CN101386611A - A method for preparing 5-hydroxymethylfurfural - Google Patents
A method for preparing 5-hydroxymethylfurfural Download PDFInfo
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- CN101386611A CN101386611A CNA2007100128414A CN200710012841A CN101386611A CN 101386611 A CN101386611 A CN 101386611A CN A2007100128414 A CNA2007100128414 A CN A2007100128414A CN 200710012841 A CN200710012841 A CN 200710012841A CN 101386611 A CN101386611 A CN 101386611A
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- Prior art keywords
- ionic liquid
- biomass
- hmf
- alkyl
- acid
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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 85
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000002028 Biomass Substances 0.000 claims abstract description 44
- 239000002608 ionic liquid Substances 0.000 claims abstract description 42
- 150000002402 hexoses Chemical class 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000011831 acidic ionic liquid Substances 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 239000000460 chlorine Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 28
- -1 alkyl disubstituted imidazole class Chemical class 0.000 claims description 26
- 229930091371 Fructose Natural products 0.000 claims description 24
- 239000005715 Fructose Substances 0.000 claims description 24
- 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 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 10
- 239000011707 mineral Substances 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- WQZGKKKJIJFFOK-PQMKYFCFSA-N alpha-D-mannose Chemical compound OC[C@H]1O[C@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-PQMKYFCFSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 240000008892 Helianthus tuberosus Species 0.000 claims description 5
- 235000003230 Helianthus tuberosus Nutrition 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 229920001202 Inulin Polymers 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims description 4
- 229940029339 inulin Drugs 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 235000009973 maize Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- GEMITLJMEMBDKW-UHFFFAOYSA-N hydrogen sulfate;1h-imidazol-3-ium Chemical compound C1=CNC=N1.OS(O)(=O)=O GEMITLJMEMBDKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 abstract description 4
- 238000013459 approach Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 230000001131 transforming effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000047 product Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000011088 calibration curve Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229940040102 levulinic acid Drugs 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GJTFIKUPXHEIDW-BTVCFUMJSA-N 3-(hydroxymethyl)furan-2-carbaldehyde;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal Chemical compound OCC=1C=COC=1C=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GJTFIKUPXHEIDW-BTVCFUMJSA-N 0.000 description 1
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- 206010000804 Acute hepatic failure Diseases 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
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Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Saccharide Compounds (AREA)
- Furan Compounds (AREA)
Abstract
The invention relates to a method for transforming biomass sugar source into 5-hydroxymethyl-furfural, in particular to a method for preparing the 5-hydroxymethyl-furfural. The method comprises the following steps: using ionic liquid as a solvent, hexose or hexose source biomass as raw material substrates, and 0.5 to 50 percent (relative to the mass of the biomass sugar source) of acidic ionic liquid, inorganic acid or organic acid as a catalyst, and performing the reaction of materials for 1.5 minutes to 23 hours at normal pressure and at a temperature of between 80 DEG C and 100 DEG C to efficiently generate HMF. The method has the advantages of high HMF selectivity, less acid consumption, moderate operating conditions, fast reaction, reusable ionic liquid, simple process, environment protection and the like, and opens up a new approach for preparing commodity chemicals and replacing fuels starting from renewable biological resources.
Description
Technical field
The present invention relates to the preparation of 5 hydroxymethyl furfural, specifically a kind of method that in ionic liquid, biomass sugar source (hexose or be rich in the biomass of hexose) efficiently is converted into 5 hydroxymethyl furfural (HMF).
Background technology
Utilize biomass energy to replace oil and prepare the feasible program that chemical preparations, plastic cement and fuel are the crises of solution world energy sources, become the research focus of domestic and international resource and energy field from the research of the general chemical of reproducible Biological resources preparation.Abundant biomass resource can change into valuable intermediate compounds such as furfural, HMF and levulinic acid under proper condition, they have high reaction activity, can synthesize a series of valuable chemical, therefore be regarded as new hardware and software platform compound recently based on biomass resource.
Wherein HMF is faint yellow needle-like crystal, is soluble in ethanol, acetone, ethyl acetate; Be dissolved in ether, benzene, chloroform; Be slightly soluble in sherwood oil; 30 ℃～34 ℃ of fusing points, 291 ℃ of boiling points.HMF is a kind of multiduty intermediate product, can transform from natural carbohydrate (comprising fructose, glucose, semi-lactosi, seminose, sorbose, sucrose and starch) to obtain.Specifically, HMF is the converted product of hexose.Contain a carbonyl in its molecule, a hydroxyl, activity is very high, and the hydrogen atom on its different functional groups has different activity, participates in reaction so not only can be used as alcohol but also can be used as aldehyde.
Since 19th century, the chemist has just carried out research extensively and profoundly to the application of HMF.Up to now, HMF and derivative thereof are widely used in every field.HMF is the important intermediate of synthesizing furan polymer and levulinic acid in the fine chemistry industry; By selective oxidation reaction, HMF can prepare the furans dioctyl phthalate, this be produce polyester (as PET, good substitute [Pentz, the K.W. of raw material terephthalic acid PBT); Br.Pat.2131014,1984; Werpy, T., Petersen, G., Top Value Added Chemicalsfrom Biomass, 2004; Http:// www.osti.gov/bridge.]; HMF is as sterilant, sterilant [Miyazawa, M. in agrochemistry; Anzai, J.; Fujioka, J.; Isikawa, Y.Natural ProductResearch, 2003,17 (5): 337.]; In electrochemistry, be used as corrosion inhibitor; In cosmetic industry, be used as odor additive.HMF still is important medicine intermediate, is neurocyte [Li Lin, the Wei Haifeng of the multiple medicine of feedstock production to repairing damage with HMF and derivative thereof, Zhang Lan, Zhao Ling, Chu Jin, the 5 hydroxymethyl furfural class is used to prepare the purposes of neural system medication, CN1565438,2005], treatment cardiovascular disorder [tight Yongqing, Zhu Danni, Chen Ting, Xia Yun, Li Zhiming, horse Xiao Hong, the medicinal use of 5 hydroxymethyl 2 furaldehyde, CN1182589,1998], the treatment septicemia, acute pneumonia, acute hepatic failure [Pu Wenying, the pharmaceutical use of 5 hydroxymethyl furfural, CN1704050,2005] etc. significant curative effect all arranged.Recently, HMF is considered to be linked in the bridge between carbohydrate resource and the petroleum industry, because with obtain after the deoxidation of HMF selective hydration 2,5-dimethyl furfural is a kind of high-grade fuel, its energy density is higher by 40% than ethanol, and volatility is very little, demonstrates the great potential [Rom á n-Leshkov, the Y. that substitute fossil oil; Barrett, C.J.; Liu, Z.Y.; Dumesic, J.A.Nature, 447,982.].
But up to the present, natural biomass sugar source efficiently being converted into HMF and derivative thereof still is a challenge.People have done to go deep into systematic research to the work that is converted into HMF by hexose, respectively [Rapp, K.M.USPat.4740605,1987.], aprotic solvent (as DMSO) [V Ge Luxin, N He Lun, G A James Halliday, CN1555368A, 2004 in water; Musau, R.M.; Munavu, R.M.Biomass, 1987,13,67.] and diphasic system (water/methyl iso-butyl ketone (MIBK)) [Mercadier, D.L.; Gaset, R.A.and Gorrichon, J.P.J.Chem.Technol.Biotechnol., 1981,31,489.] in attempted various catalyzer, for example organic acid (oxalic acid, toxilic acid), mineral acid (sulfuric acid, hydrochloric acid), salt (MgCl
2), organic catalyst (LaCl
3) and solid acid catalyst (ion exchange resin, various molecular sieve, VPO
4).Yet all these catalyst system all have remarkable defective.In water, the dehydration reaction of fructose does not have selectivity, except producing HMF, has also generated a large amount of by products; Though people such as Carlini use different solid catalysts under the lesser temps (＜370K) in the aqueous solution, prepare HMF with fructose, obtain to be higher than 80% selectivity, the transformation efficiency of fructose is low, only is 25%～50%[Carlini, C.; Patrono, P.; Galletti, A.M.R et al.Appl.Catal., A, 2004,275,111.Carlini, C.M.; Giuttari, G.; Raspolli, A.; Et al.Appl.Catal., A, 1999,183,295.]; In the two-phase catalyst system, need to use the HMF that produces in the continuous aqueous phase extracted reaction of water-fast organic solvent, because percentage extraction is low, so will use a large amount of organic solvents, energy consumption height [Mercadier, D.; Rigal, L.; Gaset, A.et al.J.Chem.Technol.Biotechnol., 1981,31,489.Peniston, Q.P.U.S.Pat., 2 750 394,1956.].Some investigators find, in high boiling organic solvent (as DMSO), and in the mixed system of polyoxyethylene glycol (PEG) and water, make spent ion exchange resin make catalyzer, fructose can high yield (〉 90%) be converted into HMF, yet, in this kind solvent, not easily separated [Nakamura, the Y. of product; And Morikawa, S.Bull.Chem.Soc.Jpn., 1980,53,3705; Musau, R.M.; Munavu, R.M.Biomass, 1987,13,67.].
Recently, people such as the scientist Zhao of USDOE Pacific Northwest National Laboratory (Pacific Northwest NationalLaboratory is called for short PNNL) and Zhang have been significant research work [Zhao, H. in this respect; Holladay, J.E.; Zhang, Z.C.; Et al.Science, 2007,316,1597.], they have attempted multiple Lewis acid metal catalyst, found that, and in ionic liquid (ionic liquid), CrCl
2Catalyzer can change into carbohydrates such as fructose and glucose hydroxymethylfurfural (HMF) effectively, for follow-up study good reference is arranged.But this method remain some economically with environment on defective, these processes adopt ionic liquids not recycle, cost is also higher, need reduce effectively that product separates, the cost of purifying, uses chromium-based catalysts to be an impediment to the Green Chemistry principle.
In a word, existing HMF preparation method or cost are too high, need further to reduce its production cost; Reaction preference is low, needs to seek better catalyst system.And up to now, be not seen in report as yet for the situation that studies in great detail of in ionic liquid, using the dehydration of protonic acid catalysis hexose to produce HMF.
Summary of the invention
The object of the present invention is to provide a kind of method that in ionic liquid, hexose or the biomass efficient that is rich in hexose is converted into 5 hydroxymethyl furfural (HMF), its HMF yield height, production cost is low, and solves the ion liquid problem that recycles.
For achieving the above object, the technical solution used in the present invention is:
A kind of method for preparing 5 hydroxymethyl furfural, with hexose or hexose source biomass is the raw material substrate, with the ionic liquid is solvent, hexose or the biomass that contain hexose are dissolved in the ion liquid solvent, with mineral acid, organic acid or the acidic ion liquid that accounts for biomass sugar source quality 0.5%-50% is catalyzer, reacts 1.5 minutes～23 hours in 80 ℃～100 ℃ under normal pressure; In the reaction process, with the productive rate of spectrophotometer monitoring HMF.After reaction finished, HMF realized separating with the method for ionic liquid-catalyzed system by column chromatography, continues to add substrate reactions in the ionic liquid of recovery, realizes recycling of catalyst system.
Described ion liquid solvent is for having the short-chain alkyl disubstituted imidazole class ionic liquid and the alkyl pyridine type ionic liquid of dissolving power to the hexose source biomass, its structural formula is shown below:
Formula 1. alkyl imidazole type ionic liquid formulas 2. alkyl pyridine type ionic liquids
Wherein, for alkyl imidazole ionic liquid, substituent R
1Be C
1-C
4Short-chain alkyl, substituent R
2Be C
2-C
12Short-chain alkyl, anionicsite is Cl
-, Br
-, can independent assortment between them; For alkyl pyridine type ionic liquid, substituent R
3Be C
2-C
8Short-chain alkyl, anionicsite is Cl
-, Br
-, can independent assortment between them.
Ionic liquid specifically can be: 1-methyl-3-alkyl imidazole bromine [C
nMIm] Br (n=2-12), 1-methyl-3-alkyl imidazole chlorine [C
nMIm] Cl (n=2-12), 1-ethyl-3-alkyl imidazole bromine [C
nEIm] Br (n=2-12), 1-ethyl-3-alkyl imidazole chlorine [C
nEIm] Cl (n=2-12), 1-propyl group-3-alkyl imidazole bromine [C
nPIm] Br (n=2-12), 1-propyl group-3-alkyl imidazole chlorine [C
nPIm] Cl (n=2-12), 1-butyl-3-alkyl imidazole bromine [C
nBIm] Br (n=2-12), 1-butyl-3-alkyl imidazole chlorine [C
nBIm] Cl (n=2-12), alkyl pyridine chlorine [C
nPy] Cl (n=2-8) or alkyl pyridine bromine [C
nPy] Br (n=2-8).
Described mineral acid is the commercially available vitriol oil (mass concentration 98%), concentrated hydrochloric acid (mass concentration 36%), concentrated nitric acid (mass concentration 65%) or strong phosphoric acid (mass concentration 85%); Organic acid is acetate (mass concentration 99%), toxilic acid (mass concentration 99.5%); Acidic ionic liquid catalysts is homemade 1-methyl-3-butyl imidazole hydrosulfate [C
4MIm] HSO
4, 1-methyl-3-4-sulfo group-butyl) imidazole bisulfate [SBMIm] HSO
4
Described hexose source biomass is fructose, glucose, semi-lactosi, seminose or sorbose, or contains the biomass of fructose, glucose, semi-lactosi, seminose or sorbose, as: maize treacle, sucrose, inulin, jerusalem artichoke powder, starch etc.
The mass percent of described biomass sugar source and solvent is 10%～200%;
When adopting acidic ion liquid to be catalyzer, its usage quantity is 1%～20% of a biomass sugar source quality;
When adopting mineral acid to be catalyzer, its usage quantity is 0.5%～50% of a biomass sugar source quality;
When adopting organic acid to be catalyzer, its usage quantity is 10%～50% of a biomass sugar source quality.
Reacted HMF can realize separating with ionic liquid-catalyzed system by column chromatography method,
With petrol ether/ethyl acetate=4:2 (v/v) is that leacheate obtains HMF; After product HMF separates, for reclaiming, the leacheate sharp separation obtains ionic liquid with methyl alcohol.
The ionic liquid that described recovery obtains can directly be used for secondary response down as reaction solvent, realizes ion liquid recycle.
The present invention has following advantage:
1. compare with the method that traditional concentrated acid dehydration prepares HMF, the acid consumption significantly reduced when the present invention used mineral acid, and the catalyzer cost is low, and less demanding to the erosion resistance of reactor, speed of response is fast;
With the traditional aqueous solution in the reacting phase ratio, transformation efficiency and selectivity that this method is produced HMF significantly improve, and operational condition gentleness, the simple cost of technology are low, environmental friendliness, extent of reaction is followed the tracks of easily and control, be close to quantitative conversion with the fructose sources during for raw material is HMF;
3. compare with the two-phase catalyst system, this method has been avoided the use of organic solvent, operational condition gentleness, environmental friendliness;
4. compare with the Chinese patent CN1555368A that E.I.Du Pont Company applies for, the solvent that the present invention uses is ionic compound, in fructose being converted into HMF reaction, have the reaction times significantly shorten, advantage such as product yield height, catalyzer and solvent load are few, and the solvent that uses in E.I.Du Pont Company's patent is nonionic compound, as methyl-sulphoxide, N,N-DIMETHYLACETAMIDE, tetramethylene sulfone, N-Methyl pyrrolidone, tetramethyl-urea, tributyl phosphate, dimethyl formamide and their combination.
5. compare with the nearest research work of PNNL, the present invention need not to use the chromium metal that is an impediment to the Green Chemistry principle catalyst based, and ionic liquid-catalyzed system can be recycled, and has reduced cost, and product separation method is simple.
6. the present invention can be applicable to multiple biomass sugar source, be specially: fructose, glucose, semi-lactosi, seminose, sorbose and the biomass that contain fructose, glucose, semi-lactosi, seminose or sorbose, as: maize treacle, sucrose, inulin, jerusalem artichoke powder and starch etc.
In a word, compared with prior art, the present invention uses the acid of catalytic amount to be catalyzer under mild conditions, and efficient conversion of biomass sugar source prepares HMF, and technology is simple, environmental friendliness, solvent are easy to recycle, product is easy to separate, cost is low.The present invention has opened up new way for making full use of the lignocellulose resource, has great application prospect aspect biomass energy and the bio-based chemical obtaining.
Embodiment
Ion liquid solvent preparation: reference literature (Yin, D.H.; Li, C.; Li, B.; Et al.Adv.Synth.Catal.2005,347,137.Webb, P.B.; Sellin, M.F.; Kunen, T.E.; Et al.J.Am.Chem.Soc.2003,125,15577.Noda, A.; Watanabe, M.Electrochimica Acta.2000,45,1265.) and patent (WO 00/16902) preparation and purifying tens kinds hexose or the biomass that contain hexose had the ionic liquid of dissolving power by force, be used for the enforcement of patent of the present invention.
Ionic-liquid catalyst [C
4MIm] HSO
4, [SBMIm] HSO
4Preparation with reference to patent (WO00/16902).
Hexose or hexose source biomass selectively dewatering system HMF: hexose or the biomass that contain hexose are dissolved in the ion liquid solvent, acidic ion liquid, mineral acid or organic acid with 0.5%-50% (with respect to the quality of substrate) are catalyzer, react 1.5 minutes～23 hours in 80 ℃～110 ℃ under normal pressure; In the reaction process, with the productive rate of spectrophotometer monitoring HMF.After reaction finished, the method by column chromatography can be separated product HMF in HMF and the ionic liquid-catalyzed system with ionic liquid, then, continue to add substrate reactions in the ion liquid system, realizes recycling of catalyst system.
Present method prepares HMF with hexose source selectively dewatering, and gained HMF productive rate is up to 98%.
Embodiment 1:
With 4 gramion liquid [C
4MIm] Cl adds in 10 milliliters of round-bottomed flasks, is heated to 80 ℃, slowly adds 0.4 gram fructose under the vigorous stirring, is stirred to dissolving.At this moment, be that 0.02 concentrated hydrochloric acid that restrains adds in the reaction system fast with quality, reacted stopped reaction 8 minutes in 80 ℃ under the normal pressure.Get 0.01 gram sample with cold water cancellation immediately reaction, with the NaOH of 0.05mol/L this sample pH value value is transferred to 7.0, obtained aqueous solution is 97% in the 282nm place with ultraviolet-visible pectrophotometer mensuration HMF productive rate by calibration curve method.
(with silica gel is filler, and leacheate is: petrol ether/ethyl acetate=4:2 (v/v)), obtain 0.269 gram dark yellow liquid product HMF, isolated yield is 96% by column chromatography for separation with part remaining in the reaction system.Product is through spectral analysis of the nuclear magnetic resonance, and data are:
1H NMR (400MHz, CDCl
3): δ 9.49 (s, 1H), 7.20 (d, 1H), 6.48 (d, 1H), 4.65 (s, 2H);
13C NMR (100 MHz, CDCl
3): δ 178.2,161.6,152.5,123.9,110.4,57.7, and the affirmation product is HMF.
Embodiment 2:
With 4 gramion liquid [C
4MIm] Cl adds in 10 milliliters of round-bottomed flasks, is heated to 80 ℃, slowly adds 4 gram fructose under the vigorous stirring, is stirred to dissolving.At this moment, be that 0.2 concentrated hydrochloric acid that restrains adds in the reaction system fast with quality, reacted 25 minutes in 80 ℃ under the normal pressure.Reaction finishes, and with cold water cancellation reaction, with the NaOH of 0.05mol/L reacting liquid pH value is transferred to 7.0, and obtained aqueous solution is 77% in the 282nm place with ultraviolet-visible pectrophotometer mensuration HMF productive rate by calibration curve method, and isolated yield is 75%.
Embodiment 3:
With 4 gramion liquid [C
4MIm] Cl adds in 10 milliliters of round-bottomed flasks, is heated to 80 ℃, slowly adds 8 gram fructose under the vigorous stirring, is stirred to dissolving.At this moment, be that 0.4 concentrated hydrochloric acid that restrains adds in the reaction system fast with quality, reacted 120 minutes in 80 ℃ under the normal pressure.Reaction finishes, and with cold water cancellation reaction, with the NaOH of 0.05mol/L reacting liquid pH value is transferred to 7.0, and obtained aqueous solution is 58% in the 282nm place with ultraviolet-visible pectrophotometer mensuration HMF productive rate by calibration curve method, and isolated yield is 55%.
Embodiment 4:
Other processing condition and experimental procedure are with embodiment 2, but functional quality is that 0.02 concentrated hydrochloric acid that restrains is a catalyzer, reacts 3 hours in 80 ℃ under the normal pressure.Reaction finishes, and with cold water cancellation reaction, with the NaOH of 0.05mol/L reacting liquid pH value is transferred to 7.0, and obtained aqueous solution is 79% in the 282nm place with ultraviolet-visible pectrophotometer mensuration HMF productive rate by calibration curve method, and isolated yield is 76%.
Embodiment 5:
Other processing condition and experimental procedure are with embodiment 2, but functional quality is [SBMIm] HSO of 0.04 gram
4Be catalyzer, reacted 3 hours in 80 ℃ under the normal pressure.Reaction finishes, and with cold water cancellation reaction, with the NaOH of 0.05mol/L reacting liquid pH value is transferred to 7.0, and obtained aqueous solution is 74% in the 282nm place with ultraviolet-visible pectrophotometer mensuration HMF productive rate by calibration curve method, and isolated yield is 70%.
Embodiment 6:
With 4 gramion liquid [C
4MIm] Cl adds in 10 milliliters of round-bottomed flasks, is heated to 80 ℃, slowly adds 6 gram fructose under the vigorous stirring, is stirred to dissolving.At this moment, be that 0.15 concentrated hydrochloric acid that restrains adds in the reaction system fast with quality, reacted 110 minutes in 80 ℃ under the normal pressure.Reaction finishes, and with cold water cancellation reaction, with the NaOH of 0.05mol/L reacting liquid pH value is transferred to 7.0, and obtained aqueous solution is 65% in the 282nm place with ultraviolet-visible pectrophotometer mensuration HMF productive rate by calibration curve method, and isolated yield is 64%.
Embodiment 7～16:
Other processing condition and experimental procedure are with embodiment 1, but use other acid of different mass to be catalyzer, the cancellation reaction the results are shown in table 1 under different time, and this tabular has gone out the productive rate (spectrophotometric determination) of kind, quality, reaction times and the HMF of catalyzer.
HMF result is produced in the reaction of table 1 different sorts catalyst fructose selectively dewatering
| Project | Catalyzer | Catalyst quality (g) | Reaction times (min) | HMF productive rate (%) |
| Embodiment 7 | Hydrochloric acid | 0.01 | 40 | 98 |
| Embodiment 8 | [SBMIm]HSO 4 | 0.08 | 7 | 90 |
| Embodiment 9 | [SBMIm]HSO 4 | 0.04 | 26 | 91 |
| Embodiment 10 | [C 4MIm]HSO 4 | 0.04 | 30 | 80 |
| Embodiment 11 | Sulfuric acid | 0.01 | 12 | 76 |
| Embodiment 12 | Nitric acid | 0.02 | 20 | 82 |
| Embodiment 13 | Toxilic acid | 0.02 | 50 | 88 |
| Embodiment 14 | Toxilic acid | 0.20 | 20 | 93 |
| Embodiment 15 | Phosphoric acid | 0.01 | 1380 | 71 |
| Embodiment 16 | Acetate | 0.01 | 1380 | 73 |
Embodiment 17:
With 2 gramion liquid [C
4MIm] Cl adds in 10 milliliters of round-bottomed flasks, is heated to 80 ℃, slowly adds 2 gram fructose under the vigorous stirring, is stirred to dissolving.At this moment, be in the concentrated hydrochloric acid adding reaction system of 0.1 gram with quality, reacted 40 minutes in 80 ℃ under the normal pressure.Stopped reaction is got 0.01 gram sample and is used for the ultraviolet-visible pectrophotometer analysis, and measuring the HMF productive rate is 80%.(with silica gel is filler, and leacheate is: petrol ether/ethyl acetate=4:2 (v/v)), obtain 1.085 gram dark yellow liquid product HMF, isolated yield 78% by column chromatography for separation with part remaining in the reaction system.
After product separated, for the leacheate sharp separation goes out ionic liquid, the following 45 ℃ of rotary evaporations of vacuum condition were removed methyl alcohol with methyl alcohol, 80 ℃ of vacuum-drying is 2 hours then, obtain reclaiming ionic liquid 1.98 grams, can be directly used in down secondary response, realize ion liquid recycle.The amount of this catalyst system can further be optimized and amplify.The recycle method of other acid/ionic liquid-catalyzed system is similar with it.
Embodiment 18:
Embodiment 17 is reclaimed the ionic liquid [C that obtains
4MIm] Cl (1.98 gram) is heated to 80 ℃ in 10 milliliters of round-bottomed flasks, slowly add 2 gram fructose under the vigorous stirring, is stirred to dissolving.At this moment, be in the concentrated hydrochloric acid adding reaction system of 0.1 gram with quality, reacted 40 minutes in 80 ℃ under the normal pressure.Stop reaction, get 0.01 gram sample and be used for the ultraviolet-visible pectrophotometer analysis, measuring the HMF productive rate is 78%.Part remaining in the reaction system by column chromatography for separation (petrol ether/ethyl acetate=4:2 (v/v)), is obtained 1.078 gram dark yellow liquid product HMF, isolated yield 77%.
Embodiment 19～24:
Other processing condition and experimental procedure are with embodiment 1, but use different ionic liquid [C
4MIm] Br, [C
2MIm] Br, [C
6MIm] Cl, [C
6MIm] Br, [C
4Py] Cl, [C
2Py] Cl etc. reacts (wherein with [C for solvent
4Py] when Cl is solvent temperature of reaction be 100 ℃), in different time cancellation reaction, partial results is listed in table 2.This tabular has gone out the productive rate (spectrophotometric determination) of ionic liquid kind, hydrochloric acid usage quantity, reaction times and HMF.
Hydrochloric acid catalysis fructose selectively dewatering produces HMF result in table 2 different ionic liquid
| Project | Ionic liquid | Hydrochloric acid usage quantity (g) | Time (min) | HMF productive rate (%) |
| Embodiment 19 | [C 4MIm]Br | 0.02 | 1.5 | 90 |
| Embodiment 20 | [C 4MIm]Br | 0.02 | 11.5 | 95 |
| Embodiment 21 | [C 2MIm]Br | 0.02 | 2 | 88 |
| Embodiment 22 | [C 4Py]Cl | 0.01 | 10 | 97 |
| Embodiment 23 | [Amim]Cl | 0.02 | 25 | 96 |
| Embodiment 24 | [C 6MIm]Cl | 0.02 | 360 | 85 |
Embodiment 25～32:
With 4 gramion liquid [C
4MIm] Cl adds in 10 milliliters of round-bottomed flasks, is heated to temperature of reaction, slowly adds the biomass sugar source of 0.4 gram different material under the vigorous stirring, is stirred to dissolving.At this moment, add the concentrated hydrochloric acid of different mass in the reaction system fast, in design temperature reaction different time, cancellation reaction then, NaOH with 0.05mol/L transfers to 7.0 with reacting liquid pH value, obtained aqueous solution is measured HMF productive rate in the 282nm place with ultraviolet-visible pectrophotometer by calibration curve method, the results are shown in table 3.This tabular has gone out the productive rate (spectrophotometric determination) of ionic liquid kind, hydrochloric acid usage quantity, reaction times and HMF.
Table 3[C
4MIm] the different biomass sugar of hydrochloric acid catalysis source selectively dewatering produces HMF result among the Cl
| Project | Raw material | Temperature of reaction (℃) | Hydrochloric acid quality (g) | Reaction times (min) | HMF productive rate (%) |
| Embodiment 25 | Inulin | 80 | 0.04 | 10 | 56 |
| Embodiment 26 | Sucrose | 80 | 0.02 | 43 | 56 |
| Embodiment 27 | The jerusalem artichoke powder | 100 | 0.04 | 60 | 30 |
| Embodiment 28 | The jerusalem artichoke powder | 80 | 0.04 | 300 | 37 |
| Embodiment 29 | Glucose | 100 | 0.12 | 60 | 31 |
| Embodiment 30 | Semi-lactosi | 100 | 0.12 | 45 | 32 |
| Embodiment 31 | Seminose | 100 | 0.12 | 180 | 23 |
| Embodiment 32 | W-Gum | 100 | 0.12 | 240 | 27 |
By above embodiment as can be seen: the present invention for a kind of be solvent with the ionic liquid, be catalyzer with acidic ion liquid, mineral acid or organic acid, the completely new approach of HMF is produced in the biomass highly selective dehydration that realizes hexose or contain hexose.With ionic liquid [C
4MIm] Cl is solvent, is catalyzer with the concentrated hydrochloric acid of 5wt%, 80 ℃ of reactions 8 minutes, fructose can reach 97% to the transformation efficiency of HMF; The conversion in other biomass sugar source has also shown certain effect.Compared with prior art, the present invention has remarkable advantage: transformation efficiency and HMF selectivity significantly improve, catalyst levels is few, operational condition is gentle, speed of response is fast, technology is simple, cost is low; Avoided the use of organic solvent, environmental friendliness; Ionic liquid-catalyzed system can be recycled; Product separation method is simple.
The present invention is efficiently utilizing the lignocellulose resource, obtains bioenergy and the bio-based field of chemicals has broad application prospects, for having opened up new way from reproducible Biological resources general chemical of preparation and alternative fuel.
Claims (9)
1. method for preparing 5 hydroxymethyl furfural, it is characterized in that: be solvent with the ionic liquid, with hexose or hexose source biomass is the raw material substrate, with acidic ion liquid, mineral acid or organic acid with respect to the 0.5%-50% of sugared source biomass quality is catalyzer, under normal pressure,, efficiently generate HMF in 80 ℃～100 ℃ reactions 1.5 minutes～23 hours.
2. in accordance with the method for claim 1, it is characterized in that: described ion liquid solvent is for having the short-chain alkyl disubstituted imidazole class ionic liquid and the alkyl pyridine type ionic liquid of dissolving power to the hexose source biomass, its structural formula is shown below:
Formula 1. alkyl imidazole type ionic liquid formulas 2. alkyl pyridine type ionic liquids
Wherein, for alkyl imidazole ionic liquid, substituent R
1Be C
1-C
4Short-chain alkyl, substituent R
2Be C
2-C
12Short-chain alkyl, anionicsite is Cl
-, Br
-, can independent assortment between them; For alkyl pyridine type ionic liquid, substituent R
3Be C
2-C
8Short-chain alkyl, anionicsite is Cl
-, Br
-, can independent assortment between them.
3. it is characterized in that in accordance with the method for claim 2: described ionic liquid is 1-methyl-3-alkyl imidazole bromine [C
nMIm] Br (n=2-12), 1-methyl-3-alkyl imidazole chlorine [C
nMIm] Cl (n=2-12), 1-ethyl-3-alkyl imidazole bromine [C
nEIm] Br (n=2-12), 1-ethyl-3-alkyl imidazole chlorine [C
nEIm] Cl (n=2-12), 1-propyl group-3-alkyl imidazole bromine [C
nPIm] Br (n=2-12), 1-propyl group-3-alkyl imidazole chlorine [C
nPIm] Cl (n=2-12), 1-butyl-3-alkyl imidazole bromine [C
nBIm] Br (n=2-12), 1-butyl-3-alkyl imidazole chlorine [C
nBIm] Cl (n=2-12), alkyl pyridine chlorine [C
nPy] Cl (n=2-8) or alkyl pyridine bromine [C
nPy] Br (n=2-8).
4. it is characterized in that in accordance with the method for claim 1: described mineral acid is the commercially available vitriol oil, concentrated hydrochloric acid, concentrated nitric acid or strong phosphoric acid; Organic acid is acetate or toxilic acid;
Described acidic ionic liquid catalysts is 1-methyl-3-butyl imidazole hydrosulfate [C
4MIm] HSO
4Or 1-methyl-3-(4-sulfo group-butyl) imidazole bisulfate [SBMIm] HSO
4
5. in accordance with the method for claim 1, it is characterized in that: described hexose source biomass is fructose, glucose, semi-lactosi, seminose or sorbose, or contains the biomass of fructose, glucose, semi-lactosi, seminose or sorbose.
6. it is characterized in that in accordance with the method for claim 1: the described biomass that contain fructose, glucose, semi-lactosi, seminose or sorbose are maize treacle, sucrose, inulin, jerusalem artichoke powder or starch.
7. it is characterized in that in accordance with the method for claim 1: the mass percent of described sugared source biomass and solvent is 10%-200%;
When adopting acidic ion liquid to be catalyzer, its usage quantity is the 1%-20% of biomass sugar source quality;
When adopting mineral acid to be catalyzer, its usage quantity is the 0.5%-50% of biomass sugar source quality;
When adopting organic acid to be catalyzer, its usage quantity is the 10%-50% of biomass sugar source quality.
8. in accordance with the method for claim 1, it is characterized in that: reacted HMF realizes separating by column chromatography method with ionic liquid-catalyzed system,
With silica gel is the column chromatography filler, is that leacheate obtains HMF with petrol ether/ethyl acetate=4:2 (v/v); After product HMF separates, for reclaiming, the leacheate sharp separation obtains ionic liquid with methyl alcohol.
9. in accordance with the method for claim 7, it is characterized in that: the ionic liquid that described recovery obtains can directly be used for secondary response down as reaction solvent, realizes ion liquid recycle.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105175366A (en) * | 2015-09-10 | 2015-12-23 | 浙江大学 | Method for producing 2,5-dimethyl furan (2,5-DMF) by fructose one-step process |
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