EP2906521A1 - Procédé d'obtention d'alditols comportant cinq à six atomes de carbone - Google Patents
Procédé d'obtention d'alditols comportant cinq à six atomes de carboneInfo
- Publication number
- EP2906521A1 EP2906521A1 EP13792247.2A EP13792247A EP2906521A1 EP 2906521 A1 EP2906521 A1 EP 2906521A1 EP 13792247 A EP13792247 A EP 13792247A EP 2906521 A1 EP2906521 A1 EP 2906521A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cellulose
- yield
- acid
- catalyst
- bar
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 150000005846 sugar alcohols Chemical class 0.000 title claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 title claims abstract description 11
- 229920002678 cellulose Polymers 0.000 claims abstract description 75
- 239000001913 cellulose Substances 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 41
- 238000005470 impregnation Methods 0.000 claims abstract description 12
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 5
- 239000007792 gaseous phase Substances 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 48
- 239000000047 product Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 34
- 229910052707 ruthenium Inorganic materials 0.000 claims description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 238000003776 cleavage reaction Methods 0.000 claims description 8
- 230000007017 scission Effects 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- -1 W0 3 Inorganic materials 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 235000010980 cellulose Nutrition 0.000 abstract description 67
- 229920000168 Microcrystalline cellulose Polymers 0.000 abstract description 26
- 235000019813 microcrystalline cellulose Nutrition 0.000 abstract description 26
- 239000008108 microcrystalline cellulose Substances 0.000 abstract description 22
- 229940016286 microcrystalline cellulose Drugs 0.000 abstract description 22
- 239000000758 substrate Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 6
- 239000007858 starting material Substances 0.000 abstract description 6
- 239000002023 wood Substances 0.000 abstract description 6
- 241000609240 Ambelania acida Species 0.000 abstract description 3
- 240000000111 Saccharum officinarum Species 0.000 abstract description 3
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- 239000010905 bagasse Substances 0.000 abstract description 3
- 230000036571 hydration Effects 0.000 abstract 1
- 238000006703 hydration reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 65
- 229910000831 Steel Inorganic materials 0.000 description 58
- 238000006243 chemical reaction Methods 0.000 description 58
- 239000010959 steel Substances 0.000 description 58
- 239000000843 powder Substances 0.000 description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 47
- 230000035484 reaction time Effects 0.000 description 46
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 30
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 29
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 29
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 29
- 229930195725 Mannitol Natural products 0.000 description 29
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 29
- 239000000594 mannitol Substances 0.000 description 29
- 235000010355 mannitol Nutrition 0.000 description 29
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 29
- 239000000600 sorbitol Substances 0.000 description 29
- 239000000811 xylitol Substances 0.000 description 29
- 235000010447 xylitol Nutrition 0.000 description 29
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 29
- 229960002675 xylitol Drugs 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 27
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 26
- 239000000706 filtrate Substances 0.000 description 24
- 239000000725 suspension Substances 0.000 description 24
- 238000004128 high performance liquid chromatography Methods 0.000 description 23
- 238000005259 measurement Methods 0.000 description 22
- 239000011541 reaction mixture Substances 0.000 description 22
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000013065 commercial product Substances 0.000 description 17
- 239000012065 filter cake Substances 0.000 description 11
- 230000007306 turnover Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 6
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 3
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 3
- 229940040102 levulinic acid Drugs 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 230000008901 benefit Effects 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
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- 229910017604 nitric acid Inorganic materials 0.000 description 2
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- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
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- 239000002028 Biomass Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
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- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/26—Hexahydroxylic alcohols
-
- 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
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
Definitions
- the present invention relates to a process for the recovery of sugar alcohols having five to six carbon atoms in high yield from cellulosic materials.
- the cellulosic starting materials e.g., microcrystalline cellulose, alpha-cellulose, wood and cellulosic residues such as sugarcane bagasse or wood chips
- the acid-containing and preferably dried starting materials are brought into contact in a second step under the action of mechanical energy, so that the cellulose-containing materials are degraded into water-soluble products.
- a third step from the water-soluble products in aqueous solution by hydrolytic hydrogenation by means of a metal-containing catalyst under high pressure hydrogen pressure and in high yield five to six carbon atoms containing sugar alcohols obtained.
- biomass as a base material for fuels and for basic chemicals is currently the subject of extensive research.
- Cellulose the main component of lignocellulosic biomass, is considered as a possible raw material. In order to obtain suitable and workable products, the cellulose must be broken up into smaller molecules.
- WO 2009/061750 discloses a process for the preparation of soluble sugars from a cellulosic material.
- the cellulosic material is contacted with a solid acid and milled together over an extended period of time to obtain a product of soluble sugars.
- the solid acid used has the disadvantage that it is virtually consumed during the process, with the result that the catalytic activity decreases in the course of the process and also a recovery of the catalyst is not completely possible.
- the conversion of cellulose-containing materials into water-soluble substances is not complete.
- the inventors have found that those containing a catalytic amount of a strong acid (eg, HCl, H 2 S0 4 and others) can be replaced by a liquid or gaseous phase carried out impregnation, also referred to as impregnation according to the invention, the cellulose-containing starting materials is a very important step to obtain under the action of mechanical forces on the acid-coated and preferably dried starting materials completely water-soluble oligomers having molecular weights lower than 2000 daltons, the then directly, preferably without further treatment of a hydrogenation treatment in aqueous solution by means of a transition metal-containing catalyst can be subjected, and thus five to produce six carbon atoms containing sugar alcohols in high yield.
- a strong acid eg, HCl, H 2 S0 4 and others
- the present invention accordingly provides a process for obtaining sugar alcohols having five to six carbon atoms from cellulosic material or mixtures thereof, in which the cellulosic material is brought into intimate contact with an acid, carried out in a liquid or gaseous phase, in contact with the acid Acid-coated and preferably dried cellulose-containing material is subjected to a mechanical treatment to reduce the degree of polymerization of the cellulose-containing material, wherein the mechanical treatment is carried out at least until the degradation or cleavage products of cellulose-containing material to more than 60 wt .-%, preferably more than 70 wt .-%, especially more than 80 wt .-%, especially more than 90 wt .-%, based on the cellulose-containing material used are water-soluble, the resulting reaction product of a hydrogenation treatment with hydrogen in the presence of a catalyst with a content of transition metal selected from the metals of groups 3 to 10 of the Periodic Table (IUPAC) or mixtures thereof, preferably in aqueous
- the cellulosic material is not limited to already purified celluloses or certain celluloses, even untreated natural products such as hay and spruce can with yields of at least 75% and 87% after 2 hours Milling, beech wood or sugar cane bagasse even with yields greater than 99% are converted into water-soluble products after 2 hours of milling, which can then be subjected to the hydrolytic hydrogenation treatment.
- cellulose is used in the present application, this means that this is pure cellulose or cellulose-containing materials. It can be used both natural products such as wood, grasses, chemically pure celluloses and cellulose-containing materials.
- an acid selected from inorganic acids, organic acids or mixtures thereof is used.
- the acid is used in the process according to the invention in catalytic amounts.
- the acid is used in an amount of 0.0001 to 1 mmol per g of cellulose.
- the impregnation of the cellulosic substrates with a strong acid is carried out in a dilute acidic solution (0.0001 to 6 mol / l) of the acid in a low boiling point solvent (eg, dimethyl ether, diethyl ether, methyl ethyl ether, tert-butyl methyl ether, acetone , Pentane, hexane, heptane, supercritical carbon dioxide, ethyl acetate, methyl acetate, methanol, dichloromethane, etc.). or mixtures thereof, which can be easily removed in a next process step, for example by applying a negative pressure or supplying heat.
- a low boiling point solvent eg, dimethyl ether, diethyl ether, methyl ethyl ether, tert-butyl methyl ether, acetone , Pentane, hexane, heptane, supercritical carbon dioxide, ethyl
- the substrate may be treated with a gaseous acid.
- cellulose or the cellulose-containing material may be exposed to gaseous HCl, S0 3 or other gaseous acids. If desired, however, it is also possible for a combination of the impregnation with the impregnation to take place by gaseous means, even with different acids
- inorganic acid has a pKa value ⁇ 3, preferably the pKa value is between -14 and 2.
- Suitable examples of inorganic acids are mineral acids such as sulfuric acid, sulfur dioxide, sulfur trioxide, hydrochloric acid, phosphoric acid, phosphotungstic acid and Nitric acid, with nitric acid being less preferred.
- Particularly good conversion results are also obtained when the organic acid has a pKa value ⁇ 3, preferably the pKa value is between -14 and 2.
- organic acids are benzenesulfonic acids and their derivatives, haloalkanoic acid, such as trifluoroacetic acid, or methanesulfonic acid, Trifluoroacetic acid and oxalic acid and derivatives thereof.
- acids having a pKa value of less than -2 Preference is given to acids having a pKa value of less than -2.
- the acid is not brought into direct contact with the cellulose, but in a first process step, the cellulose-containing material is impregnated with a solution of the acid in a suitable solvent and / or with a gaseous acid becomes.
- those solvents which do not adversely affect the reaction are suitable, such as water and organic solvents such as diethyl ether, dichloromethane, ethanol, methanol, THF, acetone; Benzene, lighter hydrocarbons (eg, four to seven carbon atom-containing hydrocarbons) and any other polar or non-polar solvent in which the acid used is soluble, or which allows a good mixing of cellulose and acid in a dispersion, and which has a boiling point of 100 ° C and below has.
- the solution or dispersion of the acid is mixed with the cellulose-containing material and optionally allowed to stand for some time from up to several hours, especially up to 2 hours.
- the solvent is removed again, for example by filtration and / or evaporation.
- a low-boiling solvent having a boiling point at normal pressure of 30 to 80 ° C is used as the solvent, this can be removed in a simple manner, either by gentle heating and / or by applying a negative pressure again.
- the acid which usually has a higher boiling point, remains on the cellulosic material.
- the mechanical treatment of the cellulose can be carried out in the presence of the acid. It has been found that the degree of conversion of the cellulose by impregnating the cellulosic material with inorganic and / or organic acid in the presence of a solvent can be substantially increased.
- the acid-containing and preferably dried cellulose-containing material will have a residual moisture content of less than 20% by weight, especially less than 16% by weight, based on the total weight of the impregnated cellulose-containing material.
- a cellulosic material is used which has a residual moisture in the range of 2 to 10 wt .-%, based on the total weight of the impregnated cellulose-containing material, which, if necessary, can be achieved by drying.
- the mechanical treatment of the acid-containing and dried cellulose-containing substrates can be carried out, for example, by grinding, extruding or kneading.
- mills those can be used which comminute the millbase using grinding media, such as.
- vibrating mills stirred mills, stirred ball mills, ball mills, etc.
- ball mills Particularly preferred are ball mills. All extruders known from the prior art can be used as extruders. If the method according to the invention is carried out in a ball mill, for example in a planetary ball mill, then turning times of 400 to 1200, preferably 800 to 1000, rpm have proven suitable.
- the speed may also be lower for large-scale installations, but the person skilled in the art will be dependent determine the speed of the material used and the mill used so that an optimized result can be achieved.
- the reaction time, d. H. the time in which the mechanical treatment is carried out is usually from 0.01 to 24 hours, with periods of 1, 5 to 12, especially 2 to 6 hours are sufficient to a mixture of products having a molecular weight lower than 2000 Da or to recover completely water-soluble products.
- the mechanical treatment is carried out according to the invention at least until the degradation or cleavage products of the cellulose-containing material to more than 60% by weight, preferably more than 70 wt .-%, especially more than 80 wt .-%, especially more than 90 Wt .-%, based on the cellulose-containing material used are water-soluble. This is usually the case when the degree of polymerization of the cellulose fragments is less than 15 anhydroglucose units. This is achieved depending on the apparatus used for the mechanical treatment and the amount of cellulose-containing material used usually with a treatment time of 2 to 6 hours, this process time can be determined by those skilled in the knowledge of the system used and the cellulose-containing materials used.
- the process of the present invention can achieve nearly quantitative conversions of the cellulosic materials to water-soluble products.
- water-soluble cellulose oligomers, cellobiose and other products whereby the formation of by-products (eg, 5-hydroxymethylfurfural, furfural, levulinic acid, etc.) can be largely avoided.
- cellulose cleavage products which are in powder form, especially after milling in a ball mill, are dissolved, optionally with separation of non-water soluble residues, in water and a hydrogenation treatment with hydrogen in the presence of a transition metal catalyst which is usually subjected to an amount of up to 10 wt .-%, transition metal based on the total weight of the transition metal used, subjected.
- heating of an aqueous solution of the resulting degradation or cleavage products of the cellulose-containing material at a temperature of more than 80 ° C, especially between 100 ° and 200 ° C, in particular from 120 ° to 160 ° C, especially between 130 ° and 150 ° C, over a period of 0.5 to 24 hours, especially from 0.25 to 12 hours, in particular from 2 to 6 hours are carried out, any resulting solid residues are separated by filtration, and then the catalyst to the filtrate of the heat aqueous solution and the hydrogenation treatment in an autoclave at a hydrogen pressure of 10 to 100 bar, especially 30 to 70 bar, in particular 40 to 60 bar, at a temperature of more than 140 ° C, especially between 150 ° and 200 ° C, be carried out over a period of 0.25 to 24 hours, especially from 0.5 to 12 hours, in particular from 1 to 6 hours.
- Metal oxides or mixed oxides of Si, W, V, Al, Ti, Ce, Zr, Sc, Y, Zr, Ta, Nb, Cr, Mo and / or lanthanides, or carbonaceous catalyst supports (eg activated carbons) are advantageous.
- suitable carriers are metal oxides or mixed oxides of Si, W, V, Al, Ti, Ce, Zr, Sc, Y, Zr, Ta, Nb, Cr, Mo and / or lanthanides, or carbon-containing catalyst supports (eg activated carbons), such as Si0 2 , Al 2 0 3 , Ti0 2 , Zr0 2 , Nb 2 0 5 , W 2 0 5 , W0 3 , W 2 0 3 , W0 2 , Ce0 2 and mixed oxides or activated carbon thereof called.
- the hydrogenation catalyst of the invention particularly comprises ruthenium present in reduced, highly dispersed form on a porous carbon support.
- the catalyst comprises at least 0.1% by weight of Ru, based on the total weight of the catalyst, to ensure at least sufficient catalyst activity.
- the metal loadings on the carbon support are 0.5 to 10.0 wt .-%, particularly 3 to 7 wt .-% ruthenium, based on the total weight of the catalyst.
- the metal catalyst such as the Ru / C catalyst for the process according to the invention preferably an activation treatment at temperatures of more than 140 ° C, especially more than 160 ° C, and up to 250 ° C, at a hydrogen pressure of at least 40 bar, particularly at least 50 bar, over a period of 0.25 to 2 hours in an autoclave is subjected to a prehydrogenation of the catalyst and thus an improved activity for the hydrolytic hydrogenation of the cellulose cleavage products already at the beginning of Hydrogenation of the cleavage products to allow.
- the catalyst in non-activated form, and the reactivity is increased in the hydrogenation in the process according to the invention.
- the hydrolytic hydrogenation is thus carried out according to the invention especially at a pressure of 10 to 100 bar, especially 30 to 70 bar, in particular 40 to 60 bar and at a temperature of more than 140 ° C, especially between 150 ° and 200 ° C.
- the reaction time in which the hydrolytic hydrogenation is carried out according to the process of the invention is usually from 0.25 to 24 hours, with periods of from 0.5 to 12, especially from 1 to 6 hours being usually sufficient.
- the catalyst After completion of the hydrogenation, the catalyst can be filtered off and reused without causing a decrease in activity due to clogging of the catalyst pores by cellulose degradation products, as seen in prior art hydrogenation processes for cellulose.
- Microcrystalline cellulose (Aldrich, 500 mg) was added to water (10 ml).
- Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst.
- the Mixture was heated to 160 ° C in an autoclave under a room temperature hydrogen pressure of 50 bar. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
- Microcrystalline cellulose (1.20 g) was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
- the rotation frequency of the main disk was 800 rpm.
- the powder thus obtained (500 mg) was dissolved in water (10 ml).
- Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst.
- the mixture was placed in an autoclave under a room temperature hydrogen pressure of 50 bar
- Reaction time started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
- the reaction mixture was filtered.
- the filter cake was washed, dried and weighed.
- the conversion was calculated by the weight difference of cellulose.
- Microcrystalline cellulose 500 mg was added to a 0.05 M sulfuric acid solution (10 ml).
- Ruthenium on carbon 100 mg, 5% by weight of ruthenium was added as a catalyst.
- the mixture was placed in an autoclave under a Room temperature hydrogen pressure of 50 bar heated to 160 ° C. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
- the reaction mixture was filtered.
- the filter cake was washed, dried and weighed.
- the conversion was calculated by the weight difference of cellulose.
- the turnover was 13%.
- the filtrate was analyzed by HPLC to determine product yield.
- the yield of C6-sugar alcohols (sorbitol, mannitol, sorbitan) was 5.6%, the yield of xylitol was 0.9%, other identified compounds together gave a yield of 0.7%.
- the rotation frequency of the main disk was 800 rpm.
- the resulting powder (500 mg) was added to 0.05 M sulfuric acid (10 ml).
- Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst. The mixture was heated to 160 ° C in an autoclave under a room temperature hydrogen pressure of 50 bar. Upon reaching the
- the autoclave was cooled in an ice-cooled water bath before it was opened.
- the filtrate was analyzed by HPLC to determine product yield.
- the yield of C6-sugar alcohols (sorbitol, mannitol, sorbitan) was 44.7%, the yield of xylitol was 3.0%, other identified compounds together gave a yield of 0.5%.
- Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of JT Baker, USA) was added dropwise. The suspension was stirred for 1 hour before the Solvent was removed under reduced pressure. A sample of the powder so obtained was derivatized with phenyl isocyanate for GPC analysis.
- the resulting powder (500 mg) was added to water (10 ml).
- Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst.
- the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 160 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
- the reaction mixture was filtered.
- the filter cake was washed, dried and weighed.
- the conversion was calculated by the weight difference of cellulose.
- the turnover was 32%.
- the filtrate was analyzed by HPLC to determine product yield.
- the yield for C6-sugar alcohols (sorbitol, mannitol, sorbitan) was 9.0%, the yield for xylitol was 1.3%, other identified compounds together gave a yield of 0.8%.
- the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 1 hour.
- the rotation frequency of the main disk was 800 rpm.
- Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- the reaction mixture was filtered.
- the filter cake was washed, dried and weighed.
- the conversion was calculated by the weight difference of cellulose.
- the turnover was 100%.
- Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of JT Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 3 hours.
- the rotation frequency of the main disk was 800 rpm.
- the reaction mixture was filtered.
- the filter cake was washed, dried and weighed.
- the conversion was calculated by the weight difference of cellulose.
- the turnover was 100%.
- ⁇ -cellulose (1.20 g) was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
- the rotation frequency of the main disk was 800 rpm.
- the thus-obtained powder (500 mg) was dissolved in 0.05 M sulfuric acid (10 ml). Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst.
- the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 160 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
- ⁇ -cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure. A sample of the powder so obtained was derivatized with phenyl isocyanate for GPC analysis.
- the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
- the rotation frequency of the main disk was 800 rpm.
- the powder thus obtained (500 mg) was dissolved in water (10 ml).
- Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst.
- the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 160 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
- the reaction mixture was filtered.
- the filter cake was washed, dried and weighed.
- the conversion was calculated by the weight difference of cellulose.
- the turnover was 100%.
- the filtrate was analyzed by HPLC to determine product yield.
- the yield for C6-sugar alcohols (sorbitol, mannitol, sorbitan) was 85.9%, the yield for xylitol was 13.7%, other identified compounds together gave a yield of 0.4%.
- Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of JT Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
- the rotation frequency of the main disk was 800 rpm.
- the powder thus obtained (500 mg) was dissolved in water (10 ml).
- Ruthenium on carbon (100 mg, 5% by weight of ruthenium) was added as a catalyst.
- the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 160 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
- the reaction mixture was filtered.
- the filter cake was washed with water (60 ml) and acetone (60 ml), dried and used several times as a catalyst by addition to a freshly prepared solution of sulfuric acid-impregnated ground microcrystalline cellulose (500 mg) in water (10 ml ) was given.
- the filtrate was analyzed by HPLC to determine product yield.
- Example 12 Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of JT Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
- the rotation frequency of the main disk was 800 rpm.
- the powder thus obtained (500 mg) was dissolved in water (10 ml).
- the catalyst was activated before the reaction.
- ruthenium on carbon 100 mg, 5% by weight of ruthenium
- the suspension was heated to 160 ° C. in an autoclave under a room temperature hydrogen pressure of 50 bar for 1 h.
- the catalyst was filtered off, washed (60 ml of water, 60 ml of acetone) and dried before being added to the solution.
- the reaction mixture was filtered. The filtrate was used to determine the
- Sorbitan was 2.8%, the yield for xylitol was 3.7%, others identified
- Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product from J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- the powder (1.20 g) obtained in this way was placed in a steel beaker with steel balls (6 steel balls, weight 3.95 g) in a Pulverisette P7 from Fritsch for 2
- the rotation frequency of the main disk was 800 rpm.
- the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 140 ° C for 1 hour. Upon reaching the reaction temperature was Measurement of the reaction time started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
- the reaction mixture was filtered.
- the filtrate was analyzed by HPLC to determine product yield.
- Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- the rotation frequency of the main disk was 800 rpm.
- the powder thus obtained (500 mg) was dissolved in water (10 ml).
- the catalyst was activated before the reaction.
- Ruthenium was suspended in water (10 ml). The suspension was heated to 160 ° C. in an autoclave under a room temperature hydrogen pressure of 50 bar for 1 h. The catalyst was filtered off, washed (60 ml of water, 60 ml of acetone) and dried before being added to the solution.
- the reaction mixture was filtered.
- the filtrate was analyzed by HPLC to determine product yield.
- Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of JT Baker, USA) was obtained added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
- the rotation frequency of the main disk was 800 rpm.
- the powder thus obtained (500 mg) was dissolved in water (10 ml).
- Ruthenium on carbon (100 mg, 5 wt.% Ruthenium) was added as a non-activated catalyst.
- the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 150 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
- the reaction mixture was filtered.
- the filtrate was analyzed by HPLC to determine product yield.
- Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 160 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened. The reaction mixture was filtered. The filtrate was analyzed by HPLC to determine product yield.
- Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product from J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
- the rotation frequency of the main disk was 800 rpm.
- the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
- the rotation frequency of the main disk was 800 rpm.
- the reaction mixture was filtered.
- the filtrate was analyzed by HPLC to determine product yield.
- Example 20 Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of JT Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
- the rotation frequency of the main disk was 800 rpm.
- the powder thus obtained (500 mg) was dissolved in water (10 ml).
- the catalyst was activated before the reaction.
- ruthenium on carbon 100 mg, 5% by weight of ruthenium
- the suspension was heated to 200 ° C. in an autoclave under a room temperature hydrogen pressure of 50 bar for 1 h.
- the catalyst was filtered off, washed (60 ml of water, 60 ml of acetone) and dried before being added to the solution.
- the reaction mixture was filtered. The filtrate was used to determine the
- Microcrystalline cellulose (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product from J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- the powder (1.20 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 2 hours.
- the rotation frequency of the main disk was 800 rpm.
- the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 150 ° C for 1 hour. When the reaction temperature was reached, the measurement of the reaction time was started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
- Beechwood sawdust was made into a powder with a kitchen mixer. The powder was sieved and the proportion of particles smaller than 250 ⁇ m was reused.
- This powder (10 g) was dispersed in tert-butyl methyl ether (150 ml) and sulfuric acid (0.52 ml, 95-97%, commercial product of J. T. Baker, USA) was added dropwise. The suspension was stirred for 1 hour before removing the solvent under reduced pressure.
- the powder (1.00 g) obtained in this way was ground in a steel beaker with steel balls (6 steel balls, individual weight 3.95 g) in a Pulverisette P7 from Fritsch for 3 hours.
- the rotation frequency of the main disk was 800 rpm.
- the resulting powder (900 mg) was dissolved in water (9 ml). The solution was heated to 145 ° C. for 1 hour, the resulting solid was separated by filtration, and the filtrate from the combined mixtures was analyzed by HPLC.
- the mixture was heated in an autoclave under a room temperature hydrogen pressure of 50 bar to 145 ° C for 1 hour. Upon reaching the reaction temperature was Measurement of the reaction time started. After a reaction time of 60 minutes, the autoclave was cooled in an ice-cooled water bath before being opened.
- the reaction mixture was filtered.
- the filtrate was analyzed by HPLC to determine product yield.
- the yield for the C6 compounds (sorbitol, mannitol and glucose) was calculated relative to the concentration of glucose and cellobiose in the reaction solution before the reaction.
- the C6 sugar alcohol yield (sorbitol, mannitol) was 84.0%, the glucose yield was 13.4%.
- the yield for xylitol (84.2%) and xylose (1 1, 7%) were calculated relative to the concentration of xylose in the reaction solution before the reaction.
- By-products further identified were gycerin, 1,3-propanediol, methanol, levulinic acid, hydroxymethylfurfural and furfural and furanic acid.
- Fig. 1 shows the degree of polymerization of the phenylcarbanylate derivatives of a-cellulose (1), MCC (2), a-cellulose ball-milled for 2 hours (3), MCC ball-milled for 2 hours (4), IMCC (5), IMCC for 1 h (6), 2 h (7) and 3 h ball-milled (8).
- Fig. 2 shows the comparison of the performance of Ru / C and Ru / C * catalysts in the hydrolytic hydrogenation of IMCC ball-milled for 2 h.
- Reaction conditions 500 mg of substrate, 10 ml of water, 100 mg of catalyst, 50 bar of H 2 ⁇ rt), 1 h.
- Fig. 4 TEM images of the Ru / C catalysts: (a) before the reaction, (b) after a run and (c) after 6 runs. The illustration at the bottom right shows the Ru particle distribution of the catalyst samples.
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Abstract
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DE102012109595.7A DE102012109595A1 (de) | 2012-10-09 | 2012-10-09 | Verfahren zur Gewinnung von Zuckeralkoholen mit fünf bis sechs Kohlenstoffatomen |
PCT/DE2013/100350 WO2014056486A1 (fr) | 2012-10-09 | 2013-10-04 | Procédé d'obtention d'alditols comportant cinq à six atomes de carbone |
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CN105289601B (zh) * | 2015-12-07 | 2018-01-02 | 中国科学院广州能源研究所 | 一种山梨醇水相加氢制取直链c5/c6烷烃催化剂及其制备方法 |
US10882804B2 (en) * | 2018-09-14 | 2021-01-05 | University Of South Carolina | Methods and compositions for hydrodeoxygenation of carbohydrates and carbohydrate analogs |
DE102019117437A1 (de) | 2019-06-27 | 2020-12-31 | Technische Universität Dresden | Mechanochemisches Syntheseverfahren unter Verwendung eines katalytisch aktiven Formkörpers |
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US8062428B2 (en) | 2007-11-06 | 2011-11-22 | University Of Central Florida Research Foundation, Inc. | Solid acid catalyzed hydrolysis of cellulosic materials |
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US9206098B2 (en) | 2015-12-08 |
MX2015004447A (es) | 2015-06-24 |
WO2014056486A1 (fr) | 2014-04-17 |
DE102012109595A1 (de) | 2014-04-24 |
JP2015535855A (ja) | 2015-12-17 |
CA2886756A1 (fr) | 2014-04-17 |
JP6212564B2 (ja) | 2017-10-11 |
BR112015007740A2 (pt) | 2018-04-24 |
IN2015DN02471A (fr) | 2015-09-04 |
EA201500401A1 (ru) | 2015-11-30 |
EA028770B1 (ru) | 2017-12-29 |
US20150274618A1 (en) | 2015-10-01 |
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