CN114805256B - 两性离子内盐催化果糖基碳水化合物脱水制备5-羟甲基糠醛的方法 - Google Patents
两性离子内盐催化果糖基碳水化合物脱水制备5-羟甲基糠醛的方法 Download PDFInfo
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- CN114805256B CN114805256B CN202210533915.3A CN202210533915A CN114805256B CN 114805256 B CN114805256 B CN 114805256B CN 202210533915 A CN202210533915 A CN 202210533915A CN 114805256 B CN114805256 B CN 114805256B
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- 150000003839 salts Chemical class 0.000 title claims abstract description 84
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 45
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 150000001720 carbohydrates Chemical class 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 17
- 230000018044 dehydration Effects 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229930091371 Fructose Natural products 0.000 claims abstract description 29
- 239000005715 Fructose Substances 0.000 claims abstract description 29
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 19
- DZBSVQJETVZTIO-UHFFFAOYSA-N 1-pyridin-2-ylbutane-1-sulfonic acid Chemical group S(=O)(=O)(O)C(CCC)C1=NC=CC=C1 DZBSVQJETVZTIO-UHFFFAOYSA-N 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 235000014633 carbohydrates Nutrition 0.000 abstract description 22
- -1 alkyl sulfonate anion Chemical class 0.000 abstract description 9
- BJHIKXHVCXFQLS-UYFOZJQFSA-N fructose group Chemical group OCC(=O)[C@@H](O)[C@H](O)[C@H](O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 abstract description 3
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 3
- 125000002757 morpholinyl group Chemical group 0.000 abstract description 3
- 125000004076 pyridyl group Chemical group 0.000 abstract description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 37
- 239000002904 solvent Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 10
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 229920001202 Inulin Polymers 0.000 description 5
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 5
- 229940029339 inulin Drugs 0.000 description 5
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- AOKJITQXBAPAJO-UHFFFAOYSA-N S(=O)(=O)(O)C(CCC)C1=NC=CN1C Chemical compound S(=O)(=O)(O)C(CCC)C1=NC=CN1C AOKJITQXBAPAJO-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- BZBRTXMUKWYFID-UHFFFAOYSA-N 4-(triethylazaniumyl)butane-1-sulfonate Chemical compound CC[N+](CC)(CC)CCCCS([O-])(=O)=O BZBRTXMUKWYFID-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
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- 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
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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
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
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- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
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Abstract
本发明提供了一种两性离子内盐催化果糖基碳水化合物脱水制备5‑羟甲基糠醛的方法,以两性离子内盐为催化剂,将果糖基碳水化合物在有机溶剂中进行选择性催化脱水反应转化为5‑羟甲基糠醛。本发明是以含有烷基磺酸根负离子(—SO3ˉ)的咪唑基、吡啶基、吡咯烷酮基、吗啉基、季铵盐基两性离子内盐为催化剂,在有机溶剂中将含有果糖结构单元的碳水化合物选择性催化脱水制备5‑羟甲基糠醛的方法;通过将内盐与有机溶剂进行搭配组合,构建“内盐‑有机溶剂”催化体系,可以实现碳水化合物中果糖结构的定向转化,生成5‑羟甲基糠醛的选择性可达到95%以上。
Description
技术领域
本发明属于生物质基杂环化合物绿色催化合成技术领域,具体涉及两性离子内盐催化果糖基碳水化合物脱水制备5-羟甲基糠醛的方法。
背景技术
5-羟甲基糠醛(HMF)是重要的含氧杂环化合物(式1),可作为制备含有呋喃环结构药物中间体或其他高附加值化学品的基础原料。此外,5-羟甲基糠醛同样可经过加氢还原、碳链增长反应制备高品质液体燃油,在一定程度上降低我国对石化基液体燃料的需求。5-羟甲基糠醛的生产主要以可再生的碳水化合物为原料,经过酸催化剂催化脱水等步骤实现。
目前,所开发的催化剂主要为均相催化剂如HCl、H2SO4、CrCl3、SnCl4、GeCl4等,以及固体多相催化剂如固体碳基磺酸、高分子磺酸树脂等。然而,传统均相催化剂除了具有酸腐蚀性强、环境毒性大等缺点外,同样存在回收使用效率低,产物分离纯化困难等不足;而固体多相催化剂体系则存在催化剂制备过程复杂,不易大规模生产,反应条件苛刻等缺陷。与此同时,5-羟甲基糠醛在上述酸催化剂体系中稳定性较差,副反应较多,进一步限制了上述酸催化剂在5-羟甲基糠醛绿色催化生产方面的应用。因此,在双碳背景下,开发催化效率高、酸腐蚀性低、环境友好、反应条件温和、易回收使用的新型催化剂体系成为5-羟甲基糠醛绿色催化合成的必然选择。
发明内容
针对现有技术中存在的上述不足,本发明的目的在于提供一种两性离子内盐催化果糖基碳水化合物脱水制备5-羟甲基糠醛的方法,本发以中性的含有烷基磺酸根负离子(—SO3ˉ)的两性离子内盐为催化剂,并与质子型和非质子型有机溶剂进行组合,构建果糖基碳水化合物催化脱水制备5-羟甲基糠醛的新型反应体系。
为实现上述目的,本发明提供如下技术方案:一种两性离子内盐催化果糖基碳水化合物脱水制备5-羟甲基糠醛的方法,以两性离子内盐为催化剂,将果糖基碳水化合物在有机溶剂中进行选择性催化脱水反应转化为5-羟甲基糠醛。
进一步,所述两性离子内盐催化果糖基碳水化合物脱水制备5-羟甲基糠醛的方法,具体包括如下步骤:
(1)将一定量的两性离子内盐加入到有机溶剂中,形成催化脱水反应体系;
(2)将一定量的果糖基碳水化合物加入到所述反应体系中,搅拌,在温度为100~200℃条件下进行催化脱水反应;
所述两性离子内盐为含有烷基磺酸根负离子(—SO3ˉ)的咪唑基、吡啶基、吡咯烷酮基、吗啉基、季铵盐基中的一种;
所述有机溶剂为质子型有机溶剂或非质子型有机溶剂中的一种。
进一步,所述两性离子内盐相对于原料中果糖基结构单元的摩尔分数为1%~30%。
进一步,所述果糖基碳水化合物与所述有机溶剂的质量体积比为(1~60)g:100mL。
进一步,所述果糖基碳水化合物为含有果糖基本结构单元的糖类化合物。
进一步,所述糖类化合物为果糖、蔗糖或菊粉。
进一步,所述质子型有机溶剂为脂肪单醇,所述脂肪单醇的碳原子数为3或4。
进一步,所述脂肪单醇为正丙醇、异丙醇、正丁醇、2-丁醇或异丁醇。
进一步,所述非质子型有机溶剂为丙酮、二甲基亚砜或四氢呋喃。
进一步,所述脱水反应的反应时间为0.5~6h。
与现有技术相比,本发明具有如下有益效果:
1、本发明是以含有烷基磺酸根负离子(—SO3ˉ)的咪唑基、吡啶基、吡咯烷酮基、吗啉基、季铵盐基两性离子内盐为催化剂,在有机溶剂中将含有果糖结构单元的碳水化合物选择性催化脱水制备5-羟甲基糠醛的方法;通过将内盐与有机溶剂进行搭配组合,构建“内盐-有机溶剂”催化体系,可以实现碳水化合物中果糖结构的定向转化,生成5-羟甲基糠醛的选择性可达到95%以上。
2、与现有制备方法相比,本发明提供的制备方法具有催化剂无酸腐蚀性、原料来源广、产物选择性高、反应条件温和、绿色环保等优点,在5-羟甲基糠醛工业生产领域具有较大的应用前景。
3、本发明两性离子内盐催化的反应体系主要是通过内盐中阴阳离子的协同作用来实现的,首先是阴阳离子与原料中合适位置的羟基形成氢键,实现对原料进行活化,促进原料分子发生逐步脱水的反应,最终形成目前产物。
附图说明
图1为本发明两性离子内盐催化反应体系的机理推测图;
图2为实施例2中两性离子内盐催化剂的重复使用结果图;
图3为反应回收两性离子内盐催化剂的核磁共振氢谱图;
图4为实施例1获得的HMF液相色谱图;
图5为液相色谱标准曲线法所得果糖浓度与色谱峰面积的关系图;
图6为液相色谱标准曲线法所得HMF浓度与色谱峰面积的关系图。
具体实施方式
下面结合具体实施例,对本发明方法进行详细说明。本发明中5-羟甲基糠醛可以简写为HMF。
一、一种两性离子内盐催化果糖基碳水化合物脱水制备5-羟甲基糠醛的方法
实施例1
一种两性离子内盐催化果糖基碳水化合物脱水制备5-羟甲基糠醛的方法,步骤如下:
1)本实施例所使用的内盐催化剂为1-磺丁基-3-甲基咪唑内盐(MimBS),通过N-甲基咪唑与1,4-丁烷磺内酯反应制备。具体方法如下:分别将0.1mol的N-甲基咪唑(8.21g),0.1mol的1,4-丁基磺酸内酯(13.64g)和50mL的甲苯加入到100mL的圆底烧瓶中,磁力搅拌,在60℃下反应24h得到白色固体粉末。通过旋转蒸发仪回收甲苯后,即可得到两性离子内盐催化剂MimBS。
2)向10mL的水热反应釜加入1.8g果糖(10mmol),内盐催化剂MimBS15mol%,异丙醇10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
实施例2
一种两性离子内盐催化果糖基碳水化合物脱水制备5-羟甲基糠醛的方法,步骤如下:
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),通过吡啶与1,4-丁烷磺内酯反应制备,制备方法同MimBS。
2)向10mL的水热反应釜加入1.8g果糖(10mmol),内盐催化剂PyBS 15mol%,异丙醇10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
实施例3
1)本实施例所使用的内盐催化剂为1-磺丁基-1-甲基吡咯烷酮内盐(NmpBS),通过N-甲基吡咯烷酮与1,4-丁烷磺内酯反应制备,制备方法同MimBS。
2)向10mL的水热反应釜加入1.8g果糖(10mmol),内盐催化剂NmpBS15mol%,异丙醇10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
实施例4
1)本实施例所使用的内盐催化剂为1-磺丁基-1-甲基吗啉内盐(NmmBS),通过N-甲基吗啉与1,4-丁烷磺内酯反应制备,制备方法同MimBS。
2)向10mL的水热反应釜加入1.8g果糖(10mmol),内盐催化剂NmmBS15mol%,异丙醇10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
实施例5
1)本实施例所使用的内盐催化剂为磺丁基三乙基铵内盐(NteBS),通过三乙胺与1,4-丁烷磺内酯反应制备,制备方法同MimBS。
2)向10mL的水热反应釜加入1.8g果糖(10mmol),内盐催化剂NteBS15mol%,异丙醇10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
实施例6
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),溶剂为二甲基亚砜(DMSO);
2)向10mL的水热反应釜加入1.8g果糖(10mmol),内盐催化剂PyBS 15mol%,二甲基亚砜10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
实施例7
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),溶剂为异丁醇;
2)向10mL的水热反应釜加入1.8g果糖(10mmol),内盐催化剂PyBS 15mol%,异丁醇10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
实施例8
1)本实施例所使用的内盐催化剂为1-磺丁基-3-甲基咪唑内盐(MimBS),溶剂为四氢呋喃(THF);
2)向10mL的水热反应釜加入1.8g果糖(10mmol),内盐催化剂MimBS15mol%,四氢呋喃10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
实施例9
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),溶剂为正丁醇;
2)向10mL的水热反应釜加入1.8g果糖(10mmol),内盐催化剂PyBS 15mol%,正丁醇10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
实施例10
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),溶剂为异丙醇;
2)向10mL的水热反应釜加入1.71g蔗糖(10mmol糖单元),内盐催化剂PyBS15mol%,异丙醇10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
实施例11
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),溶剂为二甲基亚砜(DMSO);
2)向10mL的水热反应釜加入1.8g果糖(10mmol),PyBS 1mol%,二甲基亚砜10mL,封闭反应釜,磁力搅拌,在200℃的油浴锅中反应6.0h。
实施例12
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),溶剂为二甲基亚砜(DMSO);
2)向10mL的水热反应釜加入1.8g果糖(10mmol),PyBS 30mol%,二甲基亚砜10mL,封闭反应釜,磁力搅拌,在100℃的油浴锅中反应0.5h。
实施例13
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),溶剂为异丙醇;
2)向10mL的水热反应釜加入0.1g果糖(0.56mmol),PyBS 15mol%,异丙醇10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应2.0h。
实施例14
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),溶剂为异丙醇;
2)向10mL的水热反应釜加入6.0g果糖(33.3mmol),PyBS 25mol%,异丙醇10mL,封闭反应釜,磁力搅拌,在150℃的油浴锅中反应3.0h。
实施例15
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),溶剂为异丙醇;
2)向10mL的水热反应釜加入1.62g菊粉,PyBS 15mol%,异丙醇10mL,封闭反应釜,磁力搅拌,在140℃的油浴锅中反应2.0h。
实施例16
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),溶剂为正丙醇;
2)向10mL的水热反应釜加入1.8g果糖(10mmol),内盐催化剂PyBS 15mol%,正丙醇10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
实施例17
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),溶剂为2-丁醇;
2)向10mL的水热反应釜加入1.8g果糖(10mmol),内盐催化剂PyBS 15mol%,2-丁醇10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
实施例18
1)本实施例所使用的内盐催化剂为1-磺丁基吡啶内盐(PyBS),溶剂为丙酮;
2)向10mL的水热反应釜加入1.8g果糖(10mmol),内盐催化剂PyBS 15mol%,丙酮10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h。
二、样品分析
取1mL实施例1-19获得的反应液,加入50%的乙醇溶液定容至10mL。利用安捷伦Agilent 1200高效液相色谱仪进行分析,并通过标准曲线法进行定量。果糖分析条件为:HPX-87H色谱柱(300×7.8mm,5μm)5mM H2SO4溶液为流动相,流速为0.6mL/min,柱温65℃,示差检测器(RID);HMF的分析条件为:C18反相色谱柱(250×4.6mm,5μm)1:4(v/v)CH3OH/H2O为流动相,流速为0.6mL/min,柱温30℃,紫外检测器(UV,检测波长284nm)。
标准曲线:利用不同浓度的果糖、HMF等标样进行HPLC分析,以对应峰面积为纵坐标,浓度为横坐标,建立相应的标准曲线(如图2和图3)。
根据标准曲线,通过定容后反应液对应峰面积的大小进行计算,获得原料转化率(Conv.,mol%)以HMF产率(YHMF,mol%)和选择性(SHMF,mol%)。
相应的计算公式如1-3。
表1为实施例1-18果糖的转化率以及HMF的产率、选择性
其中:实施例15由于菊粉是果糖的聚合物,反应过程中原料中的果糖结构单元逐渐转化为HMF,因此,算不出菊粉的转化率,只能根据生成的HMF和菊粉中果糖结构单元数计算HMF产率。
从表1可知,所构建的内盐催化剂对果糖基碳水化合物脱水反应制备HMF具有较好的催化活性,以PyBS为催化剂,DMSO为溶剂时(实施例6),几乎可实现原料的定向转化,HMF选择性达到95.6%。
重复实验:在实施例2反应后,使用旋转蒸发仪回收异丙醇溶剂得到粘稠状深楬色混合物(包含内盐催化剂,HMF和未反应的原料),然而分别利用10mL乙酸乙酯萃取3次,分离出HMF产物。最后剩余的深楬色混合物(包含内盐催化剂和未反应的原料)则用于重复使用研究,反应条件同实施例2。
图2为本发明两性离子内盐催化反应体系的重复使用结果图,从图可知,该催化剂同样具有较好的稳定性,重复使用4次后仍然具有较好的催化活性,HMF的产率可达到84.2%。重复使用6次后,HMF产率为74.0%,且催化剂的结构并未发生变化(见图3)。
需要说明的是,实施例1和3-18的催化剂重复使用性能与实施例2结果基本类似,在此不一一重复说明。
最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的宗旨和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (1)
1.一种两性离子内盐催化果糖基碳水化合物脱水制备5-羟甲基糠醛的方法,其特征在于,以两性离子内盐为催化剂,将果糖基碳水化合物在有机溶剂中进行选择性催化脱水反应转化为5-羟甲基糠醛,具体包括如下步骤:
向10mL的水热反应釜加入1.8g果糖,内盐催化剂15mol%,有机溶剂10mL,封闭反应釜,磁力搅拌,在120℃的油浴锅中反应1.5h;
所述内盐催化剂为1-磺丁基吡啶内盐;
所述有机溶剂为二甲基亚砜。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101812039A (zh) * | 2010-05-14 | 2010-08-25 | 天津大学 | 一种利用离子液体催化生成5-羟甲基糠醛的方法 |
CN102199136A (zh) * | 2011-03-31 | 2011-09-28 | 中国科学院西双版纳热带植物园 | 一种利用酸性离子液体制备5-羟甲基糠醛的方法 |
CN103204836A (zh) * | 2013-03-31 | 2013-07-17 | 青岛科技大学 | 一种制备5-羟甲基糠醛的方法 |
CN108084120A (zh) * | 2017-12-29 | 2018-05-29 | 山东理工大学 | 用于制备5-羟甲基糠醛的酸碱双功能固体催化剂及其制备方法和应用 |
CN110183403A (zh) * | 2019-05-20 | 2019-08-30 | 江苏大学 | 一种利用离子液体催化果糖转化为5-羟甲基糠醛的方法 |
CN111253350A (zh) * | 2020-03-20 | 2020-06-09 | 广东石油化工学院 | 一种氯代醇促进糖类化合物脱水制备5-羟甲基糠醛的方法 |
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-
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101812039A (zh) * | 2010-05-14 | 2010-08-25 | 天津大学 | 一种利用离子液体催化生成5-羟甲基糠醛的方法 |
CN102199136A (zh) * | 2011-03-31 | 2011-09-28 | 中国科学院西双版纳热带植物园 | 一种利用酸性离子液体制备5-羟甲基糠醛的方法 |
CN103204836A (zh) * | 2013-03-31 | 2013-07-17 | 青岛科技大学 | 一种制备5-羟甲基糠醛的方法 |
CN108084120A (zh) * | 2017-12-29 | 2018-05-29 | 山东理工大学 | 用于制备5-羟甲基糠醛的酸碱双功能固体催化剂及其制备方法和应用 |
CN110183403A (zh) * | 2019-05-20 | 2019-08-30 | 江苏大学 | 一种利用离子液体催化果糖转化为5-羟甲基糠醛的方法 |
CN111253350A (zh) * | 2020-03-20 | 2020-06-09 | 广东石油化工学院 | 一种氯代醇促进糖类化合物脱水制备5-羟甲基糠醛的方法 |
Non-Patent Citations (1)
Title |
---|
新型吗啉基离子液体中碳水化合物高效转化为5-羟甲基糠醛;宋金良等;科学通报(第016期);1522-1529 * |
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