CN106810518A - 一种由葡萄糖制备5-羟甲基糠醛的方法 - Google Patents
一种由葡萄糖制备5-羟甲基糠醛的方法 Download PDFInfo
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 38
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 33
- 239000008103 glucose Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 20
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 20
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004327 boric acid Substances 0.000 claims abstract description 14
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000001110 calcium chloride Substances 0.000 claims abstract description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 4
- 235000011148 calcium chloride Nutrition 0.000 claims abstract description 4
- 235000011147 magnesium chloride Nutrition 0.000 claims abstract description 4
- 239000001103 potassium chloride Substances 0.000 claims abstract description 4
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000011592 zinc chloride Substances 0.000 claims abstract description 4
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 3
- 239000011565 manganese chloride Substances 0.000 claims abstract description 3
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 3
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 5
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 4
- 150000007522 mineralic acids Chemical class 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 4
- 229930091371 Fructose Natural products 0.000 description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 4
- 239000005715 Fructose Substances 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 235000007575 Calluna vulgaris Nutrition 0.000 description 1
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 1
- 108091022917 Gluconate dehydratase Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002243 furanoses Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003214 pyranose derivatives Chemical group 0.000 description 1
- -1 slaine Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
-
- 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
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Furan Compounds (AREA)
Abstract
本发明涉及一种由葡萄糖制备5-羟甲基糠醛的方法。具体步骤为:将初始原料葡萄糖、有机溶剂、复合催化剂和水混合均匀;复合催化剂为组分A硼酸和组分B氯化钾、氯化钙、氯化镁、氯化钠、氯化铝、氯化钴、氧氯化锆、硫酸钠、氯化铁、氯化锌、氯化镍、氯化锰等无机盐中的一种或者两者以上复合而成;将混合液置于反应器中,常压下加热反应制备5-羟甲基糠醛。该方法无需添加其他固体催化剂或无机强酸,反应条件温和,操作简单,副产物少,成本低,催化剂可循环利用,具备大规模工业化应用的能力。
Description
技术领域
本发明涉及5-羟甲基糠醛,尤其是涉及一种由葡萄糖制备5-羟甲基糠醛的方法。
背景技术
随着石油、煤炭、天然气等化工资源的日益减少,未来由此引发的资源短缺和可持续发展等问题开始成为亟待解决的重大问题。生物质是地球上最为广泛的物质,碳水化合物又是组成生物质极其重要的部分,以碳水化合物为原料寻找高效的方法制备化学中间体如5-羟甲基糠醛就是生物质开发利用这一领域中极具挑战性的工作。5-羟甲基糠醛的分子中含有一个羟甲基和一个醛基,化学反应活泼,经羟醛缩合、加氢脱氧等工艺,可以制备出各种具有高附加值的产品和新型高分子材料,如粘结剂、医药、树脂类塑料、液体燃料等。
早期的研究主要集中在酸催化果糖转化为5-羟甲基糠醛的研究,然而该方法存在设备腐蚀严重,原料来源狭窄,催化效率普遍较低,副产物较多,污染严重的缺点,不符合绿色环境的发展要求。相对于果糖,葡萄糖价格便宜,来源广泛,生物质开发利用转化为5-羟甲基糠醛的关键步骤在于葡萄糖转化为5-羟甲基糠醛的过程,故由葡萄糖制备5-羟甲基糠醛更具有实际意义。但由于葡萄糖是吡喃糖,通常经由异构化为果糖(呋喃糖)、果糖在脱除三分子水两个步骤才能转化为5-羟甲基糠醛,葡萄糖的转化率和产物选择性都相对较低。为了解决这一问题,研究人员相继开发了各种各样的催化体系,质子酸、固体酸、金属盐等各种催化剂,水、有机溶剂、离子液体等各种溶剂都相继被用于葡萄糖的催化反应。其中,金属氯化物/离子液体体系的效果是最令人满意的。赵海波课题组发现CrCl2在离子液体中能有效的将葡萄糖转化为5-羟甲基糠醛 [Haibo
Zhao, Johnathan E.Holladay,
Heather Brown, Z.Conrad Zhang. Science 2007, 316,
1597],产率达到前所未有的70%,但是,离子液体价格昂贵,易受水分子的影响,循环利用差,不利于工业化生产。Thomas S. Hansen课题组报道了一种以甲基异丁基酮和水为反应溶剂,硼酸为催化剂催化葡萄糖为5-羟甲基糠醛的方法,在150℃温度下反应45min,5-羟甲基糠醛的产率仅为14%。该方法虽然避免了使用强酸催化剂腐蚀设备、酸液排放污染环境的缺陷,但是5-羟甲基糠醛的产率很低[Thomas S. Hansen, Jerrik Mielby, Anders Riisager. Green chemistry 2011, 13, 109]。
发明内容
本发明旨在提供一种无毒无害且绿色环保的催化剂,在温和的条件下催化葡萄糖制备5-羟甲基糠醛。以克服现有技术中操作复杂、成本高、污染大、普适性低等缺点。
本发明的具体步骤如下:
(1)将初始原料葡萄糖、有机溶剂、复合催化剂和水混合均匀,得到混合液;
所用复合催化剂为组分A硼酸和组分B氯化钾、氯化钙、氯化镁、氯化钠、氯化铝、氯化钴、氧氯化锆、硫酸钠、氯化铁、氯化锌、氯化镍、氯化锰等无机盐中的一种或者两种以上复合而成;
(2)将步骤(1)所得混合液置于反应器中,常压下加热反应制备5-羟甲基糠醛。
步骤(1)中,所述的葡萄糖加入量按质量百分比可为水的0.5%-20%。
所述的组分A硼酸加入量按质量比可为水的1%-24%。
所述的组分B无机盐的加入量按质量比可为水的0.5%-35%。
所述的有机溶剂为四氢呋喃、二甲基呋喃、正丁醇、异丁醇、甲基异丁基酮中的一种或者两种以上复合而成。
所述的有机溶剂与水的比例为2:1-6:1。
步骤(2)中,所述的加热反应的温度可为100℃-200℃,加热反应的时间为20min-100min。
有益效果:
与传统的无机酸催化葡萄糖脱水制备5-羟甲基糠醛相比,该复合催化剂,降低了对设备的腐蚀,可操作性高,绿色环保,5-羟甲基糠醛的产率可达60%。相比于离子液体为反应溶剂,本发明采用了廉价的有机溶剂和水为反应溶剂,具有良好的经济实用性,为5-羟甲基糠醛及其下游产品的开发提供了一种新颖的思路。
具体实施方式
下面结合实例对本发明做进一步的描述,需要说明的是,实施例并不构成对本发明要求保护范围的限定。
实施例1
将0.1g葡萄糖,0.2g硼酸,0.1g氯化铝,6.1g氯化钠,20mL水,20mL二甲基亚砜,40mL异丁醇置于反应釜中混合均匀,在油浴锅中加热到100℃,反应时间20min,反应完成后待反应混合物冷却至室温,利用高效液相色谱测得5-羟甲基糠醛产率为10.2%。
实施例2
将0.1g葡萄糖,0.4g硼酸,0.1g氯化铝,6.2g氯化钾,20mL水,20mL二甲基亚砜,40mL正丁醇置于反应釜中混合均匀,在油浴锅中加热到140℃,反应时间30min,反应完成后待反应混合物冷却至室温,利用高效液相色谱测得5-羟甲基糠醛产率为20.8%。
实施例3
将0.1g葡萄糖,0.6g硼酸,0.1g氯化铝,6.3g氯化钠,20mL水,20mL二甲基亚砜,40mL四氢呋喃置于反应釜中混合均匀,在油浴锅中加热到160℃,反应时间40min,反应完成后待反应混合物冷却至室温,利用高效液相色谱测得5-羟甲基糠醛产率为32.2%。
实施例4
将0.25g葡萄糖,0.8g硼酸,0.1g氯化铝,6.4g氯化钠,20mL水,60mL正丁醇置于反应釜中混合均匀,在油浴锅中加热到170℃,反应时间40min,反应完成后待反应混合物冷却至室温,利用高效液相色谱测得5-羟甲基糠醛产率为34.8%。
实施例5
将0.25g葡萄糖,1.4g硼酸,0.1g氧氯化锆,6.5g氯化钠,20mL水,20mL二甲基亚砜,70mL四氢呋喃置于反应釜中混合均匀,在油浴锅中加热到170℃,反应时间40min,反应完成后待反应混合物冷却至室温,利用高效液相色谱测得5-羟甲基糠醛产率为28.0%。
实施例6
将0.25g葡萄糖,1.6g硼酸,0.1g氯化铝,0.05g氯化锌,6.8g氯化钠,20mL水,70mL四氢呋喃置于反应釜中混合均匀,在油浴锅中加热到170℃,反应时间50min,反应完成后待反应混合物冷却至室温,利用高效液相色谱测得5-羟甲基糠醛产率为40.1%。
实施例7
将1g葡萄糖,2g硼酸,0.3g氯化铝,0.03g氯化钙,6.4g氯化钠,20mL水,80mL四氢呋喃置于反应釜中混合均匀,在油浴锅中加热到180℃,反应时间60min,反应完成后待反应混合物冷却至室温,利用高效液相色谱测得5-羟甲基糠醛产率为20.4%。
实施例8
将1g葡萄糖,2.4g硼酸,0.4g氯化铝,0.02g氯化镁,6.5g氯化钠,20mL水,80mL四氢呋喃置于反应釜中混合均匀,在油浴锅中加热到200℃,反应时间100min,反应完成后待反应混合物冷却至室温,利用高效液相色谱测得5-羟甲基糠醛产率为12.8%。
Claims (7)
1.一种由葡萄糖制备5-羟甲基糠醛的方法,其特征在于具体步骤如下:
(1)将初始原料葡萄糖、有机溶剂、复合催化剂和水混合均匀,得到混合液;
所用复合催化剂为组分A硼酸和组分B氯化钾、氯化钙、氯化镁、氯化钠、氯化铝、氯化钴、氧氯化锆、硫酸钠、氯化铁、氯化锌、氯化镍、氯化锰中的一种或者两种以上复合而成;
(2)将步骤(1)所得混合液置于反应器中,常压下加热反应制备5-羟甲基糠醛。
2.如权利要求1所述一种由葡萄糖制备5-羟甲基糠醛的方法,其特征在于,步骤(1)中,所述的葡萄糖的加入量按质量百分比为水的0.5%-20%。
3.如权利要求1所述一种由葡萄糖制备5-羟甲基糠醛的方法,其特征在于,步骤(1)中,所述的组分A硼酸的加入量按质量百分比为水的1%-24%。
4.如权利要求1所述一种由葡萄糖制备5-羟甲基糠醛的方法,其特征在于,步骤(1)中,所述的组分B无机盐的加入量按质量百分比为水的0.5%-35%。
5.如权利要求1所述一种由葡萄糖制备5-羟甲基糠醛的方法,其特征在于,步骤(1)中,
所述的有机溶剂为四氢呋喃、二甲基呋喃、正丁醇、异丁醇、甲基异丁基酮中的一种或者两种以上复合而成。
6.如权利要求1所述一种由葡萄糖制备5-羟甲基糠醛的方法,其特征在于,步骤(1)中,
所述的有机溶剂与水的比例为2:1-6:1。
7.如权利要求1所述一种由葡萄糖制备5-羟甲基糠醛的方法,其特征在于,步骤(2)中,所述的加热反应的温度为100-200℃,加热反应的时间为20-100min。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109999907A (zh) * | 2019-04-22 | 2019-07-12 | 淮阴师范学院 | 一种磺酸功能化无机有机杂化聚合物催化剂的制备方法及其应用 |
CN111039903A (zh) * | 2018-10-12 | 2020-04-21 | 中国科学院大连化学物理研究所 | 一种高效制备5-羟甲基糠醛的催化反应方法 |
CN113262775A (zh) * | 2021-05-27 | 2021-08-17 | 南京先进生物材料与过程装备研究院有限公司 | 一种金属掺杂二氧化钛催化剂及其在葡萄糖环合反应中的应用 |
CN117736166A (zh) * | 2023-12-16 | 2024-03-22 | 合肥利夫生物科技有限公司 | 一种5-羟甲基糠醛的合成方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080033188A1 (en) * | 2006-06-06 | 2008-02-07 | Dumesic James A | Catalytic process for producing furan derivatives in a biphasic reactor |
CN102367242A (zh) * | 2011-11-08 | 2012-03-07 | 河北师范大学 | 一种以碳水化合物制备5-羟甲基糠醛的方法 |
CN102399202A (zh) * | 2011-12-02 | 2012-04-04 | 复旦大学 | 一种利用生物质糖制备5-羟甲基糠醛的方法 |
CN102558112A (zh) * | 2012-02-27 | 2012-07-11 | 中国科学技术大学 | 纤维素转化为5-羟甲基糠醛的方法 |
CN102933567A (zh) * | 2010-04-07 | 2013-02-13 | 诺维信公司 | 产生羟甲基糠醛的方法 |
CN103951639A (zh) * | 2014-03-27 | 2014-07-30 | 中国科学院宁波材料技术与工程研究所 | 一种温和快速制备5-羟甲基糠醛的方法 |
CN103974943A (zh) * | 2011-10-12 | 2014-08-06 | 诺维信公司 | 使用单相混合的水-有机溶剂系统从果糖生产5-羟甲基糠醛 |
-
2015
- 2015-12-02 CN CN201510865405.6A patent/CN106810518A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080033188A1 (en) * | 2006-06-06 | 2008-02-07 | Dumesic James A | Catalytic process for producing furan derivatives in a biphasic reactor |
CN102933567A (zh) * | 2010-04-07 | 2013-02-13 | 诺维信公司 | 产生羟甲基糠醛的方法 |
CN103974943A (zh) * | 2011-10-12 | 2014-08-06 | 诺维信公司 | 使用单相混合的水-有机溶剂系统从果糖生产5-羟甲基糠醛 |
CN102367242A (zh) * | 2011-11-08 | 2012-03-07 | 河北师范大学 | 一种以碳水化合物制备5-羟甲基糠醛的方法 |
CN102399202A (zh) * | 2011-12-02 | 2012-04-04 | 复旦大学 | 一种利用生物质糖制备5-羟甲基糠醛的方法 |
CN102558112A (zh) * | 2012-02-27 | 2012-07-11 | 中国科学技术大学 | 纤维素转化为5-羟甲基糠醛的方法 |
CN103951639A (zh) * | 2014-03-27 | 2014-07-30 | 中国科学院宁波材料技术与工程研究所 | 一种温和快速制备5-羟甲基糠醛的方法 |
Non-Patent Citations (2)
Title |
---|
BASUDEB SAHA, ET AL.: "Zr(O)Cl2 catalyst for selective conversion of biorenewable carbohydrates and biopolymers to biofuel precursor 5-hydroxymethylfurfural in aqueous medium", 《FUEL》 * |
THOMAS S. HANSEN,ET AL.: "Synergy of boric acid and added salts in the catalytic dehydration of hexoses to 5-hydroxymethylfurfural in water", 《GREEN CHEM.》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111039903A (zh) * | 2018-10-12 | 2020-04-21 | 中国科学院大连化学物理研究所 | 一种高效制备5-羟甲基糠醛的催化反应方法 |
CN109999907A (zh) * | 2019-04-22 | 2019-07-12 | 淮阴师范学院 | 一种磺酸功能化无机有机杂化聚合物催化剂的制备方法及其应用 |
CN109999907B (zh) * | 2019-04-22 | 2020-09-15 | 淮阴师范学院 | 一种磺酸功能化无机有机杂化聚合物催化剂的制备方法及其应用 |
CN113262775A (zh) * | 2021-05-27 | 2021-08-17 | 南京先进生物材料与过程装备研究院有限公司 | 一种金属掺杂二氧化钛催化剂及其在葡萄糖环合反应中的应用 |
CN117736166A (zh) * | 2023-12-16 | 2024-03-22 | 合肥利夫生物科技有限公司 | 一种5-羟甲基糠醛的合成方法 |
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