O。将1g还原过得Cu-Zn(Al)(Zr)O用5mL除过氧的去离子水直接液封，倒入圆底烧瓶，在剧烈搅拌和N 2保护下，滴加Pt 2+溶液。之后100℃下加回流冷凝管剧烈搅拌下置换反应2h。离心分离出的泥状物用去离子水洗涤三次，在真空中40℃下干燥24h。 获得。
即制备得到Pt/Cu-Zn(Al)(Zr)O催化剂，Pt的实际负载量为0.1％，Cu的实际负载量为11％，金属中心粒径范围2～20nm。
用实施例1所得到的Pt/Cu-Zn(Al)(Zr)O催化剂催化糠醛加氢转化。高压釜内衬加入糠醛0.5g，0.03g催化剂，超纯水10mL，安装高压釜，从进气口充入H 2，置换高压釜内的空气5次，而后充入0.1MPa的H 2，密封高压釜。高压釜加热到预设温度。160℃时压力约为0.5MPa，开始计时，反应10h，过程中不断补充H 2至0.5MPa，反应结束后，冷却至室温，反应釜内的液体离心分离，对产物进行GC定量分析。测得Pt/Cu-Zn(Al)(Zr)O催化剂上糠醛转化率为100％，环戊酮选择性为99％。
实施例2
步骤A：将Cu(NO 3) 2·3H 2O(10mmol)，Zn(NO 3) 2·6H 2O(46mmol)，Al(NO 3) 3·9H 2O(12mmol)，和ZrO(NO 3) 2·6H 2O(6mmol)用200mL去离子水溶解为溶液A，NaOH(0.156mol)和Na 2CO 3(0.024mol)用200mL去离子水中溶解为溶液B。然后在恒定的pH(10.0)下，将溶液A和B同时逐滴滴加到含有200mL去离子水的四口烧瓶中。在65℃晶化12h后，将固体过滤，用去离子水多次洗涤直至滤液呈中性，之后在80℃干燥过夜，得到CuZnAlZr-LDHs样品。
步骤B：对装有步骤(A)中合成的CuZnAlZr-LDHs在管式炉中，H 2下(40mL min -1)，由室温升温至450℃并保持2h，升温速率为2℃ min -1，获得Cu-Zn(Al)(Zr)O。将1g还原过得Cu-Zn(Al)(Zr)O用5mL除过氧的去离子水直接液封，倒入圆底烧瓶，在剧烈搅拌和N 2保护下，滴加Pt 2+溶液。之后100℃下加回流冷凝管剧烈搅拌下置换反应2h。离心分离出的泥状物用去离子水洗涤三次，在真空中40℃下干燥24h。获得。
即制备得到Pt/Cu-Zn(Al)(Zr)O催化剂，Pt的实际负载量为0.1％，Cu的实际负载量为8％，金属中心粒径范围2～20nm。
用实施例2所得到的Pt/Cu-Zn(Al)(Zr)O催化剂催化糠醛加氢转化。高压釜内衬加入糠醛0.5g，0.03g催化剂，超纯水10mL，安装高压釜，从进气口充入H 2，置换高压釜内的空气5次，而后充入0.1MPa的H 2，密封高压釜。高压釜加热到预设温度。160℃时压力约为0.5MPa，开始计时，反应10h，过程中不断补充H 2至0.5MPa，反应结束后，冷却至室温，反应釜内的液体离心分离，对产物进行GC定量分析。测得Pt/Cu-Zn(Al)(Zr)O催化剂上糠醛转化率为100％，环戊酮选择性为92％。
实施例3
步骤A：将Cu(NO 3) 2·3H 2O(20mmol)，Zn(NO 3) 2·6H 2O(36mmol)，Al(NO 3) 3·9H 2O(12mmol)，和ZrO(NO 3) 2·6H 2O(6mmol)用200mL去离子水溶解为溶液A，NaOH(0.156mol)和Na 2CO 3(0.024mol)用200mL去离子水中溶解为溶液B。然后在恒定的pH(10.0)下，将溶液A和B同时逐滴滴加到含有200mL去离子水的四口烧瓶中。在65℃晶化12h后，将固体过滤，用去离子水多次洗涤直至滤液呈中性，之后在80℃干燥过夜，得到CuZnAlZr-LDHs样品。
步骤B：对装有步骤(A)中合成的CuZnAlZr-LDHs在管式炉中，H 2下(40mL min -1)，由室温升温至450℃并保持2h，升温速率为2℃ min -1，获得Cu-Zn(Al)(Zr)O。将1g还原过得Cu-Zn(Al)(Zr)O用5mL除过氧的去离子水直接液封，倒入圆底烧瓶，在剧烈搅拌和N 2保护下，滴加Pt 2+溶液。之后100℃下加回流冷凝管剧烈搅拌下置换反应2h。离心分离出的泥状物用去离子水洗涤三次，在真空中40℃下干燥24h。获得。
即制备得到Pt/Cu-Zn(Al)(Zr)O催化剂，Pt的实际负载量为0.1％，Cu的实际负载量为17％，金属中心粒径范围2～20nm。
用实施例3所得到的Pt/Cu-Zn(Al)(Zr)O催化剂催化糠醛加氢转化。高压釜内衬加入糠醛0.5g，0.03g催化剂，超纯水10mL，安装高压釜，从进气口充入H 2，置换高压釜内的空气5次，而后充入0.1MPa的H 2，密封高压釜。高压釜加热到预设温度。160℃时压力约为0.5MPa，开始计时，反应10h，过程中不断补充H 2至0.5MPa，反应结束后，冷却至室温，反应釜内的液体离心分离，对产物进行GC定量分析。测得Pt/Cu-Zn(Al)(Zr)O催化剂上糠醛转化率为100％，环戊酮选择性为90％。
对比例1
步骤A：将Cu(NO 3) 2·3H 2O(14mmol)，Zn(NO 3) 2·6H 2O(42mmol)，Al(NO 3) 3·9H 2O(12mmol)，和ZrO(NO 3) 2·6H 2O(6mmol)用200mL去离子水溶解为溶液A，NaOH(0.156mol)和Na 2CO 3(0.024mol)用200mL去离子水中溶解为溶液B。然后在恒定的pH(10.0)下，将溶液A和B同时逐滴滴加到含有200mL去离子水的四口烧瓶中。在65℃晶化12h后，将固体过滤，用去离子水多次洗涤直至滤液呈中性，之后在80℃干燥过夜，得到CuZnAlZr-LDHs样品。
步骤B：对装有步骤(A)中合成的CuZnAlZr-LDHs在管式炉中，H 2下(40mL min -1)，由室温升温至450℃并保持2h，升温速率为2℃min -1。
即制备得到Cu-Zn(Al)(Zr)O催化剂，Cu的实际负载量为11％，金属中心粒径范围2～20nm。
用对比例1所得到Cu-Zn(Al)(Zr)O催化剂催化糠醛加氢转化。高压釜内衬加入糠醛0.5g，0.03g催化剂，超纯水10mL，安装高压釜，从进气口充入H 2，置换高压釜内的空气5次，而后充入0.1MPa的H 2，密封高压釜。高压釜加热到预设温度。160℃时压力约为0.5MPa，开始计时，反应10h，过程中不断补充H 2至0.5MPa，反应结束后，冷却至室温，反应釜内的液体离心分离，对产物进行GC定量分析。测得Cu-Zn(Al)(Zr)O催化剂上糠醛转化率为24％，环戊酮选择性为9％。
由实施例和对比例的反应结果可知，Pt/Cu催化剂具有良好的糠醛加氢制环戊酮性能。

Claims (10)

  1. 一种高效催化糠醛转化制备环戊酮的催化剂，其特征在于，该催化剂由均分散的金属活性中心纳米颗粒和水滑石煅烧所得的氧化物组成，其金属活性中心为单原子Pt/Cu，即Pt单原子原位置换负载在Cu表面。
  2. 按照权利要求1所述的一种高效催化糠醛转化制备环戊酮的催化剂，其特征在于，催化剂中金属活性中心的Cu的含量为5～30wt％，Pt的含量为0.01～3wt％，金属活性中心PtCu的粒径范围为2～20nm。
  3. 按照权利要求1所述的一种高效催化糠醛转化制备环戊酮的催化剂，其特征在于，金属活性中心Cu的含量为8～20wt％，Pt的含量为0.05～1wt％，金属活性中心单原子Pt/Cu的粒径范围为2～10nm。
  4. 制备权利要求1-3任一项所述的催化剂的方法，其特征在于，以水滑石为前体制得含Cu催化剂前体，H 2气氛中还原后，然后再利用Pt 2+与含Cu催化剂前体反应，洗涤干燥，得到含金属活性中心单原子Pt/Cu的催化剂。
  5. 按照权利要求4所述的方法，其特征在于，以水滑石为前体制得含Cu催化剂前体的制备：将含Cu离子的水滑石前体在H 2气氛中还原，还原温度控制在400℃～650℃，还原时间控制在5min～6h，得到含Cu催化剂前体。
  6. 按照权利要求5所述的方法，其特征在于，含Cu离子的水滑石前体的水滑石层板二价阳离子选择Zn 2+或/和Mg 2+，三价阳离子选择Al 3+，进入层板间的金属活性中心离子为Cu 2+；水滑石层板二价阳离子Zn 2+或/和Mg 2+与进入层板间的金属活性中心离子Cu 2+摩尔比为(0～10)：1，水滑石层板二价阳Zn 2+或/和Mg 2+离子不为0，水滑石层板所有二价金属阳离子Zn 2+、Mg 2+及Cu 2+与水滑石层板所有三价金属阳离子摩尔比＝(2～5)：1。
  7. 按照权利要求6所述的方法，其特征在于，以水滑石为前体制得含Cu催化剂前体的制备过程中，水滑石前体中还含有进入层板内的四价阳离子，四价阳离子选择Zr 4+，Zr 4+与三价阳离子的摩尔比为(0.1-1):1。
  8. 按照权利要求4所述的方法，其特征在于，催化剂的制备方法包括：含Cu催化剂前体，将水滑石前体在H 2气氛中还原，还原温度控制在400℃～650℃，还原时间控制在5min～6h，得到含Cu催化剂前体，采用除氧的去离子水将其液封；在搅拌及N 2保护的条件下，向含Cu催化剂前体的液封液中滴加Pt 2+溶液，90-120℃下置换反应1-3h，分离、洗涤、干燥，得到PtCu催化剂。
  9. 采用权利要求1-3任一项所述的催化剂催化糠醛转化制备环戊酮的方法，其特征 在于，反应条件包括：反应温度为120～250℃，反应压力为0.1～5MPa.反应时间为0.5～24h，反应溶剂为超纯水。
  10. 按照权利要求9所述的方法，其特征在于，采用氢气置换反应釜中空气并充入适当压力，加入底物糠醛的质量分数为1～20wt％，反应温度为120～250℃，反应压力为0.1～5MPa，反应时间为0.5～24h，反应溶剂为超纯水。
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