WO2018157604A1 - 一种改性Pd/C直接催化碳水化合物制备2,5-二甲基呋喃的方法 - Google Patents

一种改性Pd/C直接催化碳水化合物制备2,5-二甲基呋喃的方法 Download PDF

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WO2018157604A1
WO2018157604A1 PCT/CN2017/105835 CN2017105835W WO2018157604A1 WO 2018157604 A1 WO2018157604 A1 WO 2018157604A1 CN 2017105835 W CN2017105835 W CN 2017105835W WO 2018157604 A1 WO2018157604 A1 WO 2018157604A1
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dimethylfuran
carbohydrate
modified
preparing
modifying
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李虎
杨松
赵文凤
薛伟
方真
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贵州大学
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    • 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
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
    • B01J31/124—Silicones or siloxanes or comprising such units
    • B01J31/126—Silicones or siloxanes or comprising such units the siloxanes or siloxane units, cyclic or not, comprising an additional Si-H bond, e.g. polyhydromethylsiloxane [PHMS]
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • 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
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
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    • 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
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon

Definitions

  • the present invention relates to a process for the preparation of 2,5-dimethylfuran from a modified Pd/C direct catalyzed carbohydrate.
  • Pd/C is modified with chlorosulfonic acid and trimethylchlorosilane to catalyze the biomass sugar source (hexacarbon monosaccharide or polysaccharide) under the condition that polymethylhydrogensiloxane is hydrogen donor.
  • the step" is converted to 2,5-dimethylfuran.
  • the traditional 2,5-dimethylfuran preparation method mostly uses the 5-carbon sugar downstream platform molecule 5-hydroxymethylfuran as the raw material, and the catalytic system is mostly based on Ru, Pd, Pt, Ni and Cu.
  • the medium or carrier and the hydrogen molecule are hydrogen donors [3] .
  • the above system can obtain a higher yield of 2,5-dimethylfuran, there are many disadvantages such as complicated process, high cost, and severe reaction conditions.
  • the use of carbohydrates instead of 5-hydroxymethylfuran as raw materials has the advantages of low raw material prices and sustainable greening.
  • the catalytic process often involves two or more steps of the reaction process, the product distribution is complex, and the active intermediate needs to be separated and purified in order to carry out the next transformation reaction [4] . Therefore, the development of catalytic materials or catalytic systems with high activity and high selectivity has become the key to directly and efficiently catalyze the preparation of 2,5-dimethylfuran for carbohydrates and to achieve corresponding industrial production.
  • Polymethylhydrogensiloxane is a by-product of the silicone industry and is non-toxic, inexpensive, safe to use and stable to air and water [5] .
  • polymethylhydrogensiloxane is generally used as a hydrogen donor to catalyze the reduction of compounds such as amides, esters, hydroxyl groups, nitro groups and carbonyl groups under the action of metal elements (especially Pd) [6] .
  • metal elements especially Pd
  • the conversion of directly catalyzed sugars (especially polysaccharides) to 2,5-dimethylfuran often involves a reaction step such as hydrolysis, dehydration, hydrogenation, and the like.
  • the object of the present invention is to provide an effective method for directly preparing carbohydrates for preparing 2,5-dimethylfuran.
  • the process has mild conditions, fast reaction rate and wide range of applicable substrates, so as to overcome the energy consumption of the prior art. Defects such as high cost and harsh reaction conditions.
  • the technical scheme adopted by the present invention is: a method for preparing a 2,5-dimethylfuran by directly modifying a Pd/C to catalyze a carbohydrate, comprising the following steps:
  • the second step the modified Pd/C obtained in the step (1) is used as a catalyst, and the polymethylhydrogensiloxane is used as a hydrogen donor, and the carbohydrate is dissolved in the alcohol and reacted at 80 to 140 ° C. ⁇ 5h; after the reaction is completed, the catalyst and the product are separated by centrifugation to obtain 2,5-dimethylfuran.
  • a modified Pd/C catalytic material of the present invention consists in that commercial Pd/C is sequentially treated by chlorosulfonic acid and trimethylchlorosilane, and then washed with n-hexane, vacuum dried, and ground to obtain an acidic, hydrophobic Pd/ C catalytic material, referred to as modified Pd / C.
  • the polymethylhydrogensiloxane of the present invention is used in an amount of 4 to 10 equivalents based on the amount of the carbohydrate.
  • the concentration of the carbohydrate in the alcohol of the present invention is 2 to 6 wt%.
  • reaction vessel used for the preparation of the catalyst was a 50 mL round bottom flask.
  • the stirring condition of the present invention is magnetic stirring and the number of revolutions is 600 r/min.
  • the amount of chlorosulfonic acid used in the present invention was 0.20 mL; the slow addition time was 2 min.
  • n-hexane of the present invention was washed 5 times, and the volume taken each time was 20 mL.
  • the modified Pd/C of the present invention is useful for the direct catalysis of carbohydrates for the preparation of 2,5-dimethylfuran.
  • the reaction temperature is 100 to 120 ° C, and the reaction time is 1 to 3 hours.
  • the modified Pd/C is contained in an amount of 1 to 3 mol% relative to the carbohydrate
  • the polymethylhydrogensiloxane is used in an amount of 6 to 9 equivalents relative to the carbohydrate
  • the concentration of the carbohydrate in the alcohol is 3 to 5 wt%. %.
  • the carbohydrates of the present invention are common hexoses including fructose, glucose, maltose, sucrose, cellobiose, starch, inulin, and cellulose.
  • the alcohol is methanol, ethanol, n-propanol, n-butanol or n-hexanol.
  • the regeneration of the modified Pd/C catalyst is further included: the catalyst is filtered out from the reaction solution, and washed with ethanol and n-hexane each 4-6 After drying at 90 ° C for 5 to 12 hours, the regenerated catalyst was obtained after grinding.
  • the preparation method of the catalytic material of the invention is simple, the raw material is easy to obtain, and the hydrophobicity is strong, and the acid-metal bifunctional site is contained;
  • the modified Pd/C of the invention has high catalytic activity and is easy to be separated, recovered and reused;
  • the modified Pd/C of the invention has wide applicability to different carbohydrates, and has the advantages of mild reaction conditions, high selectivity, high stability, fast reaction rate and good reusability.
  • Figure 1 shows the distribution of modified 5 wt% Pd/C in water and butanol (left) and the contact angle of the surface water droplets (right).
  • Figure 2 shows the distribution of 5 wt% Pd/C in water and butanol (left) and the surface water droplet contact angle (right).
  • Figure 3 is an XRD spectrum of the modified Pd/C after repeated use (upper) and new (lower).
  • the modified 5wt% Pd/C is uniformly dispersed in the n-butanol solvent, but is substantially immiscible with water (left); at the same time, the higher water droplet contact angle (134°) is also verified.
  • the modified 5 wt% Pd/C has good hydrophobicity (right panel).
  • the catalytic material was also confirmed to have a higher acid amount ( ⁇ 1.1 mmol/g) by acid-base titration. Thus, it can be judged that the modified 5 wt% Pd/C has both desirable hydrophobicity and acidity.
  • the 5 wt% Pd/C used was a commercial reagent purchased from Beijing Enoch Technology Co., Ltd.
  • Figure 2 shows that 5wt% Pd/C has good hydrophilicity (left) and a lower water droplet contact angle (28°) also reflects the material's poor hydrophobicity.
  • the commercially available 5 wt% Pd/C catalyzed fructose obtained in the present example was used to prepare 2,5-dimethylfuran.
  • the amount of each raw material, the reaction conditions, and the sample test method were the same as those in Example 1 (2). After the completion of the reaction, the fructose conversion rate in the mixed solution was 52% and the yield of 2,5-dimethylfuran was 43% as determined by liquid phase and gas chromatography, respectively.
  • Acidic Pd/C catalytic material can be obtained; (B) 0.25 g of acidic Pd/C catalytic material is placed in 7.5 mL of cyclohexane, and then 1.5 mL of trimethylchlorosilane is added dropwise to the above mixed system, and added dropwise After completion, stirring was continued for 12 hours under heating conditions of 60 ° C, followed by washing 5 times with n-hexane, vacuum drying at 90 ° C for 6 h, and grinding to obtain an acidic and hydrophobic Pd/C catalytic material, that is, modified 2 wt% Pd/C. .
  • Acidic Pd/C catalytic material can be obtained; (B) 0.25 g of acidic Pd/C catalytic material is placed in 7.5 mL of cyclohexane, and then 1.5 mL of trimethylchlorosilane is added dropwise to the above mixed system, and added dropwise After completion, the mixture was stirred at 60 ° C for 12 h, then washed successively with n-hexane for 5 times, vacuum dried at 90 ° C for 6 h, and ground to obtain an acidic, hydrophobic Pd/C catalytic material, which was modified 0.5 wt% Pd/ C.
  • sucrose Into a 15 mL pressure-resistant glass reaction tube, 4 wt% sucrose, 1.5 mL ethanol, 3 mol% modified 0.5 wt% Pd/C, 10 equivalents (relative to sucrose) polymethylhydrogensiloxane, heated at 100 ° C Stir for 5 h. After completion of the reaction, the solid catalyst was separated by centrifugation, and the sucrose conversion rate and the 2,5-dimethylfuran yield in the reaction liquid were respectively determined by HPLC (high performance liquid chromatography) and GC (gas chromatography). By preparing the standard curve of the corresponding standard solution, substituting the peak area of the sample to be tested to obtain the sucrose conversion The yield was 95%, and the yield of 2,5-dimethylfuran was 83%.
  • the acidic Pd/C catalytic material can be obtained; (B) 0.25 g of acidic Pd/C catalytic material is placed in 7.5 mL of cyclohexane, and then 1.5 mL of trimethylchlorosilane is added dropwise to the above mixed system. After the addition was completed, stirring was continued for 12 hours under heating at 60 ° C, followed by washing 5 times with n-hexane, vacuum drying at 90 ° C for 6 h, and grinding to obtain an acidic, hydrophobic Pd/C catalytic material, that is, modified 15 wt% Pd/ C.

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Abstract

一种酸性、疏水Pd/C催化材料的制备方法，依次通过氯磺酸、三甲基氯硅烷进行改性，再经洗涤、干燥后得到改性Pd/C催化材料。一种利用改性Pd/C直接催化碳水化合物制备2,5-甲基呋喃的方法，包括：将碳水化合物溶于醇中，以改性Pd/C为催化剂，聚甲基氢硅氧烷为氢供体，于80～140℃反应1～5h；结束后经离心将催化剂与产物分离；改性Pd/C相对于碳水化合物的含量为1～3mol％，聚甲基氢硅氧烷相对于碳水化合物的用量为4～10倍当量，醇中碳水化合物的浓度为2～6wt％。该方法能有效克服传统催化体系难直接催化碳水化合物制备2,5-二甲基呋喃的不足，并且反应条件温和、活性高。

Description

一种改性Pd/C直接催化碳水化合物制备2,5-二甲基呋喃的方法 技术领域
本发明涉及由改性Pd/C直接催化碳水化合物制备2,5-二甲基呋喃的方法。具体地说，用氯磺酸和三甲基氯硅烷改性Pd/C在聚甲基氢硅氧烷为氢供体条件下催化生物质糖源(六碳单糖或多糖)“一锅单步”转化为2,5-二甲基呋喃。
背景技术
随着世界经济和社会的飞速发展，全球性石化资源消耗与日俱增，石油价格不断上涨，燃料供应形势日趋严峻。另一方面，石油、煤等燃烧后排放的废气(如硫氧化物、氮氧化物、CO2和CO等)会造成环境的污染或温室效应，导致生态环境恶化。因此，生物燃料作为一种新型、环保、可替代的绿色能源已成为科研工作者重要的研究课题和研究热点。特别地，2,5-二甲基呋喃的能量密度(31.5kJ/mol)与汽油(35kJ/mol)的极为接近，并且较汽油具有更高的十六烷基值(RON:119>90-100)[1]。此外，2,5-二甲基呋喃在制备精细化学品(如对二甲基苯)方面也具有极大的应用潜能[2]。
传统的2,5-二甲基呋喃制备方法大多采用六碳糖下游平台分子5-羟甲基呋喃为原料，催化体系多为基于Ru,Pd,Pt,Ni和Cu的金属单质催化剂辅以酸性介质或载体、氢气分子为氢供体[3]。虽然上述体系能得到较高的2,5-二甲基呋喃产率，但存在诸如工艺复杂、成本高、反应条件苛刻等众多缺点。而采用碳水化合物替代5-羟甲基呋喃为原料，具有原料价格低廉、绿色可持续等优点。然而，催化工艺往往涉及两步或多步反应过程、产物分布复杂、活性中间体需要分离纯化才能开展下一步转化反应等诸多不足[4]。因此，具有高活性和高选择性催化材料或催化体系的研制成为直接高效催化碳水化合物制备2,5-二甲基呋喃以及实现相应工业化生产的关键。
聚甲基氢硅氧烷是一种有机硅工业生产的副产物，具有无毒、廉价、使用安全且对空气和水稳定等特性[5]。在有机合成领域，聚甲基氢硅氧烷通常被用作氢供体在金属单质(尤其是Pd)的作用下催化诸如酰胺、酯、羟基、硝基和羰基等化合物的还原反应[6]。通常地，直接催化糖(特别是多糖)转化为2,5-二甲基呋喃往往涉及水解、脱水、加氢等反应步骤。因此，如何有效调控催化剂结构和催化体系组成等实现上述“一锅单步”选择性串联多种反应是高产率制备2,5-二甲基呋喃。然而，至今没有文献和专利有过相关报道。
[1]Roman-Leshkov,Y.；Barrett,C.J.；Liu,Z.Y.；Dumesic,J.A.“Production of  dimethylfuran for liquid fuels from biomass-derived carbohydrates.”Nature,2007,447,982-985.[2]Cheng,Y.T.；Huber,G.W.“Production oftargeted aromatics by using Diels-Alder classes of reactions with furans and olefins over ZSM-5.”Green Chemistry,2012,14,3114-3125.
[3]Hu,L.；Lin,L.；Liu,S.“Chemoselective hydrogenation of biomass-derived 5-hydroxymethylfurfural into the liquid biofuel 2,5-dimethylfuran.”Industrial&Engineering Chemistry Research,2014,53,9969-9978.
[4]Kazi,F.K.；Patel,A.D.；Serrano-Ruiz,J.C.；Dumesic,J.A.；Anex,R.P.“Techno-economic analysis ofdimethylfuran(DMF)and hydroxymethylfurfural(HMF)production from pure fructose in catalytic processes.”Chemical Engineering Journal,2011,169,329-338.
[5]Senapati,K.K.Polymethylhydrosiloxane(PMHS).Synlett,2005,2005,1960-1961.
[6]Volkov,A.；Gustafson,K.P.；Tai,C.W.；Verho,O.；
Figure PCTCN2017105835-appb-000001
J.E.；Adolfsson,H.“Mild deoxygenation ofaromatic ketones and aldehydes over Pd/C using polymethylhydrosiloxane as the reducing agent.”Angewandte Chemie International Edition,2015,54,5122-5126.
发明内容
本发明的目的在于提供一种有效的直接催化碳水化合物制备2,5-二甲基呋喃的方法，此过程条件温和、反应速率快、适用底物范围广泛，以克服已有技术能耗大、成本高、反应条件苛刻等缺陷。
为实现上述目的，本发明采用的技术方案为：一种改性Pd/C直接催化碳水化合物制备2,5-二甲基呋喃的方法，包括以下步骤：
第一步、改性Pd/C的制备，将0.5g Pd/C均匀分散到15mL二氯甲烷中，在搅拌条件下缓慢滴加0.05-0.35mL氯磺酸，并在室温条件下持续搅拌12h，然后经过滤、二氯甲烷和水反复洗涤至滤液为中性、90℃条件下真空干燥6h得到酸性Pd/C催化材料；取用0.25g既得的酸性Pd/C催化材料置入7.5mL环己烷中，然后逐滴加入1.5mL三甲基氯硅烷，并在60℃加热条件搅拌12h，依次通过正己烷洗涤5次、90℃条件下真空干燥6h、研磨，随即得到改性Pd/C。
第二步：以步骤(一)所得的改性Pd/C为催化剂，另以聚甲基氢硅氧烷为氢供体，将碳水化合物溶于醇中，在80～140℃条件下反应1～5h；反应结束后经离心将催化剂与产物分离得到2,5-二甲基呋喃。
本发明的一种改性Pd/C催化材料，在于将商品化Pd/C依次通过氯磺酸和三甲基氯硅烷处理，再经正己烷洗涤、真空干燥、研磨制得酸性、疏水Pd/C催化材料，简称改性Pd/C。
本发明的聚甲基氢硅氧烷相对于碳水化合物的用量为4～10倍当量。
本发明的醇中碳水化合物的浓度为2～6wt％。
本发明中，催化剂制备所用的反应容器为50mL圆底烧瓶。
本发明的搅拌条件为磁力搅拌、转速为600r/min。
本发明的氯磺酸用量为0.20mL；所述的缓慢滴加时间为2min。
本发明的正己烷洗涤5次，每次取用的体积为20mL。
本发明的改性Pd/C在用于直接催化碳水化合物制备2,5-二甲基呋喃的应用。
优选的，反应温度为100～120℃，反应时间为1～3h。
优选的，改性Pd/C相对于碳水化合物的含量为1～3mol％，聚甲基氢硅氧烷相对于碳水化合物的用量为6～9倍当量，醇中碳水化合物的浓度为3～5wt％。
本发明的碳水化合物为常见的己糖，包括果糖、葡萄糖、麦芽糖、蔗糖、纤维二糖、淀粉、菊糖、纤维素。
所述的醇为甲醇、乙醇、正丙醇、正丁醇、正己醇。
作为直接催化碳水化合物制备2,5-二甲基呋喃的方法的优选方案，还包括改性Pd/C催化剂的再生：从反应液中将催化剂过滤出，经乙醇和正己烷各洗涤4-6次、90℃干燥5～12h、研磨后得到再生的催化剂。
和现有技术相比，本发明的有益效果在于：
(1)、本发明催化材料制备方法简便、原料易得，并且疏水性强、含有酸-金属双功能位点；
(2)、本发明改性Pd/C催化活性高、易分离回收再利用；
(3)、本发明改性Pd/C对不同碳水化合物具有广泛的适用性，同时具有反应条件温和、选择性高、稳定性高、反应速率快，重复使用性好的优点。
(4)在相同条件下，本发明的制备方法制得的改性Pd/C催化碳水化合物“一锅单步”转化为2,5-二甲基呋喃的效率(产率>85％)明显优于商品化Pd/C(<50％)和其他Co、Ni、Ru、Pt等金属催化剂(0-30％)。
附图说明：
图1为改性5wt％Pd/C在水和丁醇中的分布情况(左)以及表面水滴的接触角(右)。
图2为5wt％Pd/C在水和丁醇中的分布情况(左)以及表面水滴接触角(右)。
图3为重复使用6次后(上)和新制(下)改性Pd/C的XRD谱图。
具体实施方式
实施例1
(1)改性5wt％Pd/C的制备
主要涉及如下两步过程：(A)称取0.5g 5wt％Pd/C加入到15mL二氯甲烷中，然后搅拌至均匀分散。紧接着，缓慢滴加0.2mL氯磺酸(约2min)，在室温条件下保持搅拌12h，然后依次经过滤、二氯甲烷和水反复洗涤至滤液为中性、90℃条件下真空干燥6h即可得到酸性Pd/C催化材料；(B)取用0.25g酸性Pd/C催化材料置入7.5mL环己烷中，然后向上述混合体系中逐滴加入1.5mL三甲基氯硅烷，滴加完毕后在60℃加热条件继续搅拌12h，随后依次通过正己烷洗涤5次、90℃条件下真空干燥6h、研磨，制得酸性、疏水Pd/C催化材料，即为改性5wt％Pd/C。
通过图1可见，改性5wt％Pd/C均匀的分散在正丁醇溶剂中，但与水基本不混溶(左图)；同时，较高的水滴接触角(134°)也正好验证了改性5wt％Pd/C具有良好的疏水性(右图)。另外，通过酸碱滴定法也证实该催化材料具有较高的酸量(～1.1mmol/g)。由此，可以判定改性5wt％Pd/C同时具有较理想的疏水性和酸性。
(2)直接催化果糖制备2,5-二甲基呋喃
向15mL耐压玻璃反应管中投入6wt％果糖，正丁醇1.5mL，2mol％改性5wt％Pd/C，9倍当量(相对于果糖)聚甲基氢硅氧烷，于80℃条件下加热搅拌4h或120℃条件下加热搅拌1h。反应结束后，经离心分离出固体催化剂，反应液中果糖转化率和2,5-二甲基呋喃产率分别通过HPLC(高效液相色谱)和GC(气相色谱)测定。通过配制相应标液的标准曲线，代入待测样峰面积计算得到果糖转化率为96％、2,5-二甲基呋喃产率为88％。
(3)过滤分离出的固体催化剂经乙醇和正己烷各洗涤4-6次、90℃干燥5-12h、研磨后得到再生的催化剂，使用再生的改性5wt％Pd/C直接催化果糖制备2,5-二甲基呋喃，各原料用量、反应条件同实施例1(2)，通过液相和气相色谱检测到反应混合液中果糖转化率为98％，2,5-二甲基呋喃产率为92％。相应地，改性5wt％Pd/C在使用前后几乎一致的XRD谱图(图3)也很好地验证了该催化材料稳定的结构。
对比例1
所用5wt％Pd/C为商品化试剂，购自北京伊诺凯科技有限公司。图2表明，5wt％Pd/C具有良好的亲水性(左图)，且较低的水滴接触角(28°)也反映了该材料疏水能力不强。
采用本实施例获得的商品化5wt％Pd/C催化果糖制备2,5-二甲基呋喃，各原料用量、反应条件、样品测试方法同实施例1(2)。反应结束后，分别通过液相和气相色谱测得混合液中果糖转化率为52％、2,5-二甲基呋喃产率为43％。
相应地，5wt％Co/C、5wt％Ni/C、5wt％Ru/C、5wt％Pt/C在同样反应条件下催化 果糖转化所得2,5-二甲基呋喃的产率依次为0、0、10％、20％。
实施例2
(1)改性2wt％Pd/C的制备
主要涉及如下两步过程：(A)称取0.5g 2wt％Pd/C加入到15mL二氯甲烷中，然后搅拌至均匀分散。紧接着，缓慢滴加0.1mL氯磺酸(约1min)，在室温条件下保持搅拌12h，然后依次经过滤、二氯甲烷和水反复洗涤至滤液为中性、90℃条件下真空干燥6h即可得到酸性Pd/C催化材料；(B)取用0.25g酸性Pd/C催化材料置入7.5mL环己烷中，然后向上述混合体系中逐滴加入1.5mL三甲基氯硅烷，滴加完毕后在60℃加热条件继续搅拌12h，随后依次通过正己烷洗涤5次、90℃条件下真空干燥6h、研磨，制得酸性、疏水Pd/C催化材料，即为改性2wt％Pd/C。
(2)直接催化葡萄糖制备2,5-二甲基呋喃
向15mL耐压玻璃反应管中投入4wt％葡萄糖，正己醇1.5mL，1.5mol％改性2wt％Pd/C，5倍当量(相对于葡萄糖)聚甲基氢硅氧烷，于120℃条件下加热搅拌2h。反应结束后，经离心分离出固体催化剂，反应液中葡萄糖转化率和2,5-二甲基呋喃产率分别通过HPLC(高效液相色谱)和GC(气相色谱)测定。通过配制相应标液的标准曲线，代入待测样峰面积计算得到葡萄糖转化率为87％、2,5-二甲基呋喃产率为65％。
实施例3
(1)改性0.5wt％Pd/C的制备
主要涉及如下两步过程：(A)称取0.5g 0.5wt％Pd/C加入到15mL二氯甲烷中，然后搅拌至均匀分散。紧接着，缓慢滴加0.3mL氯磺酸(约3min)，在室温条件下保持搅拌12h，然后依次经过滤、二氯甲烷和水反复洗涤至滤液为中性、90℃条件下真空干燥6h即可得到酸性Pd/C催化材料；(B)取用0.25g酸性Pd/C催化材料置入7.5mL环己烷中，然后向上述混合体系中逐滴加入1.5mL三甲基氯硅烷，滴加完毕后在60℃加热条件继续搅拌12h，随后依次通过正己烷洗涤5次、90℃条件下真空干燥6h、研磨，制得酸性、疏水Pd/C催化材料，即为改性0.5wt％Pd/C。
(2)直接催化蔗糖制备2,5-二甲基呋喃
向15mL耐压玻璃反应管中投入4wt％蔗糖，乙醇1.5mL，3mol％改性0.5wt％Pd/C，10倍当量(相对于蔗糖)聚甲基氢硅氧烷，于100℃条件下加热搅拌5h。反应结束后，经离心分离出固体催化剂，反应液中蔗糖转化率和2,5-二甲基呋喃产率分别通过HPLC(高效液相色谱)和GC(气相色谱)测定。通过配制相应标液的标准曲线，代入待测样峰面积计算得到蔗糖转 化率为95％、2,5-二甲基呋喃产率为83％。
实施例4
(1)改性15wt％Pd/C的制备
主要涉及如下两步过程：(A)称取0.5g 15wt％Pd/C加入到15mL二氯甲烷中，然后搅拌至均匀分散。紧接着，缓慢滴加0.15mL氯磺酸(约1.5min)，在室温条件下保持搅拌12h，然后依次经过滤、二氯甲烷和水反复洗涤至滤液为中性、90℃条件下真空干燥6h即可得到酸性Pd/C催化材料；(B)取用0.25g酸性Pd/C催化材料置入7.5mL环己烷中，然后向上述混合体系中逐滴加入1.5mL三甲基氯硅烷，滴加完毕后在60℃加热条件继续搅拌12h，随后依次通过正己烷洗涤5次、90℃条件下真空干燥6h、研磨，制得酸性、疏水Pd/C催化材料，即为改性15wt％Pd/C。
(2)直接催化菊糖制备2,5-二甲基呋喃
向15mL耐压玻璃反应管中投入2wt％菊糖，甲醇1.5mL，1mol％改性15wt％Pd/C，6倍当量(相对于菊糖)聚甲基氢硅氧烷，于140℃条件下加热搅拌3h。反应结束后，经离心分离出固体催化剂，反应液中菊糖转化率和2,5-二甲基呋喃产率分别通过HPLC(高效液相色谱)和GC(气相色谱)测定。通过配制相应标液的标准曲线，代入待测样峰面积计算得到菊糖转化率为99％、2,5-二甲基呋喃产率为90％。

Claims (6)

  1. 一种改性Pd/C直接催化碳水化合物制备2,5-二甲基呋喃的方法，其特征在于：包括以下步骤：
    第一步、改性Pd/C的制备，将0.5gPd/C均匀分散到15mL二氯甲烷中，在搅拌条件下缓慢滴加0.05-0.35mL氯磺酸，并在室温条件下持续搅拌12h，然后经过滤、二氯甲烷和水反复洗涤至滤液为中性、90℃条件下真空干燥6h得到酸性Pd/C催化材料；取用0.25g既得的酸性Pd/C催化材料置入7.5mL环己烷中，然后逐滴加入1.5mL三甲基氯硅烷，并在60℃加热条件搅拌12h，反应结束后依次通过正己烷洗涤5次、再在90℃条件下真空干燥6h、研磨，随即得到改性Pd/C；
    第二步：以步骤(一)所得的改性Pd/C为催化剂，另以聚甲基氢硅氧烷为氢供体，将碳水化合物溶于醇中，在80～140℃条件下反应1～5h；反应结束后经离心将催化剂与产物分离得到2,5-二甲基呋喃。
  2. 根据权利要求1所述的一种改性Pd/C直接催化碳水化合物制备2,5-二甲基呋喃的方法，其特征在于：所述的改性Pd/C为Pd金属含量介于0.5～15wt％的商品化Pd/C。
  3. 根据权利要求1所述的一种改性Pd/C直接催化碳水化合物制备2,5-二甲基呋喃的方法，其特征在于：所述的聚甲基氢硅氧烷相对于碳水化合物的用量为4～10倍当量。
  4. 根据权利要求1所述的一种改性Pd/C直接催化碳水化合物制备2,5-二甲基呋喃的方法，其特征在于：所述的碳水化合物溶于醇中的浓度为2～6wt％。
  5. 根据权利要求1所述的一种改性Pd/C直接催化碳水化合物制备2,5-二甲基呋喃的方法，其特征在于：所述的碳水化合物为己糖，包括果糖、葡萄糖、麦芽糖、蔗糖、纤维二糖、淀粉、菊糖或纤维素。
  6. 根据权利要求1所述一种改性Pd/C直接催化碳水化合物制备2,5-二甲基呋喃的方法，其特征在于：所述的醇为甲醇、乙醇、正丙醇、正丁醇或正己醇。
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