CN115028608B - 一种5-羟甲基糠醛、5-烷酰氧基甲基糠醛和2,5-呋喃二甲酸的联产方法 - Google Patents
一种5-羟甲基糠醛、5-烷酰氧基甲基糠醛和2,5-呋喃二甲酸的联产方法 Download PDFInfo
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- CN115028608B CN115028608B CN202210493097.9A CN202210493097A CN115028608B CN 115028608 B CN115028608 B CN 115028608B CN 202210493097 A CN202210493097 A CN 202210493097A CN 115028608 B CN115028608 B CN 115028608B
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- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 76
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 119
- 230000018044 dehydration Effects 0.000 claims abstract description 112
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- 150000002402 hexoses Chemical class 0.000 claims abstract description 65
- 238000005886 esterification reaction Methods 0.000 claims abstract description 53
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 39
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 26
- 229930195729 fatty acid Natural products 0.000 claims abstract description 26
- 239000000194 fatty acid Substances 0.000 claims abstract description 26
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 50
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 37
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 28
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 claims description 24
- 229930091371 Fructose Natural products 0.000 claims description 22
- 239000005715 Fructose Substances 0.000 claims description 22
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 18
- 235000011054 acetic acid Nutrition 0.000 claims description 17
- 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 14
- 235000019253 formic acid Nutrition 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- 239000004005 microsphere Substances 0.000 claims description 10
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910013500 M-O—Si Inorganic materials 0.000 claims description 3
- BJHIKXHVCXFQLS-UYFOZJQFSA-N fructose group Chemical group OCC(=O)[C@@H](O)[C@H](O)[C@H](O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 description 38
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- 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 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 229910001509 metal bromide Inorganic materials 0.000 description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 150000002243 furanoses Chemical class 0.000 description 6
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- SHNRXUWGUKDPMA-UHFFFAOYSA-N 5-formyl-2-furoic acid Chemical compound OC(=O)C1=CC=C(C=O)O1 SHNRXUWGUKDPMA-UHFFFAOYSA-N 0.000 description 5
- 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 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 229930182830 galactose Natural products 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 5
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LKDRXBCSQODPBY-VRPWFDPXSA-N D-fructopyranose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-VRPWFDPXSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 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 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000007405 data analysis Methods 0.000 description 4
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
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- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 239000002253 acid Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 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 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 208000007976 Ketosis Diseases 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 239000006227 byproduct Substances 0.000 description 2
- 125000005626 carbonium group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 2
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 2
- UQEXUNADTVCXEU-UHFFFAOYSA-L cobalt(2+);hydrogen phosphate Chemical compound [Co+2].OP([O-])([O-])=O UQEXUNADTVCXEU-UHFFFAOYSA-L 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 2
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 2
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 2
- 150000002584 ketoses Chemical class 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
- 229910001511 metal iodide Inorganic materials 0.000 description 2
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- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- GZCGUPFRVQAUEE-UHFFFAOYSA-N 2,3,4,5,6-pentahydroxyhexanal Chemical compound OCC(O)C(O)C(O)C(O)C=O GZCGUPFRVQAUEE-UHFFFAOYSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-UHFFFAOYSA-N 3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound OC1OC(C(O)=O)C(O)C(O)C1O AEMOLEFTQBMNLQ-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910019131 CoBr2 Inorganic materials 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- UDQOBKBQZZUOJB-UHFFFAOYSA-H chromium(3+) hydrogen phosphate Chemical compound [Cr+3].[Cr+3].OP([O-])([O-])=O.OP([O-])([O-])=O.OP([O-])([O-])=O UDQOBKBQZZUOJB-UHFFFAOYSA-H 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- PPUZYFWVBLIDMP-UHFFFAOYSA-K chromium(3+);triiodide Chemical compound I[Cr](I)I PPUZYFWVBLIDMP-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- XZQOHYZUWTWZBL-UHFFFAOYSA-L chromium(ii) bromide Chemical compound [Cr+2].[Br-].[Br-] XZQOHYZUWTWZBL-UHFFFAOYSA-L 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 229960000355 copper sulfate Drugs 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- CSCNMBQITNFHLH-UHFFFAOYSA-L copper;hydrogen phosphate Chemical compound [Cu+2].OP([O-])([O-])=O CSCNMBQITNFHLH-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JBVOSZYUSFDYIN-UHFFFAOYSA-N dimethyl cyclopropane-1,2-dicarboxylate Chemical compound COC(=O)C1CC1C(=O)OC JBVOSZYUSFDYIN-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- -1 etc.) Chemical compound 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 229940046149 ferrous bromide Drugs 0.000 description 1
- 229940076136 ferrous iodide Drugs 0.000 description 1
- 229960001781 ferrous sulfate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- AOBAVABSFWTQIX-UHFFFAOYSA-L hydrogen phosphate;iron(2+) Chemical compound [Fe+2].OP([O-])([O-])=O AOBAVABSFWTQIX-UHFFFAOYSA-L 0.000 description 1
- OLYKGFYCSAJGKT-UHFFFAOYSA-L hydrogen phosphate;nickel(2+) Chemical compound [Ni+2].OP([O-])([O-])=O OLYKGFYCSAJGKT-UHFFFAOYSA-L 0.000 description 1
- LRGKLCMGBJZMTB-UHFFFAOYSA-J hydrogen phosphate;tin(4+) Chemical compound [Sn+4].OP([O-])([O-])=O.OP([O-])([O-])=O LRGKLCMGBJZMTB-UHFFFAOYSA-J 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- QWYFOIJABGVEFP-UHFFFAOYSA-L manganese(ii) iodide Chemical compound [Mn+2].[I-].[I-] QWYFOIJABGVEFP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OBBXFSIWZVFYJR-UHFFFAOYSA-L tin(2+);sulfate Chemical compound [Sn+2].[O-]S([O-])(=O)=O OBBXFSIWZVFYJR-UHFFFAOYSA-L 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- LKCUKVWRIAZXDU-UHFFFAOYSA-L zinc;hydron;phosphate Chemical compound [Zn+2].OP([O-])([O-])=O LKCUKVWRIAZXDU-UHFFFAOYSA-L 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
-
- 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
- C07D307/56—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明涉及有机合成领域,公开了一种5‑羟甲基糠醛、5‑烷酰氧基甲基糠醛和2,5‑呋喃二甲酸的联产方法,包括以下步骤:以己糖为原料,以脂肪酸或者脂肪酸的水溶液为反应溶剂,在脱水催化剂的催化下,进行脱水和酯化反应,获得含有5‑羟甲基糠醛和5‑烷酰氧基甲基糠醛的己糖脱水产物;在氧化催化剂的催化下,将己糖脱水产物与氧化剂接触,进行氧化反应,而后进行固液分离,获得2,5‑呋喃二甲酸。本发明在脱水和酯化反应后无需分离出中间产物即可直接进行氧化反应,能实现连续化生产,因而具有工艺流程短、生产成本低、收率高的优点;并且,通过固液分离即可分离出产物FDCA,产物分离过程简单快速,能耗和成本较低。
Description
技术领域
本发明涉及有机合成领域,尤其涉及一种5-羟甲基糠醛、5-烷酰氧基甲基糠醛和2,5-呋喃二甲酸的联产方法。
背景技术
目前能源和化工产品的来源主要是煤、石油等不可再生资源,全球不断增长的能源需求不仅造成了煤、石油等资源的价格上升,而且对全球环境造成了极大的压力,产生了酸雨、雾霾、气候变暖等严重的环境问题。因此,以碳水化合物等可再生生物质资源为原料生产燃料和化工产品是解决当下能源危机和环境问题的有效途径。
5-羟甲基糠醛(HMF)是一种重要的生物基平台化合物,不仅可以用来生产呋喃类、烷烃类和乙酰丙酸之类液体燃料,而且可以用来生产溶剂、医药中间体和聚酯类材料等,具有广阔的市场前景。5-烷酰氧基甲基糠醛(AMF)是一种重要的5-羟甲基糠醛衍生物,其与HMF结构相似,但具有更高的反应性、更好的亲油性和更高的稳定性,可以取代HMF作为生产呋喃基单体化合物的原料。2,5-呋喃二甲酸(FDCA)是生物质来源HMF经过氧化反应生成的一种呋喃类的衍生物,其重要用途之一是替代石油产物对苯二甲酸生产聚酯类化合物,可以充分利用生物质资源,同时减少对石油产物的消耗。由己糖出发制备HMF、AMF和FDCA的流程如下:
HMF、AMF和FDCA均为重要的生物基平台化合物,三者联产能够缩短反应流程,降低FDCA的生产成本。例如,专利CN201810373604.9公开了一种连续合成呋喃二甲酸的方法和系统,包括以下步骤:(1)将糖类溶解在有机溶剂(二甲基亚砜)中,制得质量浓度为5%~50%的糖溶液,在固体酸脱水催化剂的作用下,于60~140℃反应0.5~12小时;(2)在步骤(1)的流出液中加入碱性水溶液和氧化剂,在负载型氧化催化剂的作用下,于60~110℃、0.1~1MPa条件下反应2~12小时;(3)步骤(2)的流出液经蒸除溶剂后,加入酸化剂,调节pH<2,沉淀出呋喃二甲酸粗品;经过滤、洗涤、重结晶后得到呋喃二甲酸。该专利在脱水反应后,无需对中间体HMF进行分离提纯,即可直接进行氧化反应,因而能够实现连续反应,大大缩短反应流程,降低FDCA的生产成本,但同时也存在以下问题:采用二甲基亚砜作为脱水反应溶剂,在完成氧化反应后,产物分离过程复杂,需要通过蒸除溶剂和酸化沉淀才能获得呋喃二甲酸,造成生产时间延长,能耗和成本增加。
发明内容
为了解决现有的HMF、AMF和FDCA联产方法产物分离过程复杂的技术问题,本发明提供了一种5-羟甲基糠醛、5-烷酰氧基甲基糠醛和2,5-呋喃二甲酸的联产方法。本发明能实现HMF、AMF和FDCA的连续化生产,且通过固液分离即可分离出产物FDCA,具有产物分离过程简单快速、能耗和生产成本低的优点。
本发明的具体技术方案为:
一种5-羟甲基糠醛、5-烷酰氧基甲基糠醛和2,5-呋喃二甲酸的联产方法,包括以下步骤:
(1)以己糖为原料,以脂肪酸或者脂肪酸的水溶液为反应溶剂,在脱水催化剂的催化下,进行脱水和酯化反应,获得含有5-羟甲基糠醛和5-烷酰氧基甲基糠醛的己糖脱水产物;
(2)在氧化催化剂的催化下,将己糖脱水产物与氧化剂接触,进行氧化反应,而后进行固液分离,获得2,5-呋喃二甲酸。
本发明以易得且价格低的己糖为原料,经由脱水反应、酯化反应和氧化反应制备2,5-呋喃二甲酸,具体过程如下:在步骤(1)中,己糖脱去三分子水生成5-羟甲基糠醛(HMF),部分HMF与反应溶剂中的脂肪酸发生酯化反应,生成5-烷酰氧基甲基糠醛(AMF),完成脱水和酯化反应后获得的混合物(即己糖脱水产物)不经过分离纯化操作,可直接进行步骤(2)的氧化反应,使其中的HMF和AMF被氧化成2,5-呋喃二甲酸(FDCA),而后通过固液分离,获得的固体即为FDCA。
在上述过程中,采用脂肪酸或者脂肪酸的水溶液作为脱水反应的反应溶剂,具有以下作用:己糖脱水生成的HMF以及由HMF酯化生成的AMF经由氧化反应后,均能转变成2,5-呋喃二甲酸,并且,脂肪酸或者脂肪酸的水溶液也能够作为HMF和AMF氧化反应的反应溶剂,因此,在脱水和酯化反应后,无需分离产物,即可直接进行氧化反应,实现连续化生产,因而能够缩短反应流程,降低2,5-呋喃二甲酸的生产成本,同时还能避免分离HMF和AMF过程中出现的产物损失,提高FDCA收率;并且,由于2,5-呋喃二甲酸在脂肪酸或脂肪酸的水溶液中的溶解度较小,因此,在连续化生产过程中,氧化反应时生成的2,5-呋喃二甲酸会以固体的形式从反应体系中析出,完成反应后通过固液分离(如离心或抽滤等)即可获得2,5-呋喃二甲酸,产物分离过程简单快速,能耗和成本较低,并且,对脱水催化剂和氧化催化剂的限制较少,当采用均相催化剂或非均相催化剂时,均易实现催化剂与2,5-呋喃二甲酸的分离。
作为优选,步骤(1)中,所述脂肪酸为C1~C6的脂肪酸中的一种或多种。
进一步地,步骤(1)中,所述脂肪酸包括甲酸、乙酸和丙酸中的一种或多种。
相较于其他脂肪酸(如异丁酸、正丁酸和特戊酸等)而言,甲酸、乙酸和丙酸的电离常数较大,能使脱水反应体系具有较强的酸性,有助于促进己糖的脱水,因而能提高HMF的收率;并且,甲酸、乙酸和丙酸的分子尺寸较小,羧基进行酯化的位阻较小,容易发生酯化反应,因而能提高AMF的收率。因此,选用甲酸、乙酸和丙酸中的一种或多种作为反应溶剂,能够提高脱水和酯化反应的收率,进而提高2,5-呋喃二甲酸的收率。
作为优选,步骤(1)中,所述脱水催化剂包括酸、金属氯化物、金属溴化物、金属碘化物、金属磷酸盐、金属硝酸盐、金属硫酸盐和金属磺酸盐中的一种或多种。
其中,酸如硫酸、盐酸、氢溴酸、氢碘酸、磷酸、硝酸和Amberlyst-15;氯化物如氯化钾、氯化钠、氯化铁、氯化铁、氯化锌、氯化钴、氯化铜、氯化锰、氯化钴、氯化镍、三氯化铬、四氯化锡和二氯化锡;溴化物如溴化钠、溴化钾、溴化铁、溴化亚铁、溴化锌、溴化钴、溴化铜、溴化锰、溴化钴、溴化镍、溴化铬、溴化锡(IV)和溴化亚锡(II);碘化物如碘化钠、碘化钾、碘化铁、碘化亚铁、碘化锌、碘化钴、碘化铜、碘化锰、碘化钴、碘化镍、碘化铬、碘化锡(IV)和碘化亚锡(II);磷酸盐如磷酸铌、磷酸氢钠、磷酸氢钾、磷酸氢铁、磷酸氢亚铁、磷酸氢锌、磷酸氢钴、磷酸氢铜、磷酸氢锰、磷酸氢钴、磷酸氢镍、磷酸氢铬、磷酸氢锡(IV)和磷酸氢亚锡(II);硝酸盐如硝酸钠、硝酸钾、硝酸铁、硝酸亚铁、硝酸锌、硝酸钴、硝酸铜、硝酸锰、硝酸钴、硝酸镍、硝酸铬、硝酸锡(IV)和硝酸亚锡(II);硫酸盐如硫酸钠、硫酸氢钠、硫酸钾、硫酸铁、硫酸亚铁、硫酸锌、硫酸钴、硫酸铜、硫酸锰、硫酸钴、硫酸镍、硫酸铬、硫酸锡(IV)和硫酸亚锡(II)。
进一步地,步骤(1)中,所述脱水催化剂为金属溴化物。
当采用乙酸或乙酸水溶液作为反应溶剂时,选择金属溴化物作为脱水催化剂,具有较好的催化效果,原因在于:一方面,金属阳离子可以与己糖形成离子型配合物(如与果糖形成[M(OH)x(C6H12O6)]+),促进己醛糖氢转移生成己酮糖和后续成环反应,另一方面,金属阳离子的外层轨道未被完全充满,能与羧酸的C=O键的孤对电子进行配对,使得羰基碳原子上正电荷增加,有利于醇与之结合,对酯化反应有促进作用,而溴离子能提供孤对电子,在己糖质子化和脱水过程中可稳定生成碳正离子中间体,与金属离子发挥协同作用,提高脱水速率和产物选择性,因此,金属溴化物对己糖脱水生成HMF以及HMF酯化生成AMF的催化效果较好,因而能提高HMF和AMF的收率,进而提高FDCA的收率。
作为优选,步骤(1)中,所述脱水催化剂为金属改性空心磷酸铌催化剂;所述金属改性空心磷酸铌催化剂包括空心介孔二氧化硅微球骨架,负载于所述骨架中的磷酸铌,以及以M-O-Si形态结合在所述骨架中的改性金属M;所述改性金属M选自Sn4+、Cr3+、Zn2+、Al3+。
当采用金属改性空心磷酸铌催化剂作为脱水催化剂时,具有以下优点:二氧化硅微球骨架可有效分散活性金属位点(包括铌和改性金属M),并延长催化剂寿命。制备过程中的空心结构内部是活性金属分布较低的位点,在微观上可减少产物与产物、产物与底物、产物与副产物等的碰撞机率,从而降低副反应发生的概率,提高反应选择性。通过这种方式,能够提高HMF和AMF的收率,进而提高FDCA的收率。
作为优选,所述空心磷酸铌催化剂的制备方法包括以下步骤:
1)在水中加入表面活性剂、正硅酸乙酯及聚苯乙烯微球,加热搅拌的同时滴加碱性溶液,直至溶液中不再继续生成沉淀;过滤沉淀,水洗涤至中性,烘干,获得介孔硅酸盐骨架;
2)将步骤1)所得介孔硅酸盐骨架、磷酸、五价铌的可溶性盐和改性金属M的可溶性盐的混合溶液制成乳浊液;
3)将步骤2)所得乳浊液转移至反应器中进行水热反应实现晶化,完成水热反应后,过滤沉淀并水洗涤至中性,烘干;
4)控制升温速率8~12℃/min,将步骤3)所得沉淀在空气氛围中于400~600℃下焙烧3~5h,获得空心磷酸铌催化剂。硅酸盐及磷酸铌在焙烧过程中逐渐脱水形成Nb-P-Si-O结合的复配化合物,同时模板剂(聚苯乙烯微球)在焙烧过程中被脱出,最终形成空心磷酸铌催化剂。
本发明首先使用模板剂合成球形介孔硅酸盐骨架,再在硅酸骨架中引入磷酸铌层板及功能化的金属位点,最后在空气氛围中焙烧脱除模板即可成功制得金属改性空心磷酸铌催化剂。由于本发明是先在聚苯乙烯微球表面形成硅酸盐骨架,然后再负载金属元素,最后焙烧去除聚苯乙烯微球形成空心骨架,因此最终所得催化剂中,金属元素主要分布于骨架表层,对于催化选择性更好。
作为优选,步骤(1)中,所述脂肪酸的水溶液中,水含量为1~20wt%。
作为优选,步骤(1)中,所述己糖包括葡萄糖、果糖、半乳糖和甘露糖中的一种或多种。
进一步地,步骤(1)中,所述己糖为果糖。
相较于其他己糖(如葡萄糖、半乳糖等)而言,果糖具有更好的催化脱水效果,原因在于:果糖属于酮糖,在结晶状态下,酮糖中可能存在β-吡喃型糖,在天然产物中常常以呋喃型果糖相结合。在水溶液中,呋喃型果糖和吡喃型果糖同时存在,在20℃水溶液中大约有20%呋喃型果糖。因此,果糖更易发生脱水反应,选用果糖作为联产HMF、AMF和FDCA的原料,能够提高HMF和AMF的收率,进而提高FDCA的收率。
作为优选,步骤(1)中,所述脱水催化剂与己糖的质量比为1:(10~1000);所述脱水和酯化反应的温度为50~160℃,时间为5~500min。
作为优选,步骤(1)中,所述己糖的质量为己糖、反应溶剂和脱水催化剂总质量的1~40wt%。
作为优选,步骤(2)中,所述氧化催化剂为由钴源、锰源和溴源组成的Co/Mn/Br三元催化剂。
进一步地,所述钴源包括醋酸钴、碳酸钴、醋酸钴四水合物和溴化钴中的一种或多种;所述锰源包括醋酸锰、碳酸锰、醋酸锰四水合物和溴化锰中的一种或多种;所述溴源包括溴化氢、溴化钾和四溴乙烷中的一种或多种。
进一步地,所述Co/Mn/Br三元催化剂中,Co与Mn的摩尔比为0.5~50:1,Br的摩尔量与Co和Mn的总摩尔量之比为0.1~3:1,Co的用量为步骤(1)中反应溶剂质量的50~10000ppm。
作为优选,步骤(2)中,所述氧化剂为含氧气体,所述氧化反应的温度为50~220℃。
与现有技术相比,本发明具有以下优点:
(1)本发明在联产HMF、AMF和FDCA的过程中,脱水和酯化反应后无需分离出HMF和AMF即可直接进行氧化反应合成FDCA,能实现连续化生产,因而具有工艺流程短、生产成本低、收率高的优点;
(2)本发明通过固液分离即可分离出产物FDCA,产物分离过程简单快速,能耗和成本较低;(3)本发明采用金属改性空心磷酸铌催化剂作为脱水催化剂,能够降低副反应发生的概率,从而提高反应收率。
具体实施方式
下面结合实施例对本发明作进一步的描述。
以下实施例中,所使用的500mL高压反应釜均为钛材制造,采用间歇式操作方式,每次实验装入的反应液相约为200~400mL。反应釜的外壁和底部采用电加热,加热功率为1千瓦;电加热套的外侧包有绝缘材料,以减少釜壁的散热。釜内安装冷却盘管,内通导热油,导热油的流量由蠕动泵的转速控制。计算机通过控制反应釜壁温和盘管中的冷却油流量来控制反应温度,控制精度达±0.5℃。搅拌桨为四叶平桨,以保证良好的气泡分散和传质要求,各实施例中搅拌速率约为900rpm。进气管在桨叶下方,空气的流量由反应器入口处的微调阀手工控制,流量的控制范围0~10L/min。反应压力由背压阀控制。反应尾气由背压阀减压排出前要经过多级冷凝和深冷,凝液回流至反应釜,由背压阀排出的尾气经进一步深冷干燥后,分别进入在线的磁氧分析仪和红外在线分析仪分析尾气中的氧浓度、CO和CO2浓度,尾气浓度数据均有计算机进行数据采集与记录。同时反应釜配有三通的取样阀门,可以间隔1~30min进行取样分析。
总实施例
一种5-羟甲基糠醛、5-烷酰氧基甲基糠醛和2,5-呋喃二甲酸的联产方法,包括以下步骤:
(1)脱水和酯化反应:
以己糖为原料,以脂肪酸或者脂肪酸的水溶液为反应溶剂,在脱水催化剂的催化下,在50~160℃下进行脱水和酯化反应5~500min,所述己糖的质量为己糖、反应溶剂和脱水催化剂总质量的1~40wt%,所述脱水催化剂与己糖的质量比为1:(10~1000),获得含有5-羟甲基糠醛和5-烷酰氧基甲基糠醛的己糖脱水产物;
所述脂肪酸为C1~C6的脂肪酸中的一种或多种,优选为包括甲酸、乙酸和丙酸中的一种或多种;
所述脱水催化剂包括酸、金属氯化物、金属溴化物、金属碘化物、金属磷酸盐、金属硝酸盐、金属硫酸盐和金属磺酸盐中的一种或多种;
所述己糖包括葡萄糖、果糖、半乳糖和甘露糖中的一种或多种,优选为果糖;
(2)氧化反应:
在氧化催化剂的催化下,将己糖脱水产物与氧化剂接触,在50~220℃下进行氧化反应,而后进行固液分离,获得2,5-呋喃二甲酸;
所述氧化剂为含氧气体;
所述氧化催化剂为由钴源、锰源和溴源组成的Co/Mn/Br三元催化剂。作为一种具体实施方式,所述Co/Mn/Br三元催化剂中,Co与Mn的摩尔比为0.5~50:1,Br的摩尔量与Co和Mn的总摩尔量之比为0.1~3:1,Co的用量为步骤(1)中反应溶剂质量的50~10000ppm。
可选地,步骤(1)中,所述脱水催化剂为金属改性空心磷酸铌催化剂;所述金属改性空心磷酸铌催化剂包括空心介孔二氧化硅微球骨架,负载于所述骨架中的磷酸铌,以及以M-O-Si形态结合在所述骨架中的改性金属M;所述改性金属M选自Sn4+、Cr3+、Zn2+、Al3+。所述空心磷酸铌催化剂的制备方法包括以下步骤:
1)在水中加入表面活性剂、正硅酸乙酯及聚苯乙烯微球,加热搅拌的同时滴加碱性溶液,直至溶液中不再继续生成沉淀;过滤沉淀,水洗涤至中性,烘干,获得介孔硅酸盐骨架;
2)将步骤1)所得介孔硅酸盐骨架、磷酸、五价铌的可溶性盐和改性金属M的可溶性盐的混合溶液制成乳浊液;
3)将步骤2)所得乳浊液转移至反应器中进行水热反应实现晶化,完成水热反应后,过滤沉淀并水洗涤至中性,烘干;
4)控制升温速率8~12℃/min,将步骤3)所得沉淀在空气氛围中于400~600℃下焙烧3~5h,获得空心磷酸铌催化剂。
实施例1:脱水和酯化反应
制备己糖脱水产物:向500mL高压反应釜中加入332g反应液(由30g果糖、300g甲酸和2.0g硫酸氢钠组成的混合物),通入氮气作为保护气,使反应釜的压力达到1.5MPa,在搅拌的同时将反应液加热至140℃,维持反应液在140℃下搅拌反应1h,然后冷却至20℃,得到淡黄色液体产品,即己糖脱水产物。
分离出HMF和AMF的混合物:向己糖脱水产物中加入1mol/L的碳酸钠后静置分层,分离有机层,水相用乙酸乙酯萃取三次,合并萃取相与分离的有机层,并用无水硫酸镁干燥,而后进行过滤、洗涤,母液减压蒸馏脱出醋酸和乙酸乙酯,釜中残留物用二氯甲烷重结晶,并真空干燥,获得HMF和AMF的混合物。
实施例2~6:脱水和酯化反应
按照实施例1中的步骤,通过脱水和酯化反应制备己糖脱水产物,并从己糖脱水产物中分离出HMF和AMF的混合物。与实施例1的区别仅在于,实施例2~6中,分别将甲酸换成等质量的乙酸、丙酸、异丁酸、正丁酸和特戊酸。
实施例7:脱水和酯化反应
按照实施例1中的步骤,通过脱水和酯化反应制备己糖脱水产物,并从己糖脱水产物中分离出HMF和AMF的混合物。与实施例1的区别仅在于,将果糖换成等质量的葡萄糖,将甲酸换成等质量的乙酸。
实施例8:脱水和酯化反应
按照实施例1中的步骤,通过脱水和酯化反应制备己糖脱水产物,并从己糖脱水产物中分离出HMF和AMF的混合物。与实施例1的区别仅在于,将果糖换成等质量的半乳糖,将甲酸换成等质量的乙酸。
测试例1:脱水和酯化反应收率
检测实施例1~8中的HMF收率、AMF收率和总收率,方法如下:取0.2g的HMF和AMF的混合物,用甲醇稀释至50mL,利用安捷伦公司的高效液相色谱,分析HMF和AMF的含量,色谱柱为Sugar SH 101,流动相为硫酸水溶液,流速为0.5mL/min;柱温为60℃,示差检测器温度为40℃,进样量为20μL,同时液相产物鉴定由GC/MS(Agilent 6890/5973MSD气质连用仪)和标准品对照定性,采用外标法对产物定量。根据测得的HMF和AMF含量,计算HMF收率、AMF收率和总收率。结果见表1。
表1己糖和反应溶剂对脱水和酯化效果的影响
数据分析:
(1)根据表1中实施例1~6的数据可以看出,相较于异丁酸、正丁酸和特戊酸而言,当采用甲酸、乙酸和丙酸作为反应溶剂时,HMF和AMF的收率以及总收率较高。原因在于:甲酸、乙酸和丙酸的电离常数较大,酸性较强,能够促进己糖脱水,从而提高HMF的收率;并且,甲酸、乙酸和丙酸的分子尺寸较小,羧基酯化时的位阻较小,易于酯化,因而AMF的收率较高。
(2)根据表1中实施例2、7和8的数据可以看出,果糖的脱水效果优于葡萄糖和半乳糖。原因在于:果糖属于酮糖,在结晶状态下,酮糖中可能存在β-吡喃型糖,在天然产物中常常以呋喃型果糖相结合;在水溶液中,呋喃型果糖和吡喃型果糖同时存在,在20℃水溶液中大约有20%呋喃型果糖。因此,果糖更易发生脱水反应,采用其作为原料,能够提高HMF和AMF的收率。
实施例9:脱水和酯化反应
按照实施例1中的步骤,通过脱水和酯化反应制备己糖脱水产物,并从己糖脱水产物中分离出HMF和AMF的混合物。与实施例1的区别仅在于,将硫酸氢钠换成等质量的CrCl3,反应时间由1h延长到2h。
实施例10:脱水和酯化反应
按照实施例9中的步骤,通过脱水和酯化反应制备己糖脱水产物,并从己糖脱水产物中分离出HMF和AMF的混合物。与实施例9的区别仅在于,将CrCl3换成等质量的ZnCl2,反应时间由2h缩短到1h。
实施例11:脱水和酯化反应
按照实施例9中的步骤,通过脱水和酯化反应制备己糖脱水产物,并从己糖脱水产物中分离出HMF和AMF的混合物。与实施例9的区别仅在于,将CrCl3换成等质量的ZnCl2。
实施例12:脱水和酯化反应
按照实施例9中的步骤,通过脱水和酯化反应制备己糖脱水产物,并从己糖脱水产物中分离出HMF和AMF的混合物。与实施例9的区别仅在于,将CrCl3换成等质量的ZnCl2,反应时间由2h延长到180min。
实施例13~18:脱水和酯化反应
按照实施例9中的步骤,通过脱水和酯化反应制备己糖脱水产物,并从己糖脱水产物中分离出HMF和AMF的混合物。与实施例9的区别仅在于,实施例13~18中,分别将CrCl3换成等质量的NiCl2、NiBr2、NiSO4、CoBr2、MnCl2和FeSO4,反应时间由2h延长到180min。
测试例2:脱水和酯化反应收率
按照测试例1中的方法,检测实施例9~18中的HMF收率、AMF收率和总收率,结果见表2。
表2脱水催化剂和反应时间对脱水和酯化效果的影响
数据分析:
(1)根据表2中实施例10~12的数据可以看出,当反应时间处于60~180min范围内时,HMF和AMF的收率随时间变化不大,说明果糖在60min左右几乎完全反应,达到最大的转化率。
(2)根据表2中实施例13~15的数据可以看出,相较于金属氯化物和金属硫酸盐而言,当采用金属溴化物作为脱水催化剂时,具有更好的催化效果。原因在于:一方面,金属阳离子可以与果糖形成离子型配合物[M(OH)x(C6H12O6)]+,促进己醛糖氢转移生成己酮糖和后续成环反应,另一方面,金属阳离子的外层轨道未被完全充满,能与羧酸的C=O键的孤对电子进行配对,使得羰基碳原子上正电荷增加,有利于醇与之结合,对酯化反应有促进作用,而溴离子能提供孤对电子,在果糖质子化和脱水过程中可稳定生成碳正离子中间体,与金属离子发挥协同作用,提高脱水速率和产物选择性,所以,金属溴化物对果糖脱水和酯化反应的催化效果较好,因而HMF和AMF的收率较高。
实施例19:脱水和酯化反应
按照实施例1中的步骤,通过脱水和酯化反应制备己糖脱水产物,并从己糖脱水产物中分离出HMF和AMF的混合物。与实施例1的区别仅在于,将2.0g硫酸氢钠换成2.0g金属改性空心磷酸铌催化剂,并在获得己糖脱水产物后,先过滤,再按照实施例1中的方法从滤液中分离出HMF和AMF的混合物;所述金属改性空心磷酸铌催化剂通过以下步骤制备:
在5L水溶液中加入8g表面活性剂十六烷基三甲基溴化铵(CTAB)、70g正硅酸乙酯(TEOS)及70g粒径为100nm聚苯乙烯微球,于60℃下剧烈搅拌同时以每秒钟1滴的速率滴加1mo/L的NaOH溶液,溶液中不再继续生成沉淀时停止加碱。完成滴定后过滤沉淀,去离子水洗涤至中性,80℃下过夜烘干备用。将20g合成的粉末与7g浓度为85%的磷酸、铌酸钾和Cr(NO3)3混合制成乳浊液,控制Cr、Nb、P的摩尔比为0.3:1:1,转移至水热釜中,于130℃下晶化24小时,完成水热反应后,过滤沉淀并用去离子水洗涤至中性,80℃下过夜烘干。为保证催化剂骨架结构完整,控制升温速率10℃/min,将得到的沉淀在空气氛围中于500℃下焙烧4小时,即制得空心磷酸铌催化剂,记作SiO2@Cr0.3Nb1.0P。
测试例3:脱水和酯化反应收率
按照测试例1中的方法,检测实施例19中的HMF收率、AMF收率和总收率,结果见表3。
表3脱水催化剂对脱水和酯化效果的影响
数据分析:
从表3可以看出,采用金属改性空心磷酸铌催化剂,能够提高HMF和AMF的收率。原因在于:在金属改性空心磷酸铌催化剂中,空心结构内部是活性金属(包括Nb和改性金属Cr)分布较低的位点,在微观上可减少产物与产物、产物与底物、产物与副产物等的碰撞机率,从而降低副反应发生的概率,提高反应选择性,从而提高HMF和AMF的收率。
实施例20:脱水和酯化反应
向5000mL钛材高压反应釜中加入3315g反应液(由300g果糖、3000g醋酸和15g硫酸氢钠的混合物),通入氮气作为保护气,使反应釜的压力达到1.5MPa,在搅拌的同时将反应液加热至140℃,维持反应液在140℃下搅拌反应60min,然后冷却至20℃,得到淡黄色液体产品,即己糖脱水产物。
向己糖脱水产物中加入1mol/L的碳酸钠后静置分层,分离有机层,水相用乙酸乙酯萃取三次,合并萃取相与分离的有机层,并用无水硫酸镁干燥,而后进行过滤、洗涤,母液减压蒸馏脱出醋酸和乙酸乙酯,釜中残留物用二氯甲烷重结晶,并真空干燥,获得HMF和AMF的混合物。
按照测试例1中的方法,测得本实施例中,HMF收率为21.9%,AMF收率为29.3%,总收率为51.2%。
实施例21:氧化反应
按照实施例17中的方法,通过脱水和酯化反应制备己糖脱水产物。取制得的己糖脱水产物(未分离HMF和AMF)200g于500mL高压反应釜中,向其中加入Co/Mn/Br三元催化剂(由四水合醋酸锰、四水合醋酸钴和40wt%溴化氢水溶液)组成的混合物,以脱水和酯化反应时的反应溶剂甲酸为基准,Mn、Co、Br的用量分别为400ppm、400ppm、700ppm),用氮气置换反应釜中的空气,并充氮气至反应釜中的压力达到1MPa,加热至130℃。将反应釜的压力维持在1.6MPa,反应过程中持续不断通入高压空气,恒定的空气流量为3L/min,当反应尾气氧浓度达到21%后(因为氧化反应过程是耗氧的,没有耗氧,说明反应已经结束),将得到固液混合物进行固液分离操作,获得的固体产品。
实施例22~30:氧化反应
按照实施例20中的步骤,通过脱水和酯化反应制备己糖脱水产物,并用制得的己糖脱水产物进行氧化反应。与实施例20的区别仅在于,实施例22~30中,分别按照表3,改变氧化催化剂用量和反应温度。
测试例4:氧化反应收率
取实施例21~30中获得的固体产品,分别用甲醇溶解后进行高效液相色谱分析,检测其中的HMF、AMF、FDCA和5-甲酰基-2-呋喃甲酸含量,而后结合测试例2中测得的实施例17的HMF和AMF含量,计算HMF和AMF的转化率,并以HMF和AMF为基准计算FDCA收率和5-甲酰基-2-呋喃甲酸收率。结果见表4。
表4温度和氧化催化剂用量对氧化效果的影响
数据分析:
(1)从表3可以看出,采用本发明的方法联产HMF、AMF和FDCA,能连续化生产(即在脱水和酯化反应后不分离出HMF和AMF,直接进行氧化反应)的情况下,能获得较高的HMF和AMF转化率以及FDCA收率,其中,中间产物HMF和AMF的转化率能达到100%,FDCA收率可达70%以上。
(2)产物中有少量的5-甲酰基-2-呋喃甲酸说明5-甲酰基-2-呋喃甲酸较难氧化,是氧化反应动力学的控制步骤,通过优化氧化反应条件(反应温度和氧化催化剂用量)可以减少其生成。
本发明中所用原料、设备,若无特别说明,均为本领域的常用原料、设备;本发明中所用方法,若无特别说明,均为本领域的常规方法。
以上所述,仅是本发明的较佳实施例,并非对本发明作任何限制,凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效变换,均仍属于本发明技术方案的保护范围。
Claims (9)
1.一种5-羟甲基糠醛、5-烷酰氧基甲基糠醛和2,5-呋喃二甲酸的联产方法,其特征在于,包括以下步骤:
(1)以己糖为原料,以脂肪酸或者脂肪酸的水溶液为反应溶剂,在脱水催化剂的催化下,进行脱水和酯化反应,获得含有5-羟甲基糠醛和5-烷酰氧基甲基糠醛的己糖脱水产物;所述脱水催化剂为金属改性空心磷酸铌催化剂;所述金属改性空心磷酸铌催化剂包括空心介孔二氧化硅微球骨架,负载于所述骨架中的磷酸铌,以及以M-O-Si形态结合在所述骨架中的改性金属M;所述改性金属M为Cr3+;
(2)在氧化催化剂的催化下,将己糖脱水产物与氧化剂接触,进行氧化反应,而后进行固液分离,获得2,5-呋喃二甲酸。
2.如权利要求1所述的联产方法,其特征在于,步骤(1)中,所述脂肪酸为C1~C6的脂肪酸中的一种或多种。
3.如权利要求2所述的联产方法,其特征在于,步骤(1)中,所述脂肪酸包括甲酸、乙酸和丙酸中的一种或多种。
4.如权利要求1所述的联产方法,其特征在于,步骤(1)中,所述脂肪酸的水溶液中,水含量为1~20wt%。
5.如权利要求1所述的联产方法,其特征在于,步骤(1)中,所述己糖为果糖。
6.如权利要求1所述的联产方法,其特征在于,步骤(1)中,所述脱水催化剂与己糖的质量比为1:(10~1000);所述脱水和酯化反应的温度为50~160℃,时间为5~500min。
7.如权利要求1所述的联产方法,其特征在于,步骤(2)中,所述氧化催化剂为由钴源、锰源和溴源组成的Co/Mn/Br三元催化剂。
8.如权利要求7所述的联产方法,其特征在于,所述Co/Mn/Br三元催化剂中,Co与Mn的摩尔比为0.5~50:1,Br的摩尔量与Co和Mn的总摩尔量之比为0.1~3:1,Co的用量为步骤(1)中反应溶剂质量的50~10000ppm。
9.如权利要求1或7所述的联产方法,其特征在于,步骤(2)中,所述氧化剂为含氧气体,所述氧化反应的温度为50~220℃。
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CN107848995A (zh) * | 2015-04-14 | 2018-03-27 | 杜邦公司 | 用于生产2,5‑呋喃二甲酸及其衍生物以及由其制成的聚合物的方法 |
CN109476623A (zh) * | 2016-07-22 | 2019-03-15 | 伊士曼化工公司 | 呋喃-2,5-二甲酸净化方法 |
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