CN109970756A - A method of it improving carbohydrate and prepares levoglucosenone selectivity - Google Patents
A method of it improving carbohydrate and prepares levoglucosenone selectivity Download PDFInfo
- Publication number
- CN109970756A CN109970756A CN201910352426.6A CN201910352426A CN109970756A CN 109970756 A CN109970756 A CN 109970756A CN 201910352426 A CN201910352426 A CN 201910352426A CN 109970756 A CN109970756 A CN 109970756A
- Authority
- CN
- China
- Prior art keywords
- acid
- levoglucosenone
- selectivity
- dehydrating agent
- carbohydrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001720 carbohydrates Chemical class 0.000 title claims abstract description 32
- HITOXZPZGPXYHY-UJURSFKZSA-N levoglucosenone Chemical compound O=C1C=C[C@H]2CO[C@@H]1O2 HITOXZPZGPXYHY-UJURSFKZSA-N 0.000 title claims abstract description 31
- HITOXZPZGPXYHY-UHFFFAOYSA-N levoglucosenone Natural products O=C1C=CC2COC1O2 HITOXZPZGPXYHY-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 37
- 239000000047 product Substances 0.000 claims abstract description 26
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 15
- 230000018044 dehydration Effects 0.000 claims abstract description 13
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 12
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007086 side reaction Methods 0.000 claims abstract description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- 235000014633 carbohydrates Nutrition 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 28
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 229920002472 Starch Polymers 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- 230000004044 response Effects 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 11
- 235000019698 starch Nutrition 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 230000000903 blocking effect Effects 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002016 disaccharides Chemical class 0.000 claims description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000002772 monosaccharides Chemical class 0.000 claims description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011505 plaster Substances 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- XDJWZONZDVNKDU-UHFFFAOYSA-N 1314-24-5 Chemical compound O=POP=O XDJWZONZDVNKDU-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- AYRXSINWFIIFAE-UHFFFAOYSA-N O6-alpha-D-Galactopyranosyl-D-galactose Natural products OCC1OC(OCC(O)C(O)C(O)C(O)C=O)C(O)C(O)C1O AYRXSINWFIIFAE-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 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 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- DLRVVLDZNNYCBX-ZZFZYMBESA-N beta-melibiose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)O1 DLRVVLDZNNYCBX-ZZFZYMBESA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- DLRVVLDZNNYCBX-CQUJWQHSSA-N gentiobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)C(O)O1 DLRVVLDZNNYCBX-CQUJWQHSSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
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- 150000007522 mineralic acids Chemical class 0.000 claims description 2
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- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 2
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QNLVXLJTOLHAMA-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(O)(O)=O Chemical group N=NC=NN.N=NC=NN.C(O)(O)=O QNLVXLJTOLHAMA-UHFFFAOYSA-N 0.000 description 1
- NTXMCEIJTGBYOK-UHFFFAOYSA-N O.CC1CCC(=O)O1 Chemical compound O.CC1CCC(=O)O1 NTXMCEIJTGBYOK-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- CZSABVBCTRZESY-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].OS(O)(=O)=O Chemical compound [O-2].[O-2].[Ti+4].OS(O)(=O)=O CZSABVBCTRZESY-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000006652 catabolic pathway Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropyl acetate Chemical compound CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/10—Anhydrosugars, e.g. epoxides
-
- 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
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of methods that raising carbohydrate prepares levoglucosenone selectivity, carbohydrate is during degradation prepares levoglucosenone in polar non-solute, since the generation of dehydration can inevitably have water constantly to generate in the reaction system, so that hydrolytic side reactions product 5 hydroxymethyl furfural and furfural are constantly formed, the selectivity of anhydrousugar product levoglucosenone is caused to decline, end reaction system is complicated, is unfavorable for later separation utilization.By the way that dehydrating agent is added in the reaction system, water caused by situ absorption or consumption dehydration, to inhibit the generation of hydrolytic side reactions, the generation of by-product is reduced or avoided, raising prepares levoglucosenone selectivity, is a kind of effective ways for improving carbohydrate degradation and preparing levoglucosenone selectivity.
Description
Technical field
The invention belongs to biomass economy fields, and in particular to a kind of raising carbohydrate prepares levoglucosenone choosing
The method of selecting property.
Background technique
Levoglucosenone (LGO, 1,6- dehydration -3,4- dideoxy-β-D- pyrans thin malt sugar -2- ketone) is a kind of important new
Type biology base platform chemicals can be used as chiral synthon and be of wide application in pharmaceutical synthesis and organic reaction.LGO has
Unique rigidity bicyclic ring structures, glycosidic bond, carbonyl and carbon-carbon double bond have it in the especially chiral synthesis of organic synthesis
Huge potential using value, for example, LGO can add hydrogen to prepare 1,6- hexylene glycol, further amination obtains hexamethylene diamine, Yi Zhongchong
The industrial chemicals and material monomer wanted；LGO can prepare milk lactone after aoxidizing, the fragrance as milk fragrance in food；LGO
It is double to be also used as compound 5- ethyl -2,4- dimethyl -6,8- dioxa of the starting material for synthesizing double-ring incision class
Ring [3.2.1] octane and tetraodotoxin etc..
Conventional method prepares the main form biomass pyrolysis method of LGO.Biomass is divided under 250 DEG C~550 DEG C of aerobic conditions
For pyrolysis, burnt, three kinds of products of gas and liquid process is known as biomass pyrolytic to solution.The liquid generated after pyrolysis is known as bio oil,
Can by further converting, separation and Extraction obtain various high value chemicals.Contain many kinds of substance in bio oil, as aldehydes,
Acids, furans and phenolic resin class etc..In addition, also containing some anhydrousugars, predominantly levoglucosan and LGO.But it is logical
The anhydrousugar low yield (< 8%), reaction product complicated component, separation and Extraction for crossing the method preparation are difficult, and reaction temperature is very
Height (Green Chemistry2007,9,1137-1140；Journal of Analytical and Applied
Pyrolysis 2003,68-9,197-211；Bioresource Technology 2012,103,466-469).
It is taken off currently, Cao etc. explores cellulose acid catalysis in aprotic, polar type solvents tetrahydrofurane and gamma-valerolactone
Water prepares levoglucosan and the method for LGO.LGO is prepared compared to traditional biomass pyrolysismethod, it is non-in polarity by cellulose
In proton solvent acid-catalyzed dehydration can obtain higher yields LGO (40-50%, such as: Cao, F.et al, Energy&
Enviromental Science, 2015,8 (6): 1808-1815 and US9376451), and reaction temperature is low.Concrete fiber
Degradation pathway following formula 1 of the element in polar non-solute.
1 cellulose of formula prepares anhydrousugar process in polar non-solute.
Entire degradation process is the cracking of cellulose and hydrolyzes while carrying out, although can choose anhydrous solvent guarantees reaction system
Water is not contained initially, but can generate 2 molecular waters during LGA is dehydrated preparation LGO, and the presence of these water makes cellulose water
Solution preocess is strengthened, and the glucose for hydrolyzing generation can be further converted to 5 hydroxymethyl furfural (HMF) and furfural (FF), is caused
Complicated component in cellulose dehydration reaction product is unfavorable for the separation and utilization of subsequent LGO.For this point, Huber etc. passes through
After a small amount of water is added into anhydrous tetrahydrofuran, it was demonstrated that the presence of moisture may consequently contribute to the generation of HMF really and reduce LGO's
Yield (He J Y, et al, Green Chemistry 2017,19 (15), 3642-3653).But it was reacted for how to remove
The water generated in journey, there is presently no relevant reports, and it is total to also result in cellulose catabolite in polar non-solute in this way
It is with the presence of a variety of form of mixtures, such result can have an impact subsequent separation application.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that raising carbohydrate prepares levoglucosenone selectivity, lead to
It crosses and dehydrating agent is added into reaction system, the water that situ absorption, consumption dehydration generate inhibits the generation of hydrolytic side reactions,
So that raising prepares the selectivity of anhydrousugar product levoglucosenone and reduction forms by-product 5 hydroxymethyl furfural and furfural
Selectivity, and raising prepares the selectivity of levoglucosenone.
A method of it improving carbohydrate and prepares levoglucosenone selectivity, specifically:
Carbohydrate acid-catalyzed dehydration is prepared to be added in the reaction system of levoglucosenone and be taken off in polar non-solute
The water that aqua, situ absorption or consumption dehydration generate, inhibits the generation of hydrolytic side reactions, forms anhydrousugar production to improve
The selectivity of object levoglucosenone and reduction form the selectivity of by-product 5 hydroxymethyl furfural and furfural.
The reaction system are as follows: carbohydrate additional amount is the 0.1%~10% of solvent quality, and catalyst charge is
2.5mM~300mM, reaction temperature are 80 DEG C~350 DEG C；
In one embodiment of the invention, carbohydrate additional amount is 3%, catalyst charge 20mM of solvent quality, instead
It answers the displacement of system argon gas three times, reacts 30min under the conditions of 200 DEG C.
The dehydrating agent of addition can be hydroscopicity dehydrating agent, such as: molecular sieve, polyacrylamide, glycerol, silica gel, anhydrous sulphur
Sour sodium, anhydrous magnesium sulfate, dead plaster, anhydrous cupric sulfate, anhydrous calcium chloride etc.；Response type dehydrating agent, such as: five oxidations two
Niobium, diboron trioxide, sulfur trioxide, triethyl orthoformate, phosphorus pentoxide, diphosphorus trioxide etc..The dosage of dehydrating agent is added
It is the 0.1%~10% of solvent quality.
The hydroscopicity dehydrating agent is more preferably anhydrous sodium sulfate, anhydrous magnesium sulfate, dead plaster, anhydrous slufuric acid
Copper, anhydrous calcium chloride.
The response type dehydrating agent is more preferably phosphorus pentoxide, diphosphorus trioxide, and dosage is solvent quality
1.5%~2.5%；Preferred dehydrating agent is phosphorus pentoxide, and dosage is the 1.5% of solvent quality.
The aprotic, polar type solvent used is various oxygen-containing class solvents, such as esters: ethyl acetate, propyl acetate, acetic acid
Isopropyl ester, butyl acetate, gamma-valerolactone, dimethyl carbonate, diethyl carbonate etc.；Ketone: acetone, butanone, methylisobutylketone,
Pentanone, cyclopentanone, cyclohexanone, N-Methyl pyrrolidone etc.；Ethers: tetrahydrofuran, butyl ether, glycol dimethyl ether, 1,3- dioxy
Five rings, Isosorbide-5-Nitrae-dioxane, 2- methyltetrahydrofuran, oxinane etc..
The carbohydrate of addition is polysaccharide, disaccharides, monosaccharide and with blocking group sugar etc..Polysaccharide has starch, Portugal poly-
Sugar and cellulose etc.；Disaccharides has sucrose, lactose, cellobiose, maltose, gentiobiose and melibiose etc.；Monosaccharide have glucose,
Mannose and galactolipin etc.；Blocking group with blocking group sugar mainly protects the position the C1 hydroxyl of glucose, protection
Group can be methyl, ethyl, propyl, isopropyl, butyl, phenyl, benzyl, p-nitrophenyl etc., and blocking group forms glucosides
Key can be α or β type.Carbohydrate additional amount is the 0.1%~10% of solvent quality.
The acid catalyst of addition can be inorganic acid, such as: sulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, perchloric acid；It can also be with
It is organic acid, such as: formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, maleic acid, fumaric acid, trichloroacetic acid, trifluoroacetic acid, methylsulphur
Acid, propane sulfonic acid, trifluoromethanesulfonic acid, phthalic acid and terephthalic acid (TPA) etc.；Be also possible to solid acid, as acid ion resin,
Sulfuric acid-titanium dioxide etc..The dosage that catalyst is added is 2.5mM~300mM.
Reaction temperature is 80 DEG C~350 DEG C.
The invention has the benefit that
Present invention carbohydrate in polar non-solute, which prepares to be added in anhydrousugar reaction system through acid catalyzed degradation, to be taken off
The water that aqua, situ absorption or reaction dehydration generate, to improve the selection for forming anhydrousugar product levoglucosenone
Property, convenient for the separation of subsequent levoglucosenone.
Detailed description of the invention
The gas chromatogram of reaction system when starch is raw material in Fig. 1 reference examples, dimethyl carbonate is solvent；Fig. 2 reaction
The gas chromatogram after phosphorus pentoxide dehydrating agent is added in system.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, content described in embodiment is merely to illustrate
The present invention, without the present invention described in detail in claims should will not be limited.
Water increment refers in embodiment measures in reaction system water content in water content, with initial system after the completion of reaction
Difference.Water content is measured by karr-Fei Xiu Moisture Meter.
The content of LGO, HMF and FF pass through gas chromatograph for determination in embodiment.Wherein, with anhydrousugar product LGO's
The ratio (LGO:(HMF+FF) of molar concentration and the sum of the molar concentration of by-product HMF and FF, subsequent referred to as ratio) it represents
The selectivity of LGO is formed, ratio is higher, and the selectivity that representative forms anhydrousugar product LGO is higher；Conversely, then forming the choosing of LGO
Selecting property is lower.
Solvent used in embodiment is commercial anhydrous solvent or the process pretreated solvent of anhydrous and oxygen-free.
Reference examples: carbohydrate degradation in polar non-solute prepares anhydrousugar levoglucosenone with reference to Cao
Pass through cellulose in pole Deng (Cao, F.et al, Energy&Enviromental Science, 2015,8 (6): 1808-1815)
The method that degradation prepares anhydrousugar levoglucosenone in property aprotic solvent, is urged using different material, different solvents and difference
Agent carries out dehydration, and raw material additional amount is the 3% of solvent quality, catalyst charge 20mM, reaction system argon gas
Displacement three times, reacts 30min under the conditions of 200 DEG C, measure the concentration of water increment and product, the result is shown in the following table 1.
1 carbohydrate dehydration product ratio of table
From the data in table 1, it can be seen that different carbohydrate are in opposed polarity aprotic solvent in the case where not adding dehydrating agent
In, using different catalysts catalytic and dehydration reaction, water increment is substantially similar, in 5000-6500ppm or so, and product and secondary
The ratio of product also remains unchanged substantially, and ratio is between 2-3.This shows various carbohydrate in polar non-solute
Reaction path is substantially similar, and there are two approach of cracking and hydrolysis, and the reaction selectivity of two approach is substantially stationary, nothing
Method makes to form the raising of the selectivity of anhydrousugar LGO by changing normal condition.Wherein, starch is raw material, and solvent is carbonic acid diformazan
The system of ester, gas chromatogram are shown in Fig. 1, and reaction material liquid after concentrated by rotary evaporator, contains LGO, HMF and FF, LGO in product
Purity be 72%.
Embodiment 1: starch dehydrating proportion of products in the case of hydroscopicity dehydrating agent is used
Hydroscopicity dehydrating agent includes anhydrous salt, silica gel, glycerol and molecular sieve etc..But due to the high temperature of this reaction system, acid item
Part, and it is not all can hydroscopicity dehydrating agent reaction result can be had an impact.We have selected silica gel, 4A grade molecule
Sieve, glycerol, anhydrous cupric sulfate, anhydrous magnesium sulfate and anhydrous sodium sulfate are hydroscopicity deicer (additional amount is solvent 2.5wt%),
Starch is raw material, dimethyl carbonate is solvent, p-methyl benzenesulfonic acid is catalyst, and other conditions are identical as reference examples, reaction
30min measures the concentration of water increment and product, and the result is shown in the following table 2.
Table 2 uses starch dehydrating proportion of products in the case of hydroscopicity dehydrating agent
From data in table 2 it is found that at the end of reaction, the water increment in reaction system has increased after hydroscopicity dehydrating agent is added
Component, as being added in the component of silica gel, water increment rises to 6629ppm by 5980ppm, and ratio is also down to 2.13 by 2.69, master
If can also bring a part of water during addition into because silica gel does not play the role of water removal into system, water is caused to contain
Amount increases, and the selectivity of ratio decline, LGO reduces.After glycerol is added in system, the water increment in system is reduced, by
5980ppm is reduced to 5562, but ratio is declined, and being primarily due to glycerol can be such that LGO decomposes, so as to cause under ratio
Drop.After 4A grades of molecular sieves are added in system, there is no any reaction, this is because 4A grades of molecular sieves destroy simultaneously powder by sulfuric acid
Change.These three dehydrating agents be added component in, except the component of 4A grades of molecular sieves does not react progress, in remaining component ratio all under
It drops, explanation is not that the addition of each dehydrating agent can effectively improve the selectivity of LGO, and some dehydrating agents cannot
Be stable in the presence of in reaction system, cause it is destructurized, to make reaction system that can not carry out.Knot is reacted after anhydrous salt is added
Shu Shishui increment decreases, and is reduced to 4000-5000ppm by 5980ppm, and ratio rises to 3.4 or more by 2.69, this
Show to play expected effect after anhydrous salt hydroscopicity dehydrating agent is added, reduces the water increment in reaction system, reduce simultaneously
A possibility that side reaction occurs, improves the selectivity to form anhydrousugar LGO.
Embodiment 2: starch dehydrating proportion of products in the case of response type dehydrating agent is used
Response type dehydrating agent can react with water, the water generated in reaction process be consumed, to reduce in reaction system
Water content.We have selected phosphorus pentoxide, triethyl orthoformate and the niobium pentaoxide (additional amount 2.5wt%) to be herein
Response type dehydrating agent is verified, and phosphorus pentoxide forms phosphoric acid after reacting with water, and triethyl orthoformate is formed after reacting with water
Ethyl formate and ethyl alcohol, niobium pentaoxide form niobic acid after reacting with water.It is solvent using cellulose as raw material, tetrahydrofuran, sulphur
Acid is catalyst, and a certain amount of response type dehydrating agent is added, and other conditions are identical as reference examples, reacts 30min, measures water increment
With the concentration of product, the result is shown in the following table 3.
Table 3 uses starch dehydrating proportion of products in the case of response type dehydrating agent
From data in table 3 it is found that although the water increment in reaction system is lowered by, but ratio after triethyl orthoformate is added
But it has dropped, this is because triethyl orthoformate can be such that LGO decomposes, ratio is caused to decline.Niobium pentaoxide is added as reaction
Type dehydrating agent, effect be added anhydrous salt be it is similar, the water increment in reaction system can be reduced on a small quantity, ratio can also mention
A height of 3 or more.In comparison, the effect that phosphorus pentoxide is added is then obvious, and water content declines to a great extent at the end of reaction, by
5980ppm is reduced to 3199ppm, meanwhile, ratio improves significantly, reaches 7.72.Phosphorus pentoxide greatly inhibits side reaction
A possibility that generation, improves the selectivity for preparing anhydrousugar LGO.
Embodiment 3: influence of the different phosphorus pentoxide input amounts to starch dehydrating proportion of products
In example 2, the selectivity that phosphorus pentoxide prepares anhydrousugar product LGO for raising play the role of it is very big, at this
In we investigate after the input amount for changing response type dehydrating agent phosphorus pentoxide the variation feelings of water increment and ratio in reaction system
Condition.Using cellulose as raw material, tetrahydrofuran be solvent, sulfuric acid is catalyst, and a certain amount of phosphorus pentoxide is added as reaction
Type dehydrating agent, other conditions are identical as reference examples, react 30min, measure the concentration of water increment and product, the result is shown in the following table 4.
Table 4 is starch dehydrating proportion of products in the case of response type dehydrating agent using phosphorus pentoxide
It is found that when the input amount of phosphorus pentoxide is increased as 3.5wt%, water increment further decreases the data from table 4, but compares
Value is declined, this, which is primarily due to excessive phosphorus pentoxide, can make anhydrousugar product LGO decompose, so as to cause ratio
Decline；And after the input amount for reducing phosphorus pentoxide is 1.5wt%, water increment is compared with the component of 2.5wt% almost without increasing
Add, ratio rises to 12.33, illustrates that the input amount of phosphorus pentoxide in 2.5wt% component is also excessive；And it further decreases
When the input amount of phosphorus pentoxide is 0.5wt%, the increased amplitude of water increment in reaction system is very big, increases as 4029ppm,
Ratio is reduced to 6.22, this is because the phosphorus pentoxide amount being added is too low, the water increment in reaction system is caused to be unable to get
Effectively control, reduces ratio.In comparison, suitable phosphorus pentoxide is put into, it not only can water increment to reaction system
It is controlled well, inhibits the generation of hydrolytic side reactions, moreover it is possible to improved the selectivity for preparing LGO to a greater extent, reduce shape
At the selectivity of by-product HMF and FF.Wherein, the component reaction result for 1.5wt% phosphorus pentoxide being added is shown in Fig. 2, reaction material
After liquid is concentrated by Rotary Evaporators, LGO and FF is only contained in product, the purity of LGO is 94%.
The present invention by into polar non-solute carbohydrate acid-catalyzed dehydration prepare anhydrousugar laevoglucose
Dehydrating agent is added in the reaction system of ketone, the water in reaction system can be effectively removed, inhibits the generation of hydrolytic side reactions, makes shape
It is improved at the selectivity of target product LGO.
Claims (10)
1. a kind of method for improving carbohydrate and preparing levoglucosenone selectivity, which is characterized in that in aprotic, polar
Carbohydrate acid-catalyzed dehydration prepares and dehydrating agent is added in the reaction system of levoglucosenone in type solvent, situ absorption or
The water that dehydration generates is consumed, inhibits the generation of hydrolytic side reactions, so that raising prepares anhydrousugar product levoglucosenone
Selectivity and reduction form the selectivity of by-product 5 hydroxymethyl furfural and furfural.
2. a kind of method for improving carbohydrate and preparing levoglucosenone selectivity according to claim 1, special
Sign is that the dehydrating agent of addition can be hydroscopicity dehydrating agent, is also possible to response type dehydrating agent；The hydroscopicity dehydrating agent packet
It includes: molecular sieve, polyacrylamide, glycerol, silica gel, anhydrous sodium sulfate, anhydrous magnesium sulfate, dead plaster, anhydrous cupric sulfate, nothing
Water calcium chloride etc.；The response type dehydrating agent include: niobium pentaoxide, diboron trioxide, sulfur trioxide, triethyl orthoformate,
Phosphorus pentoxide, diphosphorus trioxide etc..
3. a kind of method for improving carbohydrate and preparing levoglucosenone selectivity according to claim 1, special
Sign is that the aprotic, polar type solvent used is various oxygen-containing class solvents, and such as esters: ethyl acetate, propyl acetate, acetic acid are different
Propyl ester, butyl acetate, gamma-valerolactone, dimethyl carbonate, diethyl carbonate etc.；Ketone: acetone, butanone, methylisobutylketone, penta
Ketone, cyclopentanone, cyclohexanone, N-Methyl pyrrolidone etc.；Ethers: tetrahydrofuran, butyl ether, glycol dimethyl ether, 1,3- dioxy five
Ring, Isosorbide-5-Nitrae-dioxane, 2- methyltetrahydrofuran, oxinane etc..
4. a kind of method for improving carbohydrate and preparing levoglucosenone selectivity according to claim 1, special
Sign is, carbohydrate is polysaccharide, disaccharides, monosaccharide and with blocking group sugar etc.；Polysaccharide has starch, glucan and fiber
Element etc.；Disaccharides has sucrose, lactose, cellobiose, maltose, gentiobiose and melibiose etc.；Monosaccharide have glucose, mannose and
Galactolipin etc.；Blocking group with blocking group sugar mainly protects the position the C1 hydroxyl of glucose molecule, blocking group
It can be methyl, ethyl, propyl, isopropyl, butyl, phenyl, benzyl, p-nitrophenyl etc., blocking group forms glycosidic bond
Configuration can be α or β type.
5. a kind of method for improving carbohydrate and preparing levoglucosenone selectivity according to claim 1, special
Sign is that the acid catalyst of addition can be inorganic acid, such as: sulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, perchloric acid；It can be
Organic acid, such as: formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, maleic acid, fumaric acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid,
Propane sulfonic acid, trifluoromethanesulfonic acid, phthalic acid and terephthalic acid (TPA) etc.；It is also possible to solid acid, such as acid ion resin, sulphur
Acid-titanium dioxide etc..
6. a kind of method for improving carbohydrate and preparing levoglucosenone selectivity according to claim 1, special
Sign is that reaction temperature is 80 DEG C ~ 350 DEG C.
7. a kind of method for improving carbohydrate and preparing levoglucosenone selectivity according to claim 2, special
Sign is that the dosage that dehydrating agent is added is the 0.1% ~ 10% of solvent quality.
8. a kind of method for improving carbohydrate and preparing levoglucosenone selectivity according to claim 3, special
Sign is that carbohydrate additional amount is the 0.1% ~ 10% of solvent quality.
9. a kind of method for improving carbohydrate and preparing levoglucosenone selectivity according to claim 5, special
Sign is that the dosage that catalyst is added is 2.5mM ~ 300mM.
10. a kind of method for improving carbohydrate and preparing levoglucosenone selectivity according to claim 2, special
Sign is, the dehydrating agent be anhydrous sodium sulfate, anhydrous magnesium sulfate, dead plaster, anhydrous cupric sulfate, anhydrous calcium chloride or
Phosphorus pentoxide, the dosage that dehydrating agent is added is the 1.5% ~ 2.5% of solvent quality.
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| CN112646596A (en) * | 2019-10-11 | 2021-04-13 | 中国科学院大连化学物理研究所 | Biomass pretreatment method for improving selectivity of high-value chemicals in pyrolysis oil |
| CN114853777A (en) * | 2022-06-14 | 2022-08-05 | 华北电力大学 | Catalytic pyrolysis method for preparing LGO |
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| CN112646596A (en) * | 2019-10-11 | 2021-04-13 | 中国科学院大连化学物理研究所 | Biomass pretreatment method for improving selectivity of high-value chemicals in pyrolysis oil |
| CN114853777A (en) * | 2022-06-14 | 2022-08-05 | 华北电力大学 | Catalytic pyrolysis method for preparing LGO |
| CN114853777B (en) * | 2022-06-14 | 2024-03-01 | 华北电力大学 | Catalytic pyrolysis method for preparing LGO |
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