JP5646325B2 - 転化方法 - Google Patents
転化方法 Download PDFInfo
- Publication number
- JP5646325B2 JP5646325B2 JP2010523596A JP2010523596A JP5646325B2 JP 5646325 B2 JP5646325 B2 JP 5646325B2 JP 2010523596 A JP2010523596 A JP 2010523596A JP 2010523596 A JP2010523596 A JP 2010523596A JP 5646325 B2 JP5646325 B2 JP 5646325B2
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- JP
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- Prior art keywords
- acid
- cellulose
- water
- ionic liquid
- liquid
- 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.)
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- 238000000034 method Methods 0.000 title claims description 51
- 238000006243 chemical reaction Methods 0.000 title claims description 16
- 229920002678 cellulose Polymers 0.000 claims description 69
- 239000001913 cellulose Substances 0.000 claims description 69
- 239000002253 acid Substances 0.000 claims description 53
- 239000002608 ionic liquid Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 230000007062 hydrolysis Effects 0.000 claims description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 239000012453 solvate Substances 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 230000011987 methylation Effects 0.000 claims 1
- 238000007069 methylation reaction Methods 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 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 5
- 239000000243 solution Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- -1 tetrafluoroborates Chemical class 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 150000002772 monosaccharides Chemical class 0.000 description 3
- 229920001542 oligosaccharide Polymers 0.000 description 3
- 150000002482 oligosaccharides Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 2
- 125000006705 (C5-C7) cycloalkyl group Chemical group 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 150000002016 disaccharides Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 150000003977 halocarboxylic acids Chemical class 0.000 description 2
- 229940071870 hydroiodic acid Drugs 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- VYGSFTVYZHNGBU-UHFFFAOYSA-N trichloromethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)(Cl)Cl VYGSFTVYZHNGBU-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- RSZZMVPSHLKFQY-UHFFFAOYSA-N 1-(furan-2-yl)-2-hydroxyethanone Chemical compound OCC(=O)C1=CC=CO1 RSZZMVPSHLKFQY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QVYAWBLDJPTXHS-UHFFFAOYSA-N 5-Hydroxymethyl-2-furfural Natural products OC1=CC=C(C=O)O1 QVYAWBLDJPTXHS-UHFFFAOYSA-N 0.000 description 1
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- 125000002353 D-glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 241001520808 Panicum virgatum Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 241001557886 Trichoderma sp. Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FKOASGGZYSYPBI-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)alumanyl trifluoromethanesulfonate Chemical compound [Al+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F FKOASGGZYSYPBI-UHFFFAOYSA-K 0.000 description 1
- RBGLVWCAGPITBS-UHFFFAOYSA-L bis(trifluoromethylsulfonyloxy)tin Chemical compound [Sn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F RBGLVWCAGPITBS-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000001461 cytolytic effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002303 glucose derivatives Chemical class 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- HITOXZPZGPXYHY-UJURSFKZSA-N levoglucosenone Chemical compound O=C1C=C[C@H]2CO[C@@H]1O2 HITOXZPZGPXYHY-UJURSFKZSA-N 0.000 description 1
- HITOXZPZGPXYHY-UHFFFAOYSA-N levoglucosenone Natural products O=C1C=CC2COC1O2 HITOXZPZGPXYHY-UHFFFAOYSA-N 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- BZQRBEVTLZHKEA-UHFFFAOYSA-L magnesium;trifluoromethanesulfonate Chemical compound [Mg+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F BZQRBEVTLZHKEA-UHFFFAOYSA-L 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 description 1
- 150000008648 triflates Chemical class 0.000 description 1
- YOIAWAIKYVEKMF-UHFFFAOYSA-N trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F YOIAWAIKYVEKMF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 1
- YISPIDBWTUCKKH-UHFFFAOYSA-L zinc;4-methylbenzenesulfonate Chemical compound [Zn+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 YISPIDBWTUCKKH-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/02—Monosaccharides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
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Description
化学的触媒、酵素触媒、微生物学的触媒及びマクロ生物学的触媒は、生成物形成に熱力学的に有利となるように選択された条件下でセルロースの加水分解を促進するために使用することができる。セルロースの化学的及び酵素を使用する加水分解は、以下の“The Encyclopaedia of Polymer Science and Technology,”2nd Ed,J.I. Kroschwitz(Ed in Chief),Wiley(New York),1985の中で考察されている。かくして、セルロースは、セルロース分解酵素(セルラーゼ)又は採取された糸状菌類、例えばトリコデルマ(Trichoderma) spを使用して加水分解することができる。しかし、化学的方法によりセルロースを加水分解すると、多くの問題が生ずる。一般的には、このような方法は、2つのアプローチのうちの1つを含む:すなわち、高温及び加圧(>100℃)での希酸処理及び/又は濃酸前処理である。希酸法は、加圧下高温で(例えば、1%硫酸を237℃で使用して)行われる。濃酸処理は、通常、初期酸濃度10%で開始し、100℃及び周囲圧力での脱水を経て70%まで上昇させる。
したがって、本発明は、水溶性のセルロース加水分解生成物を製造するための方法であって、少なくとも一部のセルロースを溶媒和又は溶解し得るイオン性液体とセルロースとを混合すること(ここで、イオン性液体がカチオン類及びアニオン類のみから構成される化合物であり且つ150℃以下の温度で液体の状態で存在し、前記イオン性液体中のカチオンは、一般式:
を有する。);及び、生ずる溶媒和物又は溶液を水の存在下酸で処理すること(ここで酸は25℃の水中で2未満のpKaを有する。)を含む方法を提供する。
化学量論的には、加水分解反応は、セルロース中の各モノマー単位につき1モル当量の水の存在を必要とする。セルロースそれ自体は、ある量の水を含有し、その正確な量は、セルロースの供給元及び物理的形態に依存し;通常、製造されるセルロースは、少なくとも10〜15重量%の水を含有する。さらに、酸水溶液が使用される場合、水が反応混合物に添加される。しかし、反応混合物中に過度に多量の水が存在すると、セルロースのイオン性液体への溶解度が低下し、及び/又は、セルロースの水溶性加水分解生成物への転化率が低下することになる。好ましくは、反応系の全含水率は、水対セルロースの重量比が1:1〜1:20、好ましくは1:5〜1:15、特に約1:10となるような量であることが好ましい。
本発明の方法の好ましい実施態様では、形成される生成物の次の処理は、バイオ燃料として使用するのに好適な低級のアルコール、特にエタノールを生成するために実施される。かくして、更なる実施態様では、本発明は、水溶性のセルロース加水分解生成物を製造するための方法であって、少なくとも若干のセルロースを溶媒和又は溶解し得るイオン性液体とセルロースとを混合すること(ここで、イオン性液体はカチオン及びアニオンのみから構成され且つ150℃以下の温度で液体の状態で存在し、前記イオン性液体中のカチオンが上記一般式Iを有する);及び、生ずる溶媒和物又は溶液を水の存在下酸で処理すること(ここで、酸は25℃の水中で2未満のpKaを有する);生ずる生成物の少なくとも一部を1種以上のアルコールに変換すること、を含む方法を提供する。水溶性セルロース加水分解生成物は、例えば発酵によりアルコール類に変換することができる。
実施例1
10gの塩化トリブチルメチルアンモニウムを丸底フラスコに入れ、120℃まで加熱して、溶融させた。シリンジから0.1mlの濃CF3COOHを滴下し、0.1gのMiscantus(0.5mmに微粉砕した)を加えて攪拌し、基質を十分に湿潤させるように攪拌速度を最大に設定した。試料を定期的に採取し、屈折率高性能クロマトグラフィーにより分析した。グルコース末端基を有する水溶性生成物の収率は、150分後、8.7%であった。
トリフルオロ酢酸の代わりに同一体積の別の酸を使用した以外は、実施例1の一般的な方法を繰り返した。その結果を以下の表1に示す。
少なくとも一部のセルロースを溶媒和又は溶解し得るイオン性液体とセルロースとを混合すること、ここで、イオン性液体がカチオン及びアニオンのみから構成される化合物であり且つ150℃以下の温度で液体の状態で存在し、前記イオン性液体中のカチオンは、一般式:
を有する;及び、
生ずる溶媒和物又は溶液を水の存在下酸で処理すること、ここで、酸は25℃の水中で2未満のpKaを有する;
を含む方法。
[2]前記イオン性液体が、セルロースが少なくともある程度の溶解度を有する液体である、[1]に記載の方法。
[3]酸が、25℃の水中で0以下のpKaを有する、[1]又は[2]に記載の方法。
[4]酸が、ハロゲン化水素、硫酸、硝酸、ハロカルボン酸、ハロスルホン酸、テトラフルオロホウ酸、ヘテロポリ酸、アリール-及びアルキル-スルホン酸、及び、ハロゲン化アルキル-及びアリールスルホン酸から選択される、[1]又は[2]のいずれかに記載の方法。
[5]酸が、p-トルエンスルホン酸、トリフルオロメタンスルホン酸、トリクロロメタンスルホン酸、トリフルオロ酢酸、塩酸、臭化水素酸、ヨウ化水素酸、テトラフルオロホウ酸、又は、硫酸である、[4]に記載の方法。
[6]酸が、トリフルオロ酢酸、硫酸、硝酸、メタンスルホン酸、トリフルオロメタンスルホン酸又は塩酸である、[5]に記載の方法。
[7]酸との反応が、50〜200℃の範囲の温度で行われる、[1]〜[6]のいずれかに記載の方法。
[8]Zが窒素原子を表す、[1]〜[7]のいずれかに記載の方法。
[9]R1がメチル基を表す、[1]〜[8]のいずれかに記載の方法。
[10]R2及びR3の各々が、独立にC4-8アルキル基を表す、[1]〜[9]のいずれかに記載の方法。
[11]R2及びR3の各々が、同一の基を表す、[1]〜[10]のいずれかに記載の方法。
[12]R4がC1-8アルキル基を表す、[1]〜[11]のいずれかに記載の方法。
[13]R2、R3及びR4の各々が、同一の基を表す、[1]〜[12]のいずれかに記載の方法。
[14]R4が、メチル基を表す、[12]に記載の方法。
[15]イオン性液体のアニオンが、ハライド、シアネート、硫酸塩、硫酸水素塩又は硝酸塩である、[1]〜[14]のいずれかに記載の方法。
[16]セルロースが、イオン性液体と5〜35重量%の量で混合される、[1]〜[15]のいずれかに記載の方法。
[17]反応系の含水率が、水対セルロースの重量比が1:1〜1:20となるような量である、[1]〜[16]のいずれかに記載の方法。
[18]反応系の含水率が、水対セルロースの重量比が1:5〜1:15となるような量である、[17]に記載の方法。
[19]1種以上のアルコールを製造するための方法であって、[1]〜[18]のいずれかに記載の方法を実施して、生ずる生成物の少なくとも一部を1種以上のアルコールに変換することを含む方法。
Claims (7)
- 水溶性のセルロース加水分解生成物を製造するための方法であって、
少なくとも一部のセルロースを溶媒和又は溶解し得るイオン性液体とセルロースとを混合すること、ここで、イオン性液体がカチオン及びアニオンのみから構成される化合物であり且つ150℃以下の温度で液体の状態で存在し、前記イオン性液体中のカチオンは、一般式:
を有する;及び、
生ずる溶媒和物又は溶液を水の存在下酸で処理すること、ここで、酸は25℃の水中で2未満のpKaを有し、ここで、酸が、トリフルオロ酢酸、硫酸、硝酸、メタンスルホン酸、トリフルオロメタンスルホン酸又は塩酸である;
を含む方法。 - 前記イオン性液体が、セルロースが少なくともある程度の溶解度を有する液体である、請求項1に記載の方法。
- 酸との反応が、50〜200℃の範囲の温度で行われる、請求項1又は2に記載の方法。
- セルロースが、イオン性液体と5〜35重量%の量で混合される、請求項1〜3のいずれか1項に記載の方法。
- 反応系の含水率が、水対セルロースの重量比が1:1〜1:20となるような量である、請求項1〜4のいずれか1項に記載の方法。
- 反応系の含水率が、水対セルロースの重量比が1:5〜1:15となるような量である、請求項5に記載の方法。
- 1種以上のアルコールを製造するための方法であって、請求項1〜6のいずれか1項に記載の方法を実施して、生ずる生成物の少なくとも一部を1種以上のアルコールに変換することを含む方法。
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US8354525B2 (en) | 2008-02-13 | 2013-01-15 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom |
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US9777074B2 (en) | 2008-02-13 | 2017-10-03 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom |
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WO2011002660A1 (en) | 2009-07-01 | 2011-01-06 | Wisconsin Alumni Research Foundation | Biomass hydrolysis |
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US9850512B2 (en) | 2013-03-15 | 2017-12-26 | The Research Foundation For The State University Of New York | Hydrolysis of cellulosic fines in primary clarified sludge of paper mills and the addition of a surfactant to increase the yield |
TW201522380A (zh) * | 2013-10-02 | 2015-06-16 | Basf Se | 含纖維素生質之加工方法 |
ITMI20132069A1 (it) * | 2013-12-11 | 2015-06-12 | Versalis Spa | Procedimento per la produzione di zuccheri da biomassa |
US9133087B2 (en) * | 2013-12-30 | 2015-09-15 | M K Carter | Direct catalytic conversion of cellulosic materials to ethanol |
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BR112017017899B1 (pt) | 2015-02-23 | 2021-12-07 | Basf Se | Método para o processamento de biomassa que contém celulose, e, uso de um composto |
CN107257807B (zh) * | 2015-02-23 | 2020-10-27 | 巴斯夫欧洲公司 | 加工含纤维素的生物质的方法 |
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EP1860201A1 (en) * | 2006-05-25 | 2007-11-28 | BP p.l.c. | Conversion method |
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CA2698655C (en) | 2017-04-18 |
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EA201000437A1 (ru) | 2010-10-29 |
US20120029247A1 (en) | 2012-02-02 |
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