CN104447638B - 一种双金属氯化物降解半乳糖制备5‑羟甲基糠醛的方法 - Google Patents

一种双金属氯化物降解半乳糖制备5‑羟甲基糠醛的方法 Download PDF

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CN104447638B
CN104447638B CN201410733592.8A CN201410733592A CN104447638B CN 104447638 B CN104447638 B CN 104447638B CN 201410733592 A CN201410733592 A CN 201410733592A CN 104447638 B CN104447638 B CN 104447638B
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galactolipin
crcl
bimetallic
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CN104447638A (zh
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王海军
王宁宁
宋展欣
杨艳
刘文涛
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Jiangnan University
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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D307/00Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34Heterocyclic 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
    • C07D307/38Heterocyclic 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
    • C07D307/40Radicals substituted by oxygen atoms
    • C07D307/46Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom

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Abstract

本发明公开了一种双金属氯化物降解半乳糖制备5‑羟甲基糠醛的方法,属于利用生物质合成可再生能源与化学品制备领域,该方法采用双金属氯化物作为催化剂,将半乳糖在二元溶剂体系中降解为5‑羟甲基糠醛。该方法以半乳糖为原料,在温和条件下,直接进行催化转化制备得到5‑羟甲基糠醛(HMF),具有快速与简便的优点,其过程简单、反应温和、高效,为半乳糖转化为大宗化学品提供了一条很有价值的新途径。其催化活性高于价格重昂贵的单金属催化剂,是催化降解糖类等碳水化合物的一种优良体系。

Description

一种双金属氯化物降解半乳糖制备5-羟甲基糠醛的方法
技术领域
本发明属于生物质资源利用领域,具体涉及一种双金属氯化物降解半乳糖制备5-羟甲基糠醛的方法。
背景技术
糖类等碳水化合物资源作为世界上储量丰富的生物质资源,具有储量丰富和零CO2排放等优点,是唯一能够直接转化为液态燃料的资源,具有替代石油基础产业的潜力。目前研究的重点主要集中在己糖(葡萄糖、果糖、半乳糖等)的催化转化。这些糖类具有获取途径广泛、储量丰富、易于得到等特点。通过催化转化可以获得5-羟甲基糠醛(HMF),被认为是基于生物质原料的一种重要的平台分子,被认为是贯穿石油基础产品和生物质的一条纽带。使用金属氯化物在离子液体中催化转化葡萄糖、纤维素都取得了较好效果。但对于另一种己糖半乳糖的研究较少,并且催化效果不佳。半乳糖是葡萄糖的C-4位的差向异构体,对于其催化转化反应,Raines等人发现,以CrCl2为催化剂,在DMSO中催化降解半乳糖为HMF,产率达到22%(Binder JB,Cefali AV,Blank JJ,Raines RT(2010)Energy Environ Sci3:765-771)。然而,这样的催化并不令人满意,并且催化剂CrCl2不稳定,很难在空气中操作,价格昂贵。因此,我们提出在二元溶剂体系[AMIM]Cl/DMF中,使用双金属氯化物作为催化剂,催化转化半乳糖为高附加值的HMF。
发明内容
本发明提供了一种双金属氯化物降解半乳糖制备制备5-羟甲基糠醛的方法,采用廉价稳定的双金属氯化物催化转化半乳糖,促进半乳糖的降解,同时获得较高产率的5-羟甲基糠醛。本发明采取的技术方案为:以1:3配比的离子液体1-烯丙基-3-甲基咪唑氯([AMIM]Cl)和有机溶剂DMF为溶剂体系,加入适量的半乳糖,分别以双金属氯化物SnCl4/CuCl2,SnCl4/MnCl2,SnCl4/CrCl3,SnCl4/FeCl3,SnCl4/ZrOCl2,SnCl4/AlCl3,CrCl3/ZrOCl2,CrCl3/AlCl3,CrCl3/CuCl2,CrCl3/MnCl2,CrCl3/SnCl4和CrCl3/FeCl3为催化剂,在110℃温度下反应3h,用冷水猝灭反应得到半乳糖降解后的混合液,高效液相色谱法测水解液中HMF的含量。然后,改变双金属催化剂的配比范围1/7~7/1,重复进行上述实验,检测降解反应液中的HMF产率。双金属氯化物CrCl3/MnCl2的催化效果最佳;催化剂CrCl3/MnCl2的最佳配比为3/1。
所述的方法是在常压和氮气保护下反应。
所述的方法采用有机溶剂DMF作为共溶剂,降低了离子液体的粘度,提高了产物HMF的稳定性和选择性。
所述的方法以[AMIM]Cl/DMF为溶剂,双金属CrCl3/MnCl2为催化剂,催化效率最好。
本发明具有如下优点:
1.所采用的双金属CrCl3/MnCl2为催化剂简单稳定,催化活性较高,选择性好,半乳糖的转化率和HMF的产率较高。
2.共溶剂的使用有利于离子液体粘度的调整,并且提高了HMF的稳定性。
具体实施方式
实施例1~12
以1:3配比的离子液体1-烯丙基-3-甲基咪唑氯([AMIM]Cl)和有机溶剂DMF为溶剂体系,加入1mmol的半乳糖,分别以双金属氯化物SnCl4/CuCl2,SnCl4/MnCl2,SnCl4/CrCl3,SnCl4/FeCl3,SnCl4/ZrOCl2,SnCl4/AlCl3,CrCl3/ZrOCl2,CrCl3/AlCl3,CrCl3/CuCl2,CrCl3/MnCl2,CrCl3/SnCl4和CrCl3/FeCl3为催化剂,双金属的配比为3/1,催化剂用量为底物半乳糖的8mol%。在110℃温度下反应3h,用冷水猝灭反应得到半乳糖降解后的混合液,高效液相色谱法测水解液中HMF的含量。实验结果见表1。
表1 不同催化剂对半乳糖降解的影响
项目 催化剂(mmol) HMF产率(%)
实施实例1 12.3
实施实例2 14.4
实施实例3 16.4
实施实例4 13.3
实施实例5 12.0
实施实例6 12.4
实施实例7 17.6
实施实例8 19.2
实施实例9 15.3
实施实例10 35.0
实施实例11 22.8
实施实例12 14.6
实施例13~18
参照实施例1的步骤,不同的是:以CrCl3/MnCl2为催化剂,改变催化剂的不同配比1/7~7/1,重复进行上述实验,检测降解反应液中的HMF含量。结果见表2。
表2 不同催化剂配比对半乳糖降解的影响
项目 催化剂配比 HMF产率(%)
实施实例13 1/7 5.5
实施实例14 1/3 7.3
实施实例15 3/5 19.3
实施实例16 1/1 20.1
实施实例17 5/3 21.7
实施实例18 7/1 16.8

Claims (2)

1.一种双金属氯化物降解半乳糖制备5-羟甲基糠醛的方法,以1:3配比的离子液体1-烯丙基-3-甲基咪唑氯和有机溶剂DMF为混合溶剂体系,加入适量的半乳糖,分别以双金属氯化物SnCl4+CuCl2,SnCl4+MnCl2,SnCl4+CrCl3,SnCl4+FeCl3,SnCl4+ZrOCl2,SnCl4+AlCl3,CrCl3+ZrOCl2,CrCl3+AlCl3,CrCl3+CuCl2,CrCl3+MnCl2,CrCl3+SnCl4和CrCl3+FeCl3为双金属协同催化体系的催化剂,在110℃温度下反应3h,用冷水猝灭反应得到半乳糖降解后的混合液,高效液相色谱法测水解液中HMF的含量,所述双金属的配比为3/1,检测降解反应液中的HMF产率。
2.根据权利要求1所述的双金属氯化物降解半乳糖制备5-羟甲基糠醛的方法,其特征是催化剂为由氯化物CrCl3+MnCl2构成的双金属协同催化体系。
CN201410733592.8A 2014-12-04 2014-12-04 一种双金属氯化物降解半乳糖制备5‑羟甲基糠醛的方法 Expired - Fee Related CN104447638B (zh)

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