CN109721631B - Method for preparing fructose through selective isomerization of glucose - Google Patents
Method for preparing fructose through selective isomerization of glucose Download PDFInfo
- Publication number
- CN109721631B CN109721631B CN201910067617.8A CN201910067617A CN109721631B CN 109721631 B CN109721631 B CN 109721631B CN 201910067617 A CN201910067617 A CN 201910067617A CN 109721631 B CN109721631 B CN 109721631B
- Authority
- CN
- China
- Prior art keywords
- fructose
- glucose
- catalyst
- reaction
- selectivity
- 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.)
- Expired - Fee Related
Links
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 title claims abstract description 121
- 229930091371 Fructose Natural products 0.000 title claims abstract description 118
- 239000005715 Fructose Substances 0.000 title claims abstract description 118
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 101
- 239000008103 glucose Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 113
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 57
- 239000002808 molecular sieve Substances 0.000 claims description 33
- 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 33
- 238000010438 heat treatment Methods 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000047 product Substances 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract 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 description 102
- 229960001031 glucose Drugs 0.000 description 102
- 239000006228 supernatant Substances 0.000 description 29
- 239000012295 chemical reaction liquid Substances 0.000 description 14
- 238000004128 high performance liquid chromatography Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- RFSUNEUAIZKAJO-VRPWFDPXSA-N D-Fructose Natural products OC[C@H]1OC(O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-VRPWFDPXSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- -1 carboxylate radical Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000004682 monohydrates Chemical class 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- QGNLHMKIGMZKJX-UHFFFAOYSA-N 3-chloro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(Cl)=C1 QGNLHMKIGMZKJX-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- ZXTFQUMXDQLMBY-UHFFFAOYSA-N alumane;molybdenum Chemical compound [AlH3].[Mo] ZXTFQUMXDQLMBY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 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
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SPFMQWBKVUQXJV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;hydrate Chemical compound O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O SPFMQWBKVUQXJV-BTVCFUMJSA-N 0.000 description 1
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- IIUJCQYKTGNRHH-UHFFFAOYSA-N 2,4-dihydroxybenzamide Chemical compound NC(=O)C1=CC=C(O)C=C1O IIUJCQYKTGNRHH-UHFFFAOYSA-N 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- JCRIDWXIBSEOEG-UHFFFAOYSA-N 2,6-dinitrophenol Chemical compound OC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O JCRIDWXIBSEOEG-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- SKZKKFZAGNVIMN-UHFFFAOYSA-N Salicilamide Chemical compound NC(=O)C1=CC=CC=C1O SKZKKFZAGNVIMN-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011830 basic ionic liquid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000008504 concentrate Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 235000021433 fructose syrup Nutrition 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 235000019534 high fructose corn syrup Nutrition 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229960000581 salicylamide Drugs 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Saccharide Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for preparing fructose by glucose selective isomerization, which adopts supported and unsupported catalysts with high reaction activity, less byproducts and high selectivity, and improves the yield of products and the selectivity of fructose. The method does not need to add a cocatalyst and an organic solvent, adopts water as a reaction solvent, is easy to obtain, environment-friendly and nontoxic, and has the advantages of simple synthesis process, low generation cost, environment-friendliness, no toxicity and the like.
Description
Technical Field
The invention belongs to the technical field of chemical reaction, and particularly relates to a method for preparing fructose by glucose selective isomerization.
Background
The vast majority of the energy and organic chemicals currently required in the world are derived from petroleum, coal and natural gas. However, with the gradual depletion of these non-renewable fossil energy sources and the aim of realizing sustainable development of human beings, renewable and degradable resources are fully utilized and become important industrial raw materials through a chemical synthesis method, which is an effective means for solving the resource depletion and environmental pollution. The biomass raw materials such as glucose, fructose, sucrose, hemicellulose, cellulose, lignin and the like are abundant in natural reserves and low in price, are important biomass resources, can be synthesized into a chemical intermediate with a high added value by a chemical method, and become an important way for reasonably utilizing the biomass resources. Compared with glucose, fructose has higher use value, such as being used as a sweetener in food, being easier to dehydrate than glucose to generate an important platform compound, namely 5-hydroxymethylfurfural (5-HMF), and the like. Although there are many studies on the isomerization of glucose to fructose, there are some disadvantages, such as low yield of sugar, low selectivity of catalyst, and more by-products. Therefore, the invention prepares a high-selectivity supported catalyst for catalyzing glucose to prepare fructose.
Reports on fructose preparation from glucose at home and abroad: qiang Yang and Troy Runge catalyzed glucose to fructose using polyethyleneimine, although fructose yield was as high as 41%, fructose selectivity was only 78%, and glucose could not be selectively catalyzed to fructose. And the preparation process of the catalyst is complex, and salts such as sodium chloride and the like need to be added into the solution, so that the purification treatment at the later stage is not facilitated. (ACS Sustainable chem. Eng.2016,4, 6951-6961-. Siquan Xu et al supported Fe on H-beta zeolite as a carrier to prepare a heterogeneous catalyst Fe-beta molecular sieve catalyst for catalyzing glucose to prepare fructose, and react for 90min at 150 ℃ with water as a solvent to obtain 55% of glucose conversion rate and 22% of fructose yield. Although the conversion of glucose is higher, the fructose yield is lower and the selectivity is only 40%. (Carbohydrate Research 446 (2017) 48-51). The Sn-Beta zeolite prepared by Manuel Moliner et al by isomorphous substitution on large-pore zeolite is used as a catalyst for preparing fructose by using glucose, and water is used as a solvent. Although the catalyst can react at 110 ℃ for 60min to obtain 46% of glucose conversion rate and 29% of fructose yield with fructose selectivity of 63%, Sn metal used by the catalyst is toxic, and the catalyst synthesis process is complicated, which is not favorable for preparing fructose by catalyzing glucose (6164-.
The preparation of multi-stage Sn-Beta molecular sieve by the hydromorphic method is used for catalyzing the isomerization of glucose into fructose. In the catalytic glucose isomerization reaction, when the mole ratio of silicon to tin of the molecular sieve is 100, the reaction temperature is 120 ℃, the reaction time is 2 hours, 40mL of glucose with the mass fraction of 10 percent and the catalyst dosage is 4g, the yield of fructose is up to 47.20 percent, and the catalyst has better regenerability and reusability. But the catalyst uses SnCl4·5H2O is a source of tin and Sn is a toxic metal. And the mass ratio of the catalyst to the substrate is large (about 1:1), and is not suitable for use as a catalyst. (modern food technology, 2017, 33 rd volume, 5 th phase, 155-
The Zhangxiong salt exchange method is used for preparing a series of alkaline functionalized ionic liquids with anions of carboxylate radical, hydroxyl radical, carbonate radical and proline radical to catalyze chemical isomerization of glucose to prepare fructose. When [ Ch ] Pro is used as a catalyst, the optimal reaction condition for preparing fructose by glucose isomerization is that the dosage of the catalyst is 20mol percent of that of glucose; the reaction temperature is 70 ℃; the reaction time is 30 min; under these conditions, the yield and selectivity of fructose were 37.6% and 77.2%, respectively. Although the fructose yield and the selectivity are high, the ionic liquid used by the method is high in preparation cost and cannot be easily separated from the product for recycling. (Zhangxiong. basic ionic liquid catalyzed glucose chemical isomerization preparation of fructose research [ D ]. southern China university of science 2017.)
The inventors of the Muxiangguang and the like adopt one or more phenolic compounds of p-bromophenol, p-chlorophenol, p-fluorophenol, o-chlorophenol, 2,4, 6-trichlorophenol, p-diphenol, p-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 2, 4-dichlorophenol, salicylamide, 4-hydroxy salicylamide, p-methylphenol, p-nitrophenol, 2, 4-dinitrophenol, 2, 6-dinitrophenol and p-methoxyphenol as catalysts, the mass fraction of glucose is 0.1-60%, the mass fraction of the catalysts is 0.1-1.5%, glucose water solution with certain mass fraction is prepared, the catalysts are added into the solution to react under the condition of atmospheric pressure and 70-100 ℃, the reaction is maintained for 1-4 hours at constant temperature, the solution after the reaction is cooled to room temperature, separating by chromatography to obtain fructose solution, and crystallizing to obtain fructose. The yield of the fructose reaches 50 percent, basically no by-product is generated, and the selectivity is more than 96 percent. However, this method uses an organic phenol compound as a catalyst, and has problems that the catalyst is not easily separated from the product, and that the phenol compound is mostly toxic (Sichuan university, chemical method for producing fructose from glucose CN201611069536.4[ P ] 2017-05-31).
The inventor of strength and the like saccharifies, decolors, ion-exchanges, concentrates, mixes, isomerizes and then ion-exchanges the glucose syrup to obtain the high fructose corn syrup with fructose content more than 43 percent. However, the patent does not mention the isomerization method adopted as an enzyme-catalyzed isomerization method or a chemical catalyst-catalyzed isomerization method, so the patent protection scope is too general. (Bengbu Feng Yuan Tushan pharmaceutical Co., Ltd.; a method for preparing fructose syrup from glucose syrup. CN201510490690.8 [ P ]2015-12-23)
The inventor of the invention, such as octogreen and the like, invents a method for preparing fructose by carrying out isomerization reaction on glucose in a high-pressure closed environment in the presence of an acid catalyst and low-carbon alcohol; wherein the acid catalyst is selected from one or more of tungsten salt, aluminum salt, chromium salt, phosphotungstic acid and silicotungstic acid. The method has mild conditions, simple process and high conversion efficiency. However, the method uses low-carbon alcohol, so that the product and the alcohol are difficult to separate; and the used salt-containing acid catalyst is possibly soluble in water and difficult to recover. (university of Anhui Master. method for preparing fructose from glucose. CN201610681628.1.[ P ]2017-01-18)
The inventor invents a method for preparing D-fructose by isomerizing D-glucose, which comprises the following process steps: (1) adding D-glucose, a solvent and a catalyst into a high-pressure reaction kettle to form a reaction system, wherein the mass concentration of the D-glucose is 0.1-99%, and the mass ratio of the catalyst to the D-glucose is 0.01-10; (2) reacting for 0.01-100 hours at the temperature of 20-400 ℃ under the protection of inert gas, and separating and purifying after the reaction is finished to obtain the D-fructose. The invention has the advantages that: the catalyst used in the invention is cheap and easy to obtain, has no toxicity, is green and environment-friendly, and has high product yield. However, the stability of the catalyst is not mentioned. (Nanjing forestry university, a method for preparing D-fructose by D-glucose isomerization, CN201610285364.8 [ P ] 2016-08-10).
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above-mentioned technical drawbacks.
Accordingly, in one aspect of the present invention, the present invention overcomes the deficiencies of the prior art by providing a process for the selective isomerization of glucose to produce fructose.
In order to solve the technical problems, the invention provides the following technical scheme:
a process for the selective isomerization of glucose to fructose comprising: adding glucose, solvent and catalyst, introducing inert gas, heating for reaction, cooling, and centrifuging to obtain fructose.
As a preferred embodiment of the process for producing fructose by selective isomerization of glucose according to the present invention, wherein: the solvent is one or more of water, alcohols, ketones, furans, aromatic hydrocarbons and derivatives thereof, dimethyl sulfoxide, N-methyl pyrrolidone, ketone ammonium, N-methylmorpholine-N-oxide, N-dimethylformamide, N-dimethylacetamide, acetonitrile, diethyl ether, chloroform and ionic liquid; the inert gas is nitrogen; the catalyst is a supported catalyst of metal Mo and/or an unsupported catalyst of metal Mo.
As a preferred embodiment of the process for producing fructose by selective isomerization of glucose according to the present invention, wherein: the catalyst is one or more of metal Mo salt, metal Mo oxide, metal Mo acid, metal Mo organic complex, metal Mo/molecular sieve catalyst, metal Mo/activated carbon catalyst, metal Mo/zirconium dioxide catalyst, metal Mo/silicon oxide catalyst and metal Mo/aluminum oxide catalyst.
As a preferred embodiment of the process for producing fructose by selective isomerization of glucose according to the present invention, wherein: the catalyst is MoO3One or more of Mo/beta molecular sieve and Mo/AC.
As a preferred embodiment of the process for producing fructose by selective isomerization of glucose according to the present invention, wherein: the Mo/beta molecular sieve catalyst has a Mo/Al ratio of 0.1-0.3; the Mo/AC catalyst has a Mo loading of 5 wt%.
As a preferred embodiment of the process for producing fructose by selective isomerization of glucose according to the present invention, wherein: the mass ratio of the glucose to the solvent is 1 (20-60), and the mass ratio of the catalyst to the glucose is 1 (5-20).
As a preferred embodiment of the process for producing fructose by selective isomerization of glucose according to the present invention, wherein: the mass ratio of the glucose to the solvent is 1: 40, and the mass ratio of the catalyst to the glucose is 1: 10.
As a preferred embodiment of the process for producing fructose by selective isomerization of glucose according to the present invention, wherein: adding glucose, a solvent and a catalyst, introducing inert gas, heating for reaction, cooling and centrifuging, wherein the pressure of the inert gas is 1MPa, the heating speed is 5 ℃/min, the temperature is raised to 60-150 ℃, and the reaction time is 30-180 min.
As a preferable embodiment of the process for producing fructose by selective isomerization of glucose according to the present invention, wherein: preparing fructose by using the Mo/beta molecular sieve, heating to 120 ℃, wherein the reaction time is 120 min; the Mo/AC catalyst is used, the temperature is raised to 100 ℃, and the reaction time is 120 min; using the MoO3The catalyst was heated to 75 ℃ and the reaction time was 60 min.
As another object of the present invention, there is provided fructose selectively produced by glucose isomerization.
To solve the above technical problem, according to an aspect of the present invention, the present invention provides the following technical solutions: fructose prepared by a process for the selective isomerisation of glucose to fructose, wherein: preparing fructose by using the Mo/beta molecular sieve, wherein the yield of the fructose is 32.61 percent, and the selectivity of the fructose is 99.92 percent; the yield of fructose by using the Mo/AC catalyst is 28.08 percent, and the selectivity of the fructose by using the Mo/AC catalyst is 99.57 percent; using the MoO3The catalyst had a fructose yield of 25.69% and a fructose selectivity of 99.40.
The invention has the beneficial effects that: the invention provides a method for preparing fructose by glucose selective isomerization, which adopts supported and unsupported catalysts with high reaction activity, less byproducts and high selectivity, and improves the yield of products and the selectivity of fructose. The method does not need to add a cocatalyst and an organic solvent, adopts water as a reaction solvent, is easy to obtain, is environment-friendly and nontoxic, and has the advantages of simple synthesis process, low generation cost, environment friendliness, no toxicity and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 shows the effect of molecular sieve catalysts with Mo/Al ratios of 0.1, 0.3, and 0.6 and H-Beta molecular sieve catalysts on glucose isomerization.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying specific embodiments of the present invention are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
taking a proper amount of ammonium molybdate to be put in a quartz reaction tube, heating the quartz reaction tube to 550 ℃ from room temperature at the speed of 5 ℃/min under the oxygen atmosphere of 60ml/min, then preserving the temperature for 2h, and naturally cooling to the room temperature to prepare the molybdenum oxide catalyst.
Example 2:
preparing a Mo/AC catalyst by adopting an impregnation method: weighing a certain amount of ammonium molybdate according to Mo loading in the Mo/AC catalyst, dissolving the ammonium molybdate in deionized water with a certain volume, adding a certain amount of 60-100-mesh coconut shell activated carbon, stirring overnight, and evaporating water to dryness to obtain a solid. And (3) heating the solid to 500 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, and roasting for 2 hours to obtain the Mo/AC catalyst. The amounts of ammonium molybdate, activated carbon, used to prepare Mo/AC catalysts of varying Mo loadings are given in the table below.
The 60-100 mesh active carbon is selected, and the particle is large, so that the active carbon is easy to separate and recover from the reaction liquid.
TABLE 1 Mo/AC catalyst raw material usage amount with different Mo loading
| Mo Loading amount/wt% | Ammonium molybdate/g | Activated carbon/g |
| 1 | 0.0167 | 1.5020 |
| 5 | 0.0751 | 1.4970 |
| 10 | 0.2005 | 2.0090 |
Example 3:
taking the H-Beta molecular sieve raw material, heating the H-Beta molecular sieve raw material from room temperature to 500 ℃ at the speed of 5 ℃/min in the oxygen atmosphere of 60mL/min, preserving the heat for 2H, and then naturally cooling the H-Beta molecular sieve raw material to the room temperature to obtain the H-Beta molecular sieve catalyst.
The molybdenum/beta catalyst is prepared by calculating the mass of ammonium molybdate according to different molybdenum-aluminum ratios, dissolving the ammonium molybdate by 50ml of pure water, adding a certain amount of molecular sieve according to the mass of the beta molecular sieve calculated according to the different molybdenum-aluminum ratios, stirring the mixture at room temperature for 24 hours, then rotationally evaporating the mixture at 40 ℃ to dry, then drying the dried catalyst in a 105 ℃ oven overnight, then heating the dried catalyst to 550 ℃ at room temperature at the speed of 5 ℃/min under the oxygen of 60ml/min, preserving the heat for 2 hours, and then naturally cooling the dried catalyst to room temperature.
The change in the ratio of molybdenum to aluminum is essentially a change in the loading of the catalyst, and in general, increasing the loading of the catalyst increases the activity of the catalyst, but the higher the loading is not the better. Too high a loading reduces the selectivity of the catalyst to the desired product and produces other by-products.
Example 4:
weighing ferrous sulfate and an H-Beta molecular sieve catalyst according to different molar ratios, placing the ferrous sulfate and the H-Beta molecular sieve catalyst into a round-bottom flask, adding 40mL of deionized water, and soaking and stirring the mixture for 24 hours at room temperature under the protection of 50mL/min nitrogen. And then, carrying out suction filtration on the slurry by using a vacuum pump, washing a filter cake for 2h by using 100mL of deionized water, carrying out suction filtration, repeatedly washing for three times, and placing the filter cake in an oven at 105 ℃ for drying overnight. And (3) putting the dried catalyst into a quartz tube, heating the dried catalyst to 500 ℃ from the normal temperature at the speed of 5 ℃/min under the oxygen atmosphere of 60m L/min, preserving the temperature for 2h, and cooling to the room temperature to obtain the Fe/beta molecular sieve catalyst with different Fe/Al molar ratios.
Example 5:
adding 0.560g of glucose monohydrate, 0.0513g of the molybdenum oxide catalyst prepared in the example 1 and 20mL of water into a 50mL high-pressure reaction kettle, introducing nitrogen to exhaust air, and keeping the nitrogen pressure of 1 MPa; heating to 75 ℃ from room temperature by a temperature controller at the heating rate of 5 ℃/min, and then reacting for 60 min. And after the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating a catalyst and the liquid, fixing the volume of the collected supernatant to 122mL, and then taking a small amount of supernatant to analyze the concentrations of glucose and fructose by using high performance liquid chromatography, so that the conversion rate of glucose is 29.64%, the yield of fructose is 29.35%, and the selectivity of fructose is 99.03%.
Example 6:
0.5528g of glucose monohydrate, 0.0502g of the molybdenum oxide catalyst prepared in example 1 and 20mL of water were placed in a 50mL autoclave, and nitrogen was introduced to purge air and maintain a nitrogen pressure of 1 MPa; heating to 120 ℃ from room temperature at a heating rate of 5 ℃/min by using a temperature controller, and then reacting for 60 min. And after the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating a catalyst and the liquid, fixing the volume of the collected supernatant to 111mL, and then taking a small amount of supernatant to analyze the concentrations of glucose and fructose by using high performance liquid chromatography, so that the conversion rate of glucose is 61.93%, the yield of fructose is 36.79% and the selectivity of fructose is 59.41%.
Example 7:
0.5535g of glucose monohydrate, 0.050g of the molybdenum oxide catalyst prepared in example 1 and 20mL of water are added into a 50mL high-pressure reaction kettle, nitrogen is introduced to exhaust air, and the nitrogen pressure of 1MPa is maintained; heating to 150 deg.C at a temperature rising rate of 5 deg.C/min, and reacting for 60 min. After the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating catalyst and liquid, fixing the volume of the collected supernatant to 180mL, taking a small amount of supernatant, and analyzing the concentrations of glucose and fructose by using high performance liquid chromatography, so that the conversion rate of glucose is 82.03%, the yield of fructose is 20.97%, and the selectivity of fructose is 25.57%.
Because the glucose raw material or the generated fructose generates side reaction at higher temperature, the glucose is converted into a byproduct, and the conversion rate is increased; the product fructose undergoes degradation reaction, and the fructose yield is reduced. Therefore, the proper reaction temperature plays a key role in the conversion of glucose, the yield of fructose and the selectivity of fructose.
Example 8:
0.5575g of glucose monohydrate, 0.0502g of the 10 wt.% Mo/AC catalyst prepared in example 2, and 20mL of water were charged into a 50mL autoclave, and nitrogen was purged to keep the nitrogen pressure at 1 MPa; heating to 120 deg.C at a temperature rising rate of 5 deg.C/min, and reacting for 120 min. After the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating catalyst and liquid, fixing the volume of the collected supernatant to 101mL, and then taking a small amount of supernatant to analyze the concentration of glucose and fructose by using high performance liquid chromatography, so that the conversion rate of glucose is 41.06%, the yield of fructose is 34.54%, and the selectivity of fructose is 84.12%.
Example 9:
0.5588g of glucose monohydrate, 0.0501g of the 10 wt.% Mo/AC catalyst prepared in example 2, and 20mL of water were charged into a 50mL autoclave, and air was purged by introducing nitrogen gas while maintaining a nitrogen pressure of 1 MPa; heating to 100 deg.C at a temperature rising rate of 5 deg.C/min, and reacting for 120 min. And after the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating a catalyst and the liquid, fixing the volume of the collected supernatant to 100mL, and then taking a small amount of supernatant to analyze the concentrations of glucose and fructose by using high performance liquid chromatography, so that the conversion rate of glucose is 31.93%, the yield of fructose is 30.50% and the selectivity of fructose is 95.54%.
Example 10:
0.5560g of glucose monohydrate, 0.050g of the 10 wt.% Mo/AC catalyst prepared in example 2, and 20mL of water were added to a 50mL autoclave, and nitrogen was purged to remove air and maintain a nitrogen pressure of 1 MPa; heating to 75 ℃ from room temperature by a temperature controller at the heating rate of 5 ℃/min, and then reacting for 60 min. And after the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating a catalyst and the liquid, fixing the volume of the collected supernatant to 100mL, and then taking a small amount of supernatant to analyze the concentrations of glucose and fructose by using high performance liquid chromatography, so that the conversion rate of glucose is 12.67%, the yield of fructose is 11.15%, and the selectivity of fructose is 88.03%.
Example 11:
0.5505g of glucose monohydrate, 0.0501g of the 1 wt.% Mo/AC catalyst prepared in example 2, and 20mL of water were charged into a 50mL autoclave, and nitrogen was purged to keep the nitrogen pressure at 1 MPa; heating to 100 deg.C at a temperature rising rate of 5 deg.C/min, and reacting for 120 min. And after the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating a catalyst and the liquid, fixing the volume of the collected supernatant to 100mL, and then taking a small amount of supernatant to analyze the concentrations of glucose and fructose by using high performance liquid chromatography, so that the conversion rate of glucose is 11.37%, the yield of fructose is 11.18%, and the selectivity of fructose is 98.26%.
Example 12:
0.5568g of glucose monohydrate, 0.0502g of the 5 wt.% Mo/AC catalyst prepared in example 2, and 20mL of water were charged into a 50mL autoclave, and nitrogen was purged to keep the nitrogen pressure at 1 MPa; heating to 100 deg.C at a temperature rising rate of 5 deg.C/min, and reacting for 120 min. And after the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating a catalyst and the liquid, fixing the volume of the collected supernatant to 100mL, and then taking a small amount of supernatant to analyze the concentrations of glucose and fructose by using high performance liquid chromatography, so that the conversion rate of glucose is 28.17%, the yield of fructose is 28.08% and the selectivity of fructose is 99.57%.
Example 13:
2.1906g of glucose monohydrate, 0.1919g of the molybdenum oxide catalyst prepared in example 1 and 20mL of water are added into a 50mL high-pressure reaction kettle, nitrogen is introduced to exhaust air, and the nitrogen pressure of 1MPa is maintained; heating to 75 ℃ from room temperature by a temperature controller at the heating rate of 5 ℃/min, and then reacting for 60 min. And after the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating a catalyst and the liquid, fixing the volume of the collected supernatant to 400mL, and then taking a small amount of supernatant to analyze the concentrations of glucose and fructose by using high performance liquid chromatography, so that the conversion rate of glucose is 28.82%, the yield of fructose is 26.85% and the selectivity of fructose is 93.13%.
Example 14:
0.5503g of glucose monohydrate, 0.0106g of the molybdenum oxide catalyst prepared in example 1 and 20mL of water were put into a 50mL high-pressure reaction vessel, and nitrogen was introduced to purge air and maintain a nitrogen pressure of 1 MPa; heating to 75 ℃ from room temperature by a temperature controller at the heating rate of 5 ℃/min, and then reacting for 60 min. After the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating catalyst and liquid, fixing the volume of the collected supernatant to 100mL, taking a small amount of supernatant, and analyzing the concentrations of glucose and fructose by using high performance liquid chromatography, so that the conversion rate of the glucose is 25.84%, the yield of the fructose is 25.69%, and the selectivity of the fructose is 99.40%.
Example 15:
the Mo/AC catalyst after the reaction in example 14 was separated, and the separated Mo/AC catalyst was added to the reaction mixture according to the reaction procedure and the amount of the raw material used in example 14, and reacted again. The conversion of glucose was 14.94%, the yield of fructose was 13.74%, and the selectivity of fructose was 92.00%.
Similarly, the catalyst used in the above reaction was separated and recycled once again, and the conversion of glucose was 8.76%, the yield of fructose was 8.55%, and the selectivity of fructose was 97.63%.
Example 16:
0.5500g of monohydrate glucose, 0.050g of Mo/beta molecular sieve catalyst prepared in example 3 and having Mo/Al ratios of 0.05, 0.1, 0.3, 0.6 and 1 respectively and 20mL of water are added into a 50mL high-pressure reaction kettle, nitrogen is introduced to exhaust air, and the nitrogen pressure of 1MPa is maintained; heating to 120 ℃ from room temperature at a heating rate of 5 ℃/min by using a temperature controller, and then reacting for 120 min. And after the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating the catalyst and the liquid, fixing the volume of the collected supernatant to 100mL, and then taking a small amount of supernatant to analyze the concentrations of glucose and fructose in the supernatant by using high performance liquid chromatography.
The results of glucose conversion, fructose yield and fructose selectivity obtained are shown in the following table, wherein fructose selectivities obtained were very high, reaching 99.92% and 99.30% respectively, when the Mo/Al ratio in the Mo/β molecular sieve catalyst was 0.1 and 0.3.
TABLE 2 influence of Mo/beta molecular sieve catalysts of different Mo/Al on glucose conversion, fructose yield and fructose selectivity
Example 17:
respectively adding 0.050g of Mo/Beta molecular sieve catalyst and H-Beta molecular sieve catalyst which are prepared in example 3 and have Mo/Al ratios of 0.1, 0.3 and 0.6 into 4 parts of 0.5500g of monohydrate glucose, respectively adding 20mL of water, respectively adding into a 50mL high-pressure reaction kettle, introducing nitrogen to exhaust air, and keeping the nitrogen pressure of 0.5 MPa; heating to 140 ℃ from room temperature by a temperature controller at a heating rate of 5 ℃/min, and then reacting for 120 min. And after the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating the catalyst and the liquid, fixing the volume of the collected supernatant to 100mL, and then taking a small amount of supernatant to analyze the concentrations of glucose and fructose in the supernatant by using high performance liquid chromatography.
The results of glucose conversion, fructose yield and fructose selectivity obtained are shown in the following figure, wherein the glucose conversion, fructose yield and fructose selectivity obtained when the Mo/Al ratio in the Mo/beta molecular sieve catalyst is 0.1 are higher, reaching 25%, 6% and 24%, respectively, and are shown in detail in figure 1. As can be seen from FIG. 1, the catalytic effect of the Mo/Beta molecular sieve catalyst is significantly improved compared with that of the H-Beta molecular sieve catalyst.
Example 18:
respectively adding Fe/beta molecular sieve catalysts with Fe/Al ratios of 0.06, 0.1 and 0.18 into 4 parts of monohydrate glucose, respectively adding 25mL of water into 50mL of high-pressure reaction kettle, respectively introducing nitrogen to exhaust air, and keeping the nitrogen pressure of 0.5 MPa; the temperature controller is used for carrying out the reaction from room temperature at the heating rate of 5 ℃/min, and the specific addition amount and the operation parameters are shown in the following table. And after the reaction is finished and the temperature is reduced to room temperature, collecting reaction liquid, centrifugally separating the catalyst and the liquid, fixing the volume of the collected supernatant to 100mL, and then taking a small amount of supernatant to analyze the concentrations of glucose and fructose in the supernatant by using high performance liquid chromatography.
The results of the conversion of glucose, the yield of fructose and the selectivity of fructose obtained are shown in the following table, wherein when the Fe/Al ratio in the Fe/beta molecular sieve catalyst is 0.06 and the addition amount is 30% of the dosage of glucose, the conversion of glucose, the yield of fructose and the selectivity of fructose are higher and respectively reach 36%, 22% and 52%.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (2)
1. A method for preparing fructose by glucose selective isomerization is characterized in that: the method comprises the following steps: adding glucose, a solvent and a catalyst, introducing inert gas, heating for reaction, cooling and centrifuging to obtain fructose, wherein the pressure of the inert gas is 1MPa, and the heating speed is 5 ℃/min;
the solvent is water, and the inert gas is nitrogen;
the catalyst is MoO3One or more of Mo/beta molecular sieve and Mo/AC; wherein, the Mo/beta molecular sieve catalyst has a Mo/Al ratio of 0.1-0.3, and the Mo/AC catalyst has a Mo loading of 5 wt%;
the mass ratio of the glucose to the solvent is 1 (20-60), and the mass ratio of the catalyst to the glucose is 1 (5-20);
preparing fructose by using the Mo/beta molecular sieve, heating to 120 ℃, wherein the reaction time is 120 min; the Mo/AC catalyst is used, the temperature is raised to 100 ℃, and the reaction time is 120 min; using the MoO3The catalyst was heated to 75 ℃ and the reaction time was 60 min.
2. The process for the selective isomerization of glucose to fructose as claimed in claim 1 wherein: the mass ratio of the glucose to the solvent is 1: 40, and the mass ratio of the catalyst to the glucose is 1: 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910067617.8A CN109721631B (en) | 2019-01-24 | 2019-01-24 | Method for preparing fructose through selective isomerization of glucose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910067617.8A CN109721631B (en) | 2019-01-24 | 2019-01-24 | Method for preparing fructose through selective isomerization of glucose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109721631A CN109721631A (en) | 2019-05-07 |
| CN109721631B true CN109721631B (en) | 2022-05-20 |
Family
ID=66299932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910067617.8A Expired - Fee Related CN109721631B (en) | 2019-01-24 | 2019-01-24 | Method for preparing fructose through selective isomerization of glucose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109721631B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121616B (en) * | 2019-12-31 | 2022-08-12 | 中国石油化工股份有限公司 | Method for preparing fructose through glucose chemical isomerization |
| CN111454304B (en) * | 2020-04-30 | 2021-07-20 | 华南理工大学 | Method for preparing fructose by catalyzing glucose isomerization through guanidino ionic liquid |
| CN112028949B (en) * | 2020-08-31 | 2021-09-28 | 安徽师范大学 | Method for preparing fructose by glucose catalysis |
| CN113788865B (en) * | 2021-06-29 | 2024-03-19 | 华南理工大学 | Method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organic metal framework material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837643A (en) * | 2016-05-04 | 2016-08-10 | 南京林业大学 | Method for preparing D-fructose through isomerization of D-glucose |
| CN106032386A (en) * | 2015-03-16 | 2016-10-19 | 中国科学院宁波材料技术与工程研究所 | Catalytic conversion method of aldose into ketose |
-
2019
- 2019-01-24 CN CN201910067617.8A patent/CN109721631B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106032386A (en) * | 2015-03-16 | 2016-10-19 | 中国科学院宁波材料技术与工程研究所 | Catalytic conversion method of aldose into ketose |
| CN105837643A (en) * | 2016-05-04 | 2016-08-10 | 南京林业大学 | Method for preparing D-fructose through isomerization of D-glucose |
Non-Patent Citations (2)
| Title |
|---|
| Asep Bayu，等.Polyoxomolybdates catalysed cascade conversions of cellulose to glycolic acid with molecular oxygen via selective aldohexoses pathways (an epimerization and a [2+4] Retro-aldol reaction).《Catalysis Today》.2018,第332卷28-34. * |
| Polyoxomolybdates catalysed cascade conversions of cellulose to glycolic acid with molecular oxygen via selective aldohexoses pathways (an epimerization and a [2+4] Retro-aldol reaction);Asep Bayu，等;《Catalysis Today》;20180517;第332卷;28-34 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109721631A (en) | 2019-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109721631B (en) | Method for preparing fructose through selective isomerization of glucose | |
| CN105418561B (en) | Method for preparing 2, 5-furandicarboxylic acid by catalyzing fructose through supported bifunctional catalyst | |
| Xia et al. | Synergetic effects of bimetals in modified beta zeolite for lactic acid synthesis from biomass-derived carbohydrates | |
| CN109092309B (en) | Preparation method of catalyst for preparing 5-hydroxymethylfurfural from cellulose | |
| CN111377890B (en) | Method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural | |
| US8835694B2 (en) | Process for transformation of lignocellulosic biomass or cellulose by catalysts based on tin oxide and/or antimony oxide and a metal that is selected from the groups 8 to 11 | |
| Xia et al. | Efficient production of lactic acid from biomass-derived carbohydrates under synergistic effects of indium and tin in In–Sn-Beta zeolites | |
| EP3587431A1 (en) | Method for preparing levoglucosenone by catalytic pyrolysis of biomass | |
| Zuo et al. | Biochar catalysts for efficiently 5-Hydroxymethylfurfural (HMF) synthesis in aqueous natural deep eutectic solvent (A-NADES) | |
| CN105622419B (en) | A kind of method that carbohydrate prepares ethyl glycolate | |
| CN113198492A (en) | Catalyst for preparing pyruvate by photocatalytic oxidation of lactate and method thereof | |
| Shiwei et al. | Selective conversion of glucose into lactic acid with immobilized ytterbium triflate | |
| CN111978164B (en) | Method for preparing aromatic aldehyde by visible light catalytic oxidation of lignin | |
| JP6900801B2 (en) | Method for producing carboxylic acid ester or carboxylic acid | |
| CN114573529B (en) | Method for continuously and efficiently catalyzing poplar to convert furfural | |
| Li | Current approaches of the functional and synergetic catalytic systems for converting renewable carbohydrates into 2, 5-diformylfuran | |
| CN113979852B (en) | Method for preparing lactic acid by catalyzing cellulose with zinc chloride molten salt hydrate at low temperature and normal pressure | |
| CN112062673B (en) | Method for directionally synthesizing methyl lactate by catalytically converting fructose by one-pot method | |
| CN113509931B (en) | Cu (copper) alloy 2 Preparation of O/CuO@CA photocatalyst and application of O/CuO@CA photocatalyst in synthesis of lactic acid by photocatalytic oxidation of xylose | |
| CN114308132A (en) | Protonated CdS-COF-366-M composite photocatalyst and preparation method thereof | |
| JP2013006142A (en) | Catalyst for hydrolysis of plant-base material, and method of manufacturing saccharide | |
| CN115709073B (en) | Preparation method of tin-based catalyst and application of tin-based catalyst in catalyzing biomass sugar to prepare methyl lactate | |
| CN106984361B (en) | Activated carbon-loaded cobalt tetraaminophthalocyanine and application thereof as catalyst in preparation of dimethyl disulfide | |
| CN111925346B (en) | Method for preparing 5-hydroxymethyl furoic acid by utilizing visible light to catalyze selective oxidation | |
| CN114890966B (en) | Catalyst for limonene epoxidation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220520 |