CN116082278A - Method for improving selectivity of preparation of 5-hydroxymethyl-2-furaldehyde - Google Patents
Method for improving selectivity of preparation of 5-hydroxymethyl-2-furaldehyde Download PDFInfo
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- CN116082278A CN116082278A CN202111308323.3A CN202111308323A CN116082278A CN 116082278 A CN116082278 A CN 116082278A CN 202111308323 A CN202111308323 A CN 202111308323A CN 116082278 A CN116082278 A CN 116082278A
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- furaldehyde
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 8
- 229930091371 Fructose Natural products 0.000 claims abstract description 43
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 43
- 239000005715 Fructose Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 230000001105 regulatory effect Effects 0.000 claims abstract description 15
- 150000008040 ionic compounds Chemical class 0.000 claims abstract description 12
- 239000003607 modifier Substances 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 56
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- QVYAWBLDJPTXHS-UHFFFAOYSA-N 5-Hydroxymethyl-2-furfural Natural products OC1=CC=C(C=O)O1 QVYAWBLDJPTXHS-UHFFFAOYSA-N 0.000 claims description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- JFYZBXKLRPWSGV-UHFFFAOYSA-N 1-methyl-3-propyl-2h-imidazole Chemical class CCCN1CN(C)C=C1 JFYZBXKLRPWSGV-UHFFFAOYSA-N 0.000 claims description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 3
- 235000019743 Choline chloride Nutrition 0.000 claims description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 3
- 229960003178 choline chloride Drugs 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- -1 tetraethylpyridinium bromide Chemical compound 0.000 claims description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005303 weighing Methods 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
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The application discloses a method for improving selectivity of preparing 5-hydroxymethyl-2-furaldehyde, which is characterized by comprising the following steps: a reaction system containing fructose, an ion regulator and a solvent is used for preparing 5-hydroxymethyl-2-furaldehyde by dehydration of fructose; wherein the ionic modifier comprises an ionic compound and/or a polar covalent compound; the ionic strength of the reaction system is regulated to be 0.2-10 mol/L by the ionic regulator. The selectivity of HMF can reach more than 95%, and a novel method is provided for preparing HMF with high yield.
Description
Technical Field
The invention relates to a method for improving selectivity of preparing 5-hydroxymethyl-2-furaldehyde, and belongs to the technical field of biomass chemical industry.
Background
5-hydroxymethyl-2-furaldehyde (HMF) is a platform compound that can be prepared from biomass, is a versatile, key intermediate in the biofuel chemistry and petroleum industry, and is one of the "bridges" connecting the petrochemical industry and the biochemical industry. The HMF molecule contains a furan ring, an aldehyde group and a hydroxyl group, has active chemical properties, and can generate hydrogenation, oxidation, esterification, halogenation, polymerization, hydrolysis and other chemical reactions, so that the HMF has great application prospects in the fields of fine chemical engineering, medicines, bio-based high polymer materials and the like.
Due to the active chemical property of HMF, the degradation of HMF, the polymerization of HMF and fructose and the polymerization of HMF and intermediate products exist in the preparation process of HMF; meanwhile, as the fructose is polyhydroxy compound, various side reactions such as self-polymerization of the fructose, polymerization of the fructose and intermediate products and the like exist in the HMF preparation process, so that the problem of low HMF selectivity is generally existed in the HMF preparation process at present. In order to improve the selectivity of HMF in the preparation process, researchers have conducted a great deal of research on reaction solvents and catalysts, but neither documents nor patents for improving the selectivity of HMF preparation by adjusting the ionic strength of a solution have been reported. The method for improving the ionic strength of the solution by adding the ionic strength regulator improves the selectivity in the process of preparing HMF by dehydrating fructose.
Disclosure of Invention
The ionic strength of the solution is regulated mainly by adding ionic compounds and/or polar covalent compounds, so that the hydrogen bond interactions among substances in the solution and the dissociation property of the solution are changed, and the selectivity of HMF is improved; meanwhile, due to the addition of the ionic compound/polar covalent compound, water generated in the reaction process can be removed from the solvent, so that the contact probability of the water and the HMF is reduced, the stability of the HMF is improved, and the selectivity of the HMF is improved.
The invention demonstrates that the selectivity of HMF can be improved by adjusting the ionic strength of the solution by adding ionic compounds and/or polar covalent compounds by the following scheme: due to the difference of ionic strength, the hydrogen bond strength among substances in the solution and the dissociation coefficient of the substances are different, so that the micro dispersity of fructose molecules, the activity states of hydroxyl and hydrogen atoms and the like are regulated, and the effect of improving the selectivity of preparing HMF by dehydrating fructose is achieved.
The present application provides a method for improving selectivity of preparing 5-hydroxymethyl-2-furfural by adjusting ionic strength of a solution, the method comprising:
the ionic strength of the solution is regulated to 0.2-10 mol/L by adding ionic compounds and/or polar covalent compounds, and in the solution with the ionic strength range, different solvents and reaction conditions are combined for carrying out fructose dehydration to prepare 5-hydroxymethyl-2-furaldehyde so as to improve the selectivity of the 5-hydroxymethyl-2-furaldehyde.
As one embodiment of the present application, a reaction system containing fructose, an ion modifier and a solvent is subjected to dehydration of fructose to prepare 5-hydroxymethyl-2-furfural;
wherein the ionic modifier comprises an ionic compound and/or a polar covalent compound; the ionic strength of the reaction system is regulated to be 0.2-10 mol/L by the ionic regulator.
Alternatively, the selectivity of the 5-hydroxymethyl-2-furfural is above 95.8% using HPLC detection.
Alternatively, the selectivity of the 5-hydroxymethyl-2-furfural is above 96.7% using HPLC detection.
Alternatively, the selectivity of the 5-hydroxymethyl-2-furfural was above 97.5% using HPLC detection.
Alternatively, the selectivity of the 5-hydroxymethyl-2-furfural is above 98.5% using HPLC detection.
Alternatively, the selectivity of the 5-hydroxymethyl-2-furfural is above 98.6% using HPLC detection.
Alternatively, the selectivity of the 5-hydroxymethyl-2-furfural is above 99.6% using HPLC detection.
Optionally, the ionic compounds include, but are not limited to, monovalent, divalent, and multivalent organic or/and inorganic compounds.
Optionally, the ionic compounds include monovalent compounds, divalent compounds, and multivalent compounds.
Optionally, the monovalent compound includes, but is not limited to, one or more of sodium chloride, potassium bromide, potassium dihydrogen phosphate, potassium acetate, sodium nitrate, and the like.
Optionally, the monovalent compound regulates the ionic strength of the solution to be 0.2-2 mol/L, and combines ketone or ester as a solvent to prepare the 5-hydroxymethyl-2-furaldehyde at 150-220 ℃. The ketone or ester solvents include, but are not limited to, acetone, methyl isobutyl ketone, ethyl acetate, and the like.
Optionally, the divalent compound includes, but is not limited to, one or more of magnesium sulfate, zinc chloride, copper chloride, magnesium sulfate, disodium hydrogen phosphate, cobalt acetate, sodium sulfite, and the like.
Optionally, the divalent compound regulates the ionic strength of the reaction system to be 0.5-3 mol/L, and combines alcohols as solvents to prepare the 5-hydroxymethyl-2-furaldehyde at 130-200 ℃.
Alternatively, the alcohols include, but are not limited to, methanol, ethanol, isopropanol, n-butanol, sec-butanol, and the like.
Optionally, the multivalent compound includes, but is not limited to, one or more of tin tetrachloride, aluminum chloride, molybdenum nitrate, boron trichloride, ferric sulfate, and the like.
Optionally, the multivalent compound regulates the ionic strength of the reaction system to be 1-10 mol/L, and combines aprotic polar solvent as solvent to prepare 5-hydroxymethyl-2-furaldehyde at 100-180 ℃.
Optionally, the aprotic polar solvent includes, but is not limited to, acetonitrile, dimethylformamide, dimethylsulfoxide, and the like.
Alternatively, the polar covalent compound includes, but is not limited to, tetrabutylammonium chloride, tetramethylammonium bromide, acetic acid, ethanol, hydrochloric acid, aluminum chloride, oxalic acid, and the like.
Optionally, the polar covalent compound regulates the ionic strength of the reaction system to be 5-10 mol/L, and is combined with a quaternary ammonium salt aqueous solution as a solvent to prepare the 5-hydroxymethyl-2-furaldehyde at 120-200 ℃.
Alternatively, the quaternary ammonium salts include, but are not limited to, 1-propyl-3-methylimidazole salt, choline chloride, tetraethylammonium bromide, tetramethylammonium chloride, tetraethylpyridinium bromide, and the like.
As one embodiment of the present application, a reaction system containing fructose, an ion modifier and a solvent is subjected to dehydration of fructose to prepare 5-hydroxymethyl-2-furfural;
wherein the ionic modifier comprises an ionic compound and/or a polar covalent compound; the ionic strength of the reaction system is regulated to be 0.2-10 mol/L by the ionic regulator;
the mass ratio of the fructose to the solvent is 1-5:10. In the method, the mass ratio of the fructose to the solvent is large, the substrate concentration is high, and the method has remarkable mass production benefits.
Optionally, the mass ratio of fructose to solvent is 1:10, 2:10, 3:10, 4:10, 5:10 and ranges between any two ratios.
As one embodiment of the present application, a reaction system containing fructose, an ion modifier, a catalyst and a solvent is subjected to dehydration of fructose to prepare 5-hydroxymethyl-2-furfural;
wherein the ionic modifier comprises an ionic compound and/or a polar covalent compound; the ionic strength of the reaction system is regulated to be 0.2-10 mol/L by the ionic regulator.
Optionally, the catalyst comprises a molecular sieve and a solid acid catalyst.
Optionally, the catalyst comprises HZSM-5 molecular sieves.
Compared with the prior art, the invention has the advantages that:
1) By adjusting the ionic strength in different solvents, the hydrogen bond interaction and dissociation properties among substances in the solution are changed, and the selectivity of HMF is improved;
2) By adjusting the ionic strength of the solution, water generated in the fructose dehydration process can be timely transferred out of the organic solvent, so that the contact probability of the water and HMF is reduced, and the stability of the HMF is enhanced;
3) The invention obviously improves the HMF selectivity, provides a new method for preparing the HMF, and has great promotion effect on the development of furan biochemical industry.
Detailed Description
The present invention will be further described with reference to examples, but the scope of the present invention is not limited to the examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Calculation of the total selectivity of HMF and etherification products in the examples of the present application:
(molar amount of hmf+molar amount of HMF etherification product)/(molar amount of initial fructose-molar amount of remaining fructose) ×100
Selective calculation of HMF in embodiments of the present application:
HMF molar amount/(initial fructose molar amount-residual fructose molar amount) ×100
Example 1:
100g of ethyl acetate and 5g of water are weighed and mixed, hydrochloric acid and sodium dihydrogen phosphate (molar ratio 1:3) are added into the solution to adjust the ionic strength of the solution to 0.2mol/L, the solution is added into a reaction kettle, 20g of fructose is weighed and added into the reaction kettle, sulfuric acid is used for adjusting the pH of the solution to 1.0, stirring is carried out for 30min at room temperature, heating is started to 150 ℃ for reaction for 30min, cooling is carried out, and the concentration of fructose and HMF in the solution is detected by HPLC, wherein the total selectivity reaches 96.7%.
Example 2:
100g of dimethyl sulfoxide is weighed, sodium citrate and aluminum chloride (molar ratio 1:1) are added into the solution, the ionic strength of the solution is adjusted to 5mol/L, the solution is added into a reaction kettle, 20g of fructose is weighed and added into the reaction kettle, the pH of the solution is adjusted to 3.5 by using ferric chloride, the solution is heated to 180 ℃ for 60min and then cooled, and the concentration of HMF and fructose in the solution is detected by using HPLC, so that the selectivity reaches 98.5%.
Example 3:
100g of isopropanol and 10g of water are weighed and mixed uniformly, magnesium sulfate and acetic acid (the molar ratio is 1:2) are added into the solution, the ionic strength of the solution is regulated to 3mol/L, the solution is added into a reaction kettle, 20g of fructose is weighed and added into the reaction kettle, the pH of the solution is regulated to 1.5 by oxalic acid, the solution is heated to 130 ℃ for 120min and then cooled, and the concentration of fructose, HMF and HMF etherification products in the solution is detected by HPLC, so that the total selectivity reaches 95.8%.
Example 4:
100g of 1-propyl-3-methylimidazole salt and 10g of water are weighed and mixed, then the mixture is added into a reaction kettle, after the mixture is heated to 50 ℃, tetramethyl ammonium chloride is added into the solution to adjust the ionic strength of the solution to 6mol/L, 20g of fructose is weighed and added into the reaction kettle, the pH of the solution is adjusted to 2.0 by using hydrochloric acid, the mixture is heated to 120 ℃ and reacted for 120min, then the temperature is reduced, and the concentration of HMF and fructose in the solution is detected by using HPLC, wherein the selectivity reaches 97.5%.
Example 5:
90g of choline chloride and 10g of water are weighed, mixed, added into a reaction kettle, heated to 80 ℃, oxalic acid is added into the solution to adjust the ionic strength of the solution to 7.5mol/L, 20g of fructose is weighed, added into the reaction kettle, heated to 120 ℃ for reaction for 120min, cooled, and the concentration of HMF and fructose in the solution is detected by HPLC, wherein the selectivity reaches 98.5%.
Example 6:
10g of fructose was weighed and dissolved in 100g of dimethyl sulfoxide, the ionic strength of the solution was adjusted to 0.5mol/L using boron trichloride, and the pH of the solution was adjusted to between 1 and 2. The solution was pumped into a tubular reactor using a constant flow pump to react, incubated at 200℃for 60s, and the concentration of HMF and fructose in the solution was checked using HPLC, with a selectivity of 99.6%.
Example 7:
weighing 100g of dimethyl carbonate as a solution 1; 15g of fructose was weighed and dissolved in 5g of water, and the ionic strength of the solution was adjusted to 1mol/L using sodium chloride to prepare solution 2. Solution 1: solution 2 volume ratio=10:1 was fed into a tubular reactor equipped with HZSM-5 (Si/ai molar ratio=300) molecular sieve catalyst using a constant flow pump to react, incubated at 220 ℃ for 60s, and HMF and fructose concentrations in the solution were detected using HPLC, with a selectivity of 98.6%.
Comparative example 1:
100g of ethyl acetate, 20g of fructose and 5g of water are weighed and added into a reaction kettle, after being uniformly mixed, sulfuric acid is used for adjusting the pH value of the solution to 1.0, the solution is heated to 150 ℃ for reaction for 30min and then cooled, and the concentration of HMF and fructose in the solution is detected by HPLC, so that the selectivity reaches 65.5%.
Comparative example 2:
100g of isopropanol and 20g of fructose 10g of water are weighed and added into a reaction kettle, after being uniformly mixed, oxalic acid is used for regulating the pH value of the solution to 1.5, the solution is heated to 130 ℃ for reaction for 120min and then cooled, and HPLC is used for detecting the concentration of fructose HMF and etherified products thereof in the solution, so that the total selectivity reaches 66.7%.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the present invention.
Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.
It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (10)
1. A method for increasing selectivity for the preparation of 5-hydroxymethyl-2-furfural, the method comprising:
a reaction system containing fructose, an ion regulator and a solvent is used for preparing 5-hydroxymethyl-2-furaldehyde by dehydration of fructose;
wherein the ionic modifier comprises an ionic compound and/or a polar covalent compound; the ionic strength of the reaction system is regulated to be 0.2-10 mol/L by the ionic regulator.
2. The method of claim 1, wherein the ionic compound comprises a monovalent compound, a divalent compound, and a multivalent compound.
3. The method of claim 2, wherein the monovalent compound comprises at least one of sodium chloride, potassium bromide, potassium dihydrogen phosphate, potassium acetate, and sodium nitrate.
4. The method according to claim 2, wherein the monovalent compound controls the ionic strength of the reaction system to be 0.2-2 mol/L, and is combined with ketones or esters as solvents to prepare 5-hydroxymethyl-2-furaldehyde at 150-220 ℃;
preferably, the ketone or ester solvent comprises at least one of acetone, methyl isobutyl ketone and ethyl acetate.
5. The method of claim 2, wherein the divalent compound comprises at least one of magnesium sulfate, zinc chloride, copper chloride, magnesium sulfate, disodium hydrogen phosphate, cobalt acetate, and sodium sulfite.
6. The method according to claim 2, wherein the ionic strength of the divalent compound regulating reaction system is in the range of 0.5-3 mol/L, and 5-hydroxymethyl-2-furaldehyde is prepared at 130-200 ℃ by combining alcohols as solvents;
preferably, the alcohol comprises at least one of methanol, ethanol, isopropanol, n-butanol and sec-butanol.
7. The method of claim 2, wherein the multivalent compound comprises at least one of tin tetrachloride, aluminum chloride, molybdenum nitrate, boron trichloride, and ferric sulfate.
8. The method according to claim 2, wherein the ionic strength of the polyvalent compound regulating solution is in the range of 1 to 10mol/L, and the 5-hydroxymethyl-2-furaldehyde is prepared at 100 to 180 ℃ by combining an aprotic polar solvent as a solvent;
preferably, the aprotic polar solvent comprises at least one of acetonitrile, dimethylformamide and dimethyl sulfoxide.
9. The method of claim 1, wherein the polar covalent compound comprises at least one of tetrabutylammonium chloride, tetramethylammonium bromide, acetic acid, ethanol, hydrochloric acid, aluminum chloride, oxalic acid.
10. The method according to claim 1, wherein the ionic strength of the polar covalent compound regulating reaction system is 5-10 mol/L, and the polar covalent compound regulating reaction system is combined with a quaternary ammonium salt aqueous solution as a solvent to prepare 5-hydroxymethyl-2-furaldehyde at 120-200 ℃;
preferably, the quaternary ammonium salt comprises at least one of 1-propyl-3-methylimidazole salt, choline chloride, tetraethylammonium bromide, tetramethylammonium chloride and tetraethylpyridinium bromide.
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| CN109053642A (en) * | 2018-08-23 | 2018-12-21 | 南京工业大学 | Method for converting fructose into 5-hydroxymethylfurfural by inorganic salt-gluconic acid system |
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| CN111315729A (en) * | 2017-09-28 | 2020-06-19 | Ifp 新能源公司 | Method for producing 5-hydroxymethylfurfural in the presence of an organic dehydration catalyst and a chloride source |
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