WO2020258408A1 - 一种高效加氢转化糠醇的方法及高分散负载型Pt催化剂 - Google Patents

一种高效加氢转化糠醇的方法及高分散负载型Pt催化剂 Download PDF

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WO2020258408A1
WO2020258408A1 PCT/CN2019/096266 CN2019096266W WO2020258408A1 WO 2020258408 A1 WO2020258408 A1 WO 2020258408A1 CN 2019096266 W CN2019096266 W CN 2019096266W WO 2020258408 A1 WO2020258408 A1 WO 2020258408A1
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catalyst
furfuryl alcohol
reaction
conversion
hydrotalcite
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何静
赵文芳
朱彦儒
安哲
宋红艳
舒心
项顼
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Beijing University of Chemical Technology
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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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
    • 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
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms
    • 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
    • C07D307/36—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms

Definitions

  • the invention belongs to the technical field of biomass catalytic conversion, and in particular provides a method for efficient hydrogenation to convert furfuryl alcohol and a highly dispersed supported Pt catalyst.
  • Furfural is one of the most important platform molecules in biomass and is considered to be one of the most important chemicals for the production of lignocellulosic biomass.
  • Furfural is mainly achieved by acid-catalyzed pentosan in biomass raw materials.
  • Furfural/furfuryl alcohol can be hydrogenated to produce a series of high value-added fine chemicals. Selective hydrogenation and hydrogenolysis are considered to be the most effective methods for converting furan compounds into valuable chemicals. Furfural/furfuryl alcohol can be converted into various fuel components and fine chemicals through selective hydrogenation. For example: when the C-O bond on the side chain of the FA/FFA furan ring undergoes hydrogenolysis, the product is 2-methylfuran (2-MF). 2-MF is a flammable and water-insoluble colorless liquid. It can be used as a solvent and raw material for the production of antimalarial drugs, pesticides, methyltetrahydrofuran, and perfume intermediates.
  • THFA tetrahydrofurfuryl alcohol
  • Tetrahydrofurfuryl alcohol is a water-soluble furan chemical that can be used as a solvent for fats and resins. Tetrahydrofurfuryl alcohol is also considered to be an environmentally friendly solvent. It is less toxic and easily degraded in nature. It is widely used in various fields in industry.
  • the selective hydrogenolysis of the C-O bond on the FA/FFA furan ring produces 1,2-pentanediol and 1,5-pentanediol.
  • 1,2-Pentanediol (1,2-PeD) is a water-soluble polyol with antibacterial activity and can be used as a preservative in cosmetics and disinfectants.
  • 1,5-Pentanediol (1,5-PeD) is an important chemical intermediate, which is widely used in various fields in the chemical industry, such as polyurethane, polyester, plasticization and fragrance. All these components have their own important applications in industry, but their synthesis under green reaction conditions is a major challenge.
  • the purpose of the present invention is to provide a method for efficient hydrogenation and conversion of furfuryl alcohol and a highly dispersed supported Pt catalyst.
  • the catalyst is a Pt-containing catalyst, and the reaction pressure is 0-3MPa and not 0.
  • the ethanol solution of furfuryl alcohol enters the vaporization chamber of the device through a liquid pressure pump and is mixed with the reaction gas H 2 It enters the reactor uniformly, and the reaction temperature is between 160°C and 300°C.
  • the ratio of furfuryl alcohol to H 2 is 1/100 mol.
  • the catalyst is used to catalyze the hydrogenation reaction of furfuryl alcohol to prepare 1,2-pentanediol.
  • the Pt-containing catalyst of the present invention is composed of uniformly dispersed Pt metal active centers and a composite oxide obtained by calcining hydrotalcite.
  • the catalyst active centers are Pt metal active centers.
  • the content of the catalyst Pt metal active centers is 0.08 to 1.67 wt%
  • the active center of Pt metal is a single atom or cluster of atoms (particle size is 0.9-1.6nm).
  • double metal composite hydroxides are also called hydrotalcite (Layered Double Hydroxides, abbreviated as LDHs) as the carrier, the hydrotalcite laminates choose Mg 2+ for divalent cations and Al 3+ for trivalent cations.
  • LDHs Hydrotalcite
  • the hydrotalcite is grown in-situ on the surface of ⁇ -Al 2 O 3 .
  • the prepared hydrotalcite carrier is immersed in Pt 2+ solution, and the precursor of the hydrotalcite sample impregnated with Pt 2+ is reduced in H 2 atmosphere.
  • the reduction temperature is controlled at 300-400°C and the reduction time is controlled at 60-120min.
  • Pt-containing catalyst such as Pt/Mg(Al)O-IR.
  • calcination in air is carried out before H 2 reduction, the calcination temperature is 300-400°C, and the time is controlled at 60-120min.
  • the catalyst of the present invention is composed of evenly dispersed metal active center platinum and carrier magnesium aluminum composite oxide.
  • the elements of the hydrotalcite laminates are uniformly dispersed at the atomic level, and the lattice induction effect is used to prepare a highly dispersed Pt catalyst at the atomic level in situ.
  • the catalytic performance can remain stable for a long time, and its reaction activity and product selectivity can quickly reach a stable value after the reaction.
  • the preparation method of the supported Pt catalyst of the present invention is simple and is beneficial to be applied in the process of industrial production.
  • the present invention can make the conversion rate of furfuryl alcohol reach 100%, and the selectivity of the product 1,2-pentanediol is relatively high.
  • the conversion rate of furfuryl alcohol is 87%, and the selectivity of 2-methylfuran reaches 93%.
  • the conversion rate of furfuryl alcohol is 100%, and the selectivity of 1,2-pentanediol reaches 86%.
  • the Pt catalyst is applied to the reaction process of catalyzing the conversion of furfuryl alcohol to prepare high value-added chemicals.
  • the evaluation device includes two gas feed paths and a liquid feed path.
  • the gas feed paths are generally H 2 and N 2 , and the liquid feed path pumps the liquid reactant into the device through a pressure pump.
  • Step A Use the in-situ growth method to grow MgAl-LDHs on the surface of ⁇ -Al 2 O 3 in situ.
  • Step B Pt 2+ is loaded on MgAl-LDHs@Al 2 O 3 by the incipient wetness dipping method. Dissolve [Pt(NH 3 ) 4 ](NO 3 ) 2 in deionized water. The well-mixed solution was added dropwise to the successfully prepared MgAl-LDHs@Al 2 O 3 10ml flask, and then placed in a shaker and shaken for 1 hour. Dried overnight at 60 deg.] C to give Pt 2+ theoretical loading of 0.10% by Pt 2+ / MgAl-LDHs @ Al 2 O 3 precursor.
  • the precursor obtained above was used in a microtubular catalyst evaluation device. 1g of the Pt metal catalyst precursor was weighed and put into the thermocouple and the reaction tube, and the remaining part was filled with quartz sand. First, the catalyst was reduced in situ online, and air was introduced. The volumetric space velocity was set in an air atmosphere (40 mL min -1 ), and the temperature was raised to 400 °C for 5 °C min for 2 h. Switch to N 2 and perform purge. After the temperature drops to 300°C, switch to H 2 and keep it for 1 hour to obtain a Pt single-atom catalyst. After the reaction tube is cooled to the reaction temperature of 200° C., the pressure of the entire device is increased to 3 MPa through the back pressure valve.
  • the ethanol solution of furfuryl alcohol was injected into the reactor at a rate of 100 ⁇ l ⁇ min -1 through the liquid feed pump, the circulating condenser was turned on, and the liquid product was collected in the gas-liquid separation tank, and samples were taken every 1 hour.
  • the catalytic product was analyzed by gas chromatography on-line, and it was determined that the conversion rate of furfuryl alcohol was 87% and the selectivity of 2-methylfuran was 93% under the steady state of the reaction.
  • Step A Use the in-situ growth method to grow MgAl-LDHs on the surface of ⁇ -Al 2 O 3 in situ.
  • Step B Pt 2+ is loaded on MgAl-LDHs@Al 2 O 3 by the incipient wetness dipping method.
  • [Pt(NH 3 ) 4 ](NO 3 ) 2 is dissolved in deionized water.
  • the well-mixed solution was added dropwise to the successfully prepared MgAl-LDHs@Al 2 O 3 10ml flask, and then placed in a shaker and shaken for 1 hour. Dry overnight at 60°C to obtain Pt 2+ /MgAl-LDHs@Al 2 O 3 with a theoretical Pt 2+ loading of 1.80%.
  • the Pt metal catalyst precursor of Example 2 was used on a microtubular catalyst evaluation device. Weigh 1g of the Pt metal catalyst precursor, put it into the thermocouple and the reaction tube, and fill the remaining part with quartz sand. Firstly, the catalyst was reduced in situ online, and reducing gas H 2 was introduced . The volumetric space velocity was set under H 2 atmosphere (40 mL min -1 ), and the temperature was raised to 400 °C for 5 °C min for 2 h. The average size of the Pt metal center is about 1.6 nm clusters.
  • the pressure of the entire device is increased to 3MPa through the back pressure valve, and then the temperature of the preheating box is increased to 160°C, and the temperature of the pipeline insulation heating belt is increased to 140°C.
  • the ethanol solution of furfuryl alcohol was injected into the reactor at a rate of 100 ⁇ l ⁇ min -1 through the liquid feed pump, the circulating condenser was turned on, and the liquid product was collected in the gas-liquid separation tank, and samples were taken every 1 hour.
  • the catalytic product was analyzed by gas chromatography on-line, and it was determined that the conversion rate of furfuryl alcohol was 100% and the selectivity of 1,2-pentanediol was 86% under the steady state of the reaction.
  • the selectivity of tetrahydrofurfuryl alcohol is 6%.
  • Step A Use the in-situ growth method to grow MgAl-LDHs on the surface of ⁇ -Al 2 O 3 in situ.
  • Step B Pt 2+ is loaded on MgAl-LDHs@Al 2 O 3 by the incipient wetness dipping method.
  • [Pt(NH 3 ) 4 ](NO 3 ) 2 is dissolved in deionized water.
  • the well-mixed solution was added dropwise to the successfully prepared MgAl-LDHs@Al 2 O 3 10ml flask, and then placed in a shaker and shaken for 1 hour. Dry overnight at 60°C to obtain Pt 2+ /MgAl-LDHs@Al 2 O 3 with a theoretical Pt 2+ loading of 0.10%.
  • the catalytic performance evaluation of the Pt metal catalyst of Comparative Example 2 was performed on a microtubular catalyst evaluation device. Weigh 1g of the Pt metal catalyst precursor, put it into the thermocouple and the reaction tube, and fill the remaining part with quartz sand. Firstly, the catalyst was reduced in situ online, and reducing gas H 2 was introduced . The volumetric space velocity was set under H 2 atmosphere (40 mL min -1 ), and the temperature was raised to 400 °C for 5 °C min for 2 h. The average size of Pt metal center is less than 0.8nm clusters. After the reaction tube is cooled to the reaction temperature of 200° C., the pressure of the entire device is increased to 3 MPa through the back pressure valve.
  • the ethanol solution of furfuryl alcohol was injected into the reactor at a rate of 100 ⁇ l ⁇ min -1 through the liquid feed pump, the circulating condenser was turned on, and the liquid product was collected in the gas-liquid separation tank, and samples were taken every 1 hour.
  • the catalytic product was analyzed by gas chromatography on-line, and it was determined that the conversion rate of furfuryl alcohol was 41% and the selectivity of 1,2-pentanediol was 43% under the steady state of the reaction.
  • the selectivity of tetrahydrofurfuryl alcohol is 37%.
  • Step A Use the in-situ growth method to grow MgAl-LDHs on the surface of ⁇ -Al 2 O 3 in situ.
  • Step B Pt 2+ is loaded on MgAl-LDHs@Al 2 O 3 by the incipient wetness dipping method.
  • [Pt(NH 3 ) 4 ](NO 3 ) 2 is dissolved in deionized water.
  • the well-mixed solution was added dropwise to the successfully prepared MgAl-LDHs@Al 2 O 3 10ml flask, and then placed in a shaker and shaken for 1 hour. Dry overnight at 60°C to obtain Pt 2+ /MgAl-LDHs@Al 2 O 3 with a theoretical Pt 2+ loading of 0.15%.
  • the Pt metal catalyst precursor of Example 3 was used on a microtubular catalyst evaluation device. Weigh 1g of the Pt metal catalyst precursor, put it into the thermocouple and the reaction tube, and fill the remaining part with quartz sand. Firstly, the catalyst was reduced in situ online, and reducing gas H 2 was introduced . The volumetric space velocity was set under H 2 atmosphere (40 mL min -1 ), and the temperature was raised to 400 °C for 5 °C min for 2 h. The average size of the Pt metal center is about 0.9nm clusters. After the reaction tube is cooled to the reaction temperature of 200° C., the pressure of the entire device is increased to 3 MPa through the back pressure valve.
  • the ethanol solution of furfuryl alcohol was injected into the reactor at a rate of 100 ⁇ l ⁇ min -1 through the liquid feed pump, the circulating condenser was turned on, and the liquid product was collected in the gas-liquid separation tank, and samples were taken every 1 hour.
  • the catalytic product was analyzed by gas chromatography on-line, and it was determined that the conversion rate of furfuryl alcohol was 65% and the selectivity of 1,2-pentanediol was 64% under the steady state of the reaction.
  • the selectivity of tetrahydrofurfuryl alcohol is 15%.
  • Step A Use the in-situ growth method to grow MgAl-LDHs on the surface of ⁇ -Al 2 O 3 in situ.
  • Step B Pt 2+ is loaded on MgAl-LDHs@Al 2 O 3 by the incipient wetness dipping method.
  • [Pt(NH 3 ) 4 ](NO 3 ) 2 is dissolved in deionized water.
  • the well-mixed solution was added dropwise to the successfully prepared MgAl-LDHs@Al 2 O 3 10ml flask, and then placed in a shaker and shaken for 1 hour. Dry overnight at 60°C to obtain Pt 2+ /MgAl-LDHs@Al 2 O 3 with a theoretical Pt 2+ loading of 0.78%.
  • the Pt metal catalyst precursor of Example 4 was used on a microtubular catalyst evaluation device. Weigh 1g of the Pt metal catalyst precursor, put it into the thermocouple and the reaction tube, and fill the remaining part with quartz sand. Firstly, the catalyst was reduced in situ online, and reducing gas H 2 was introduced . The volumetric space velocity was set under H 2 atmosphere (40 mL min -1 ), and the temperature was raised to 400 °C for 5 °C min for 2 h. The average size of the Pt metal center is about 1.2nm. After the reaction tube is cooled to the reaction temperature of 200° C., the pressure of the entire device is increased to 3 MPa through the back pressure valve.
  • the ethanol solution of furfuryl alcohol was injected into the reactor at a rate of 100 ⁇ l ⁇ min -1 through the liquid feed pump, the circulating condenser was turned on, and the liquid product was collected in the gas-liquid separation tank, and samples were taken every 1 hour.
  • the catalytic product was analyzed by gas chromatography on-line, and it was determined that the conversion rate of furfuryl alcohol was 98% and the selectivity of 1,2-pentanediol was 83% under the steady state of the reaction. Tetrahydrofurfuryl alcohol selectivity 7%

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Abstract

一种高效加氢转化糠醇的方法及高分散负载型Pt催化剂，属于生物质催化转化领域。采用高分散负载型Pt催化剂，属于生物质催化转化领域。在微型固定床反应装置上在线进行，在一定的H 2压力和反应温度下，糠醇通过液体压力泵进入装置气化室与反应气氢气混合均匀进入反应器。含Pt金属催化剂为均匀分散的Pt金属活性中心及水滑石煅烧所得的复合氧化物组成，催化剂活性中心原子水平高分散的Pt单原子和Pt原子簇。本发明优点在于反应能够长期连续稳定运行，催化剂中Pt与载体形成强相互作用。在单原子Pt上，糠醇转化率87％，2-甲基呋喃选择性达到93％。在原子簇Pt上，糠醇转化率100％，1,2-戊二醇选择性达到86％。

Description

一种高效加氢转化糠醇的方法及高分散负载型Pt催化剂 技术领域
本发明属于生物质催化转化技术领域，特别是提供了一种高效加氢转化糠醇的方法及高分散负载型Pt催化剂。
背景技术
生物质资源具有分布广泛，储量丰富和可再生等特点，由生物质及其平台分子生产燃料和精细化学品逐渐引起广泛的关注。糠醛(FFA)是生物质中最重要的平台分子之一，被认为是木质纤维素生物质生产的最重要的化学品之一。目前，糠醛的生产主要是通过酸催化生物质原料中的戊聚糖来实现的。糠醇(FA)，通过糠醛C＝O键的加氢得到，是来自糠醛加氢产物中最重要的一种化学品。据估计，全球每年生产的糠醛中有62％转化为了糠醇。糠醛/糠醇可通过加氢反应，生产一系列高附加值精细化学品。选择性加氢和氢解被认为是将呋喃化合物转化为有价值化学品的最有效方法。糠醛/糠醇可以通过选择性加氢转化为各种燃料成分和精细化学品。例如：当FA/FFA呋喃环侧链上的C-O键发生氢解时，产物为2-甲基呋喃(2-MF)。2-MF是一种易燃且不溶于水的无色液体，可用作溶剂和生产抗疟药物，农药，甲基四氢呋喃，香料中间体的原料。FA/FFA呋喃环上两个C＝C加氢可生成四氢糠醇(THFA)。它是一种水溶性呋喃化学品，可用作脂肪和树脂的溶剂。四氢糠醇也被认为是一种环保型的溶剂，毒性较小且容易在自然界中降解，广泛用于工业中的各种领域。FA/FFA呋喃环上的C-O键发生选择性氢解会生成1,2-戊二醇和1,5-戊二醇。1,2-戊二醇(1,2-PeD)是一种具有抗菌活性的水溶性多元醇，可用作化妆品和消毒剂中的防腐剂。此外，它还可被用作主链中含有酯官能团的聚酯单体。这种聚酯具有广泛的应用，如纺织品，包装材料和工程塑料。1,5-戊二醇(1,5-PeD)是一种重要的化工中间体，被广泛用于化学工业中的各个领域，如聚氨酯、聚酯、增塑和香料。所有这些组分在工业上都有各自重要的应用，但它们在绿色反应条件下的合成是一项重大挑战。
由于生物质及其平台分子中化学键的多样性(C＝C,C-O-C,C-O-H和C＝O)，反应中往往存在竞争或连续的反应过程，特定化学键的选择性活化和定向转化是一个巨大的挑战，存在目标产物选择性不高的问题。生物质平台分子加氢转化为高附加值化学品过程中应对催化剂结构进行有效的控制。然而，控制合成具有高 活性和针对目标产物高选择性的金属催化剂仍然是一个难点。可以改变金属催化剂的尺寸、形状以及电子结构等来调控活性位的电子结构和几何结构。通过对金属催化剂结构控制，可以显著提高催化剂加氢性能。
发明内容
本发明的目的在于提供一种高效加氢转化糠醇的方法及高分散负载型Pt催化剂。
为实现上述目的，在微型固定床反应装置上进行，催化剂为含Pt催化剂，反应压力在0～3MPa且不为0，糠醇的乙醇溶液通过液体压力泵进入装置气化室与反应气体H 2混合均匀进入反应器，反应温度在160℃～300℃。优选糠醇与H 2的比例为1/100mol。
所述的催化剂用于催化糠醇加氢反应制备1,2-戊二醇。
本发明的含Pt催化剂为由均匀分散的Pt金属活性中心及水滑石煅烧所得的复合氧化物组成，催化剂活性中心为Pt金属活性中心，优选催化剂Pt金属活性中心的含量为0.08～1.67wt％，Pt金属活性中心为单原子或原子簇(粒径为0.9-1.6nm)。
含Pt催化剂的制备：双金属复合氢氧化物又称为水滑石(Layered Double Hydroxides,简写为LDHs)为载体，水滑石层板二价阳离子选择Mg 2+，三价阳离子选择Al 3+。利用原位生长法，将水滑石原位生长在γ-Al 2O 3表面。制备的水滑石载体浸渍Pt 2+溶液，将浸渍Pt 2+后的水滑石样品前驱体在H 2气氛中还原，还原温度控制在300-400℃，还原时间控制在60-120min，即可得到含Pt催化剂，如Pt/Mg(Al)O-IR。为了得到单原子的Pt金属活性中心在H 2还原之前进行在空气中煅烧，煅烧的温度为300-400℃，时间控制在60-120min。
本发明具有如下优点：
1.本发明催化剂由均分散的金属活性中心铂和载体镁铝复合氧化物组成。利用水滑石层板元素呈原子级均分散，晶格诱导效应原位制备了原子水平高分散的Pt催化剂。
2.催化性能能够长时间保持稳定，其反应活性和产物选择性在反应后能够迅速达到一个稳定值。
3.本发明的负载型Pt催化剂制备方法简单，有利于应用在工业生产的过程中。
4、本发明可以使糠醇得转化率达到100％，产品1,2-戊二醇的选择性比较高。
如在单原子Pt上，糠醇转化率87％，2-甲基呋喃选择性达到93％。在原子簇Pt上，糠醇转化率100％，1,2-戊二醇选择性达到86％。
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。
所述的Pt催化剂应用于催化糠醇转化制备高附加值化学品的反应过程。反应条件如下：负载的Pt催化剂的催化性能评价催化在微型管式催化剂评价装置上进行，反应管的规格是内径d＝10mm，长度l＝380mm。评价装置包含俩条气体进料路和一条液体进料路，气体进料路一般为H 2和N 2，液体进料路通过压力泵将液体反应物泵入装置。鉴于催化剂评价反应需要高温条件，同时存在H 2、乙醇等易燃易爆物质，因此在每一次装管评价反应前必须进行憋压、验漏测验，确保装置气密性良好，无漏气、漏液现象。
实施例1
步骤A：利用原位生长法，将MgAl-LDHs原位生长在γ-Al 2O 3表面。首先，用5.5mL去离子水将11mmol Mg(NO 3) 2·6H 2O和33mmol尿素溶解，配置成Mg 2+-尿素溶液。然后，将配置好的溶液倒入已经装有γ-Al 2O 3小球(5g)的15ml高压反应釜中，随后放入摇床内，振荡1h。最后，在120℃烘箱中晶化12h。晶化结束后，将得到的固体用去离子水冲洗多次直到呈中性。在60℃下干燥过夜。制得MgAl-LDHs@Al 2O 3。
步骤B：采用初湿浸渍法在MgAl-LDHs@Al 2O 3上负载Pt 2+。将[Pt(NH 3) 4](NO 3) 2溶解在去离子水中。将混合均匀的溶液逐滴加入到装有已经制备成功的MgAl-LDHs@Al 2O 3 10ml烧瓶中，随后放入摇床内，振荡1h。在60℃下干燥过夜得到Pt 2+理论负载量分别为0.10％的Pt 2+/MgAl-LDHs@Al 2O 3前驱体。
用上述所得的前驱体在微型管式催化剂评价装置上进行，称取1g Pt金属催化剂前体，装入热电偶所及反应管之处，剩余部分用石英砂填充。首先将催化剂在线原位还原，通入空气，体积空速设为在空气氛围下(40mL min -1),5℃ min升温至400℃保持2h。切换成N 2，进行吹扫。待温度降到300℃后，切换成H 2，保温1h，得到Pt单原子催化剂。待反应管降温至反应温度200℃后，通过背压阀将整个装置的压力升至3MPa。通过液体进料泵将糠醇的乙醇溶液以 100μl·min -1注入反应器，打开循环冷凝装置，在气液分离罐内收集液体产物，每间隔1h取一次样。催化产物采用气相色谱在线分析，测得反应稳定状态下，糠醇转化率87％，2-甲基呋喃选择性93％。
实施例2
步骤A：利用原位生长法，将MgAl-LDHs原位生长在γ-Al 2O 3表面。首先，用5.5mL去离子水将11mmol Mg(NO 3) 2·6H 2O和33mmol尿素溶解，配置成Mg 2+-尿素溶液。然后，将配置好的溶液倒入已经装有γ-Al 2O 3小球(5g)的15ml高压反应釜中，随后放入摇床内，振荡1h。最后，在120℃烘箱中晶化12h。晶化结束后，将得到的固体用去离子水冲洗多次直到呈中性。在60℃下干燥过夜。制得MgAl-LDHs@Al 2O 3
步骤B：采用初湿浸渍法在MgAl-LDHs@Al 2O 3上负载Pt 2+。首先将[Pt(NH 3) 4](NO 3) 2溶解在去离子水中。将混合均匀的溶液逐滴加入到装有已经制备成功的MgAl-LDHs@Al 2O 3 10ml烧瓶中，随后放入摇床内，振荡1h。在60℃下干燥过夜得到Pt 2+理论负载量分别为1.80％的Pt 2+/MgAl-LDHs@Al 2O 3。
用实施例2的Pt金属催化剂前驱体在微型管式催化剂评价装置上进行。称取1g Pt金属催化剂前体，装入热电偶所及反应管之处，剩余部分用石英砂填充。首先将催化剂在线原位还原，通入还原气H 2，体积空速设为在H 2氛围下(40mL min -1),5℃ min升温至400℃保持2h。得到Pt金属中心平均尺寸约为1.6nm原子簇。待反应管降温至反应温度200℃后，通过背压阀将整个装置的压力升至3MPa，然后将预热箱的温度升至160℃，管路保温加热带的温度升温至140℃。通过液体进料泵将糠醇的乙醇溶液以100μl·min -1注入反应器，打开循环冷凝装置，在气液分离罐内收集液体产物，每间隔1h取一次样。催化产物采用气相色谱在线分析，测得反应稳定状态下，糠醇转化率100％，1,2-戊二醇选择性86％。四氢糠醇选择性6％。
对比例2
步骤A：利用原位生长法，将MgAl-LDHs原位生长在γ-Al 2O 3表面。首先，用5.5mL去离子水将11mmol Mg(NO 3) 2·6H 2O和33mmol尿素溶解，配置成Mg 2+-尿素溶液。然后，将配置好的溶液倒入已经装有γ-Al 2O 3小球(5g)的15ml高压反应釜中，随后放入摇床内，振荡1h。最后，在120℃烘箱中晶化12h。晶化结束后，将得到的固体用去离子水冲洗多次直到呈中性。在60℃下干燥过 夜。制得MgAl-LDHs@Al 2O 3。
步骤B：采用初湿浸渍法在MgAl-LDHs@Al 2O 3上负载Pt 2+。首先将[Pt(NH 3) 4](NO 3) 2溶解在去离子水中。将混合均匀的溶液逐滴加入到装有已经制备成功的MgAl-LDHs@Al 2O 3 10ml烧瓶中，随后放入摇床内，振荡1h。在60℃下干燥过夜得到Pt 2+理论负载量分别为0.10％的Pt 2+/MgAl-LDHs@Al 2O 3。
用对比例2的Pt金属催化剂的催化性能评价在微型管式催化剂评价装置上进行。称取1g Pt金属催化剂前体，装入热电偶所及反应管之处，剩余部分用石英砂填充。首先将催化剂在线原位还原，通入还原气H 2，体积空速设为在H 2氛围下(40mL min -1),5℃ min升温至400℃保持2h。得到Pt金属中心平均尺寸小于0.8nm原子簇。待反应管降温至反应温度200℃后，通过背压阀将整个装置的压力升至3MPa。通过液体进料泵将糠醇的乙醇溶液以100μl·min -1注入反应器，打开循环冷凝装置，在气液分离罐内收集液体产物，每间隔1h取一次样。催化产物采用气相色谱在线分析，测得反应稳定状态下，糠醇转化率41％，1,2-戊二醇选择性43％。四氢糠醇选择性37％。
实施例3
步骤A：利用原位生长法，将MgAl-LDHs原位生长在γ-Al 2O 3表面。首先，用5.5mL去离子水将11mmol Mg(NO 3) 2·6H 2O和33mmol尿素溶解，配置成Mg 2+-尿素溶液。然后，将配置好的溶液倒入已经装有γ-Al 2O 3小球(5g)的15ml高压反应釜中，随后放入摇床内，振荡1h。最后，在120℃烘箱中晶化12h。晶化结束后，将得到的固体用去离子水冲洗多次直到呈中性。在60℃下干燥过夜。制得MgAl-LDHs@Al 2O 3
步骤B：采用初湿浸渍法在MgAl-LDHs@Al 2O 3上负载Pt 2+。首先将[Pt(NH 3) 4](NO 3) 2溶解在去离子水中。将混合均匀的溶液逐滴加入到装有已经制备成功的MgAl-LDHs@Al 2O 3 10ml烧瓶中，随后放入摇床内，振荡1h。在60℃下干燥过夜得到Pt 2+理论负载量分别为0.15％的Pt 2+/MgAl-LDHs@Al 2O 3。
用实施例3的Pt金属催化剂前驱体在微型管式催化剂评价装置上进行。称取1g Pt金属催化剂前体，装入热电偶所及反应管之处，剩余部分用石英砂填充。首先将催化剂在线原位还原，通入还原气H 2，体积空速设为在H 2氛围下(40mL min -1),5℃ min升温至400℃保持2h。得到Pt金属中心平均尺寸约为0.9nm原子簇。待反应管降温至反应温度200℃后，通过背压阀将整个装置的压力升 至3MPa。通过液体进料泵将糠醇的乙醇溶液以100μl·min -1注入反应器，打开循环冷凝装置，在气液分离罐内收集液体产物，每间隔1h取一次样。催化产物采用气相色谱在线分析，测得反应稳定状态下，糠醇转化率65％，1,2-戊二醇选择性64％。四氢糠醇选择性15％。
实施例4
步骤A：利用原位生长法，将MgAl-LDHs原位生长在γ-Al 2O 3表面。首先，用5.5mL去离子水将11mmol Mg(NO 3) 2·6H 2O和33mmol尿素溶解，配置成Mg 2+-尿素溶液。然后，将配置好的溶液倒入已经装有γ-Al 2O 3小球(5g)的15ml高压反应釜中，随后放入摇床内，振荡1h。最后，在120℃烘箱中晶化12h。晶化结束后，将得到的固体用去离子水冲洗多次直到呈中性。在60℃下干燥过夜。制得MgAl-LDHs@Al 2O 3
步骤B：采用初湿浸渍法在MgAl-LDHs@Al 2O 3上负载Pt 2+。首先将[Pt(NH 3) 4](NO 3) 2溶解在去离子水中。将混合均匀的溶液逐滴加入到装有已经制备成功的MgAl-LDHs@Al 2O 3 10ml烧瓶中，随后放入摇床内，振荡1h。在60℃下干燥过夜得到Pt 2+理论负载量分别为0.78％的Pt 2+/MgAl-LDHs@Al 2O 3。
用实施例4的Pt金属催化剂前驱体在微型管式催化剂评价装置上进行。称取1g Pt金属催化剂前体，装入热电偶所及反应管之处，剩余部分用石英砂填充。首先将催化剂在线原位还原，通入还原气H 2，体积空速设为在H 2氛围下(40mL min -1),5℃ min升温至400℃保持2h。得到Pt金属中心平均尺寸约为1.2nm的原子簇。待反应管降温至反应温度200℃后，通过背压阀将整个装置的压力升至3MPa。通过液体进料泵将糠醇的乙醇溶液以100μl·min -1注入反应器，打开循环冷凝装置，在气液分离罐内收集液体产物，每间隔1h取一次样。催化产物采用气相色谱在线分析，测得反应稳定状态下，糠醇转化率98％，1,2-戊二醇选择性83％。四氢糠醇选择性7％

Claims (5)

  1. 一种高效加氢转化糠醇的方法，其特征在于，在微型固定床反应装置上进行，催化剂为含Pt催化剂，反应压力在0～3MPa且不为0，糠醇的乙醇溶液通过液体压力泵进入装置气化室与反应气体H 2混合均匀进入反应器，反应温度在160℃～300℃。
  2. 按照权利要求所述的一种高效加氢转化糠醇的方法，其特征在于，糠醇与H 2的比例为1/100mol。
  3. 按照权利要求所述的一种高效加氢转化糠醇的方法，其特征在于，含Pt催化剂为由均匀分散的Pt金属活性中心及水滑石煅烧所得的复合氧化物组成，催化剂活性中心为Pt金属活性中心，优选催化剂Pt金属活性中心的含量为0.08～1.67wt％，Pt金属活性中心为单原子或原子簇，原子簇粒径为0.9-1.6nm。
  4. 按照权利要求1所述的一种高效加氢转化糠醇的方法，其特征在于，用于催化糠醇加氢反应制备1,2-戊二醇。
  5. 制备权利要求3中所述的含Pt催化剂的方法，其特征在于，包括以下步骤：含Pt催化剂的制备：双金属复合氢氧化物又称为水滑石(Layered Double Hydroxides,简写为LDHs)为载体，水滑石层板二价阳离子选择Mg 2+，三价阳离子选择Al 3+。利用原位生长法，将水滑石原位生长在γ-Al 2O 3表面。制备的水滑石载体浸渍Pt 2+溶液，将浸渍Pt 2+后的水滑石样品前驱体在H 2气氛中还原，还原温度控制在300-400℃，还原时间控制在60-120min，即可得到含Pt催化剂；为了得到单原子的Pt金属活性中心在H 2还原之前进行在空气中煅烧，煅烧的温度为300-400℃，时间控制在60-120min。
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CN114950412A (zh) * 2022-07-12 2022-08-30 清华大学 一种原子重构制备单原子与纳米簇协同负载型催化剂的方法
CN121130883A (zh) * 2025-11-18 2025-12-16 北京化工大学 一种生物基糠醇加氢催化剂及其制备方法和生物基糠醇加氢制备1,2-戊二醇的工艺

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