WO2014007295A1 - 植物性バイオマスの分解方法及びグルコースの製造方法 - Google Patents
植物性バイオマスの分解方法及びグルコースの製造方法 Download PDFInfo
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- WO2014007295A1 WO2014007295A1 PCT/JP2013/068277 JP2013068277W WO2014007295A1 WO 2014007295 A1 WO2014007295 A1 WO 2014007295A1 JP 2013068277 W JP2013068277 W JP 2013068277W WO 2014007295 A1 WO2014007295 A1 WO 2014007295A1
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- Prior art keywords
- plant biomass
- temperature
- reaction
- acid
- cellulose
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- 239000002028 Biomass Substances 0.000 title claims abstract description 62
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 54
- 239000008103 glucose Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 33
- 239000011949 solid catalyst Substances 0.000 claims abstract description 33
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 26
- 230000007062 hydrolysis Effects 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 239000001913 cellulose Substances 0.000 claims description 49
- 229920002678 cellulose Polymers 0.000 claims description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- -1 water vapor activated activated carbon Chemical class 0.000 claims description 3
- 241000196324 Embryophyta Species 0.000 description 39
- 239000000758 substrate Substances 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 238000010298 pulverizing process Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 235000000346 sugar Nutrition 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000008163 sugars Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 241000609240 Ambelania acida Species 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 244000082204 Phyllostachys viridis Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000010905 bagasse Substances 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 150000004804 polysaccharides Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 241001133760 Acoelorraphe Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- FYGDTMLNYKFZSV-ZWSAEMDYSA-N cellotriose 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)O[C@@H](O[C@@H]2[C@H](OC(O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-ZWSAEMDYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
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- 238000006911 enzymatic reaction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 230000009229 glucose formation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
Definitions
- the present invention relates to a method for hydrolyzing plant biomass. More specifically, the present invention relates to a method for hydrolyzing a plant biomass-derived polysaccharide with a high saccharification yield by a reaction using a solid catalyst and a method for producing glucose.
- the hydrolysis reaction of cellulose by hydrothermal reaction using a solid catalyst is a solid-solid reaction, and the contact property between the catalyst and cellulose (substrate) is rate-determined. Therefore, in order to realize a highly efficient reaction, the reactivity A treatment method for improving the temperature and a highly active catalyst are being studied.
- Patent Document 1 describes a method of pre-mixing a pulverized substrate, a catalyst, and preliminary steam.
- Kai 2010-98994 Patent Document 2 describes a method of reacting a catalyst and a substrate under microwave irradiation.
- Patent Document 1 discloses that cellulose is decomposed by about 70%, there is no specific description about the yield of sugar as a decomposition product, and the effect is unknown.
- Patent Document 2 also has a problem in practicality in that the glucose yield is about 30%, a high reaction yield is not obtained, and the introduction of an expensive microwave irradiation device is necessary. .
- Patent Document 3 describes a method using an activated carbon solid acid catalyst treated with sulfuric acid as the solid catalyst.
- the glucose yield is only about 40%, and it is a problem to further improve the glucose yield for practical use.
- Japanese Patent Application Laid-Open No. 2008-271787 (US Pat. No. 8,382,905 / Patent Document 4) adds cellulose to a cluster acid catalyst in a pseudo-molten state. And the method of hydrolysis is described.
- Patent Document 4 it is difficult to control the water during the reaction, and a multi-step process is required for separating the catalyst and the product, and an organic solvent is used, so that there is a problem in practicality.
- Patent Document 5 As a method for increasing the saccharification rate in the cellulose hydrolysis reaction by hydrothermal treatment without using a solid catalyst, Japanese Patent Application Laid-Open No. 2011-206044 (Patent Document 5) contacts a raw material containing cellulose and an aqueous solution containing an inorganic acid. A method for obtaining a glucose yield of 60% or more by heating and pressurizing is described. However, in Patent Document 5, perchloric acid is used as an inorganic acid at a high concentration of 0.1 mol / L, and the pH of the reaction solution is extremely low, 0.8 to 0.9. There are problems such as later neutralization and purification treatment, corrosion of equipment materials, etc., and there is a problem in practicality.
- An object of the present invention is to provide a method capable of improving glucose yield and glucose selectivity in a method for hydrolyzing plant biomass.
- the present inventors have conducted a hydrolysis reaction of plant biomass using a solid catalyst in the presence of an inorganic acid.
- the inventors have found that the selectivity can be improved and have completed the present invention. That is, the present invention includes the following plant biomass hydrolysis methods [1] to [10] and glucose production method [11].
- a method for hydrolyzing plant biomass comprising heating a mixture comprising plant biomass, a solid catalyst for catalyzing hydrolysis of the biomass, an inorganic acid and water.
- the method for hydrolyzing plant biomass according to item 1 above wherein the pH of the mixture containing plant biomass, solid catalyst, inorganic acid and water is 1.0 to 4.0.
- the method for hydrolyzing plant biomass according to item 2 above wherein the pH of the mixture containing plant biomass, solid catalyst, inorganic acid and water is 2.0 to 3.0.
- the temperature-time product ((treatment temperature ⁇ 160 ° C.) ⁇ time) of the portion exceeding 160 ° C. is 200 to 800 ° C./min. 6.
- the carbon material is alkali activated carbon, water vapor activated activated carbon, or mesoporous carbon.
- a method for producing glucose comprising performing the hydrolysis method according to any one of items 1 to 10.
- the glucose yield and glucose selectivity can be improved.
- plant biomass (hereinafter sometimes referred to as a solid substrate) means, for example, rice straw, straw, sugarcane straw, rice husk, bagasse, hardwood, bamboo, conifer, kenaf, furniture waste, and building waste. It is a biomass mainly containing cellulose and hemicellulose, such as waste paper and food residues.
- biomass generally refers to “renewable biological organic resources excluding fossil resources”. Plant biomass can be used either purified or unpurified.
- What has been refined is treated with alkaline sulfite, alkaline sulfite, neutral sulfite, alkaline sodium sulfide, ammonia, etc., then subjected to delignification by separating the solid and liquid and washing with water. And those containing two or more of hemicellulose and lignin. Furthermore, industrially prepared cellulose, xylan, cellooligosaccharide, xylooligosaccharide and the like may be used. Impurities may contain ash such as silicon, aluminum, calcium, magnesium, potassium and sodium derived from plant biomass.
- Plant biomass may be dry or wet, and may be crystalline or non-crystalline. It is desirable to pulverize the plant biomass prior to the reaction. The contact property with the solid catalyst is increased by the pulverization, and the hydrolysis reaction is promoted. Therefore, it is desirable that the plant biomass has a shape and size suitable for pulverization. Examples of such shapes and sizes include powders having a particle size of 20 ⁇ m or more and several thousand ⁇ m or less.
- Solid catalyst is not particularly limited as long as it can catalyze the hydrolysis of plant biomass, but it is represented by ⁇ -1,4 glycosidic bond between glucose forming cellulose as the main component. It preferably has an activity of hydrolyzing a glycosidic bond.
- solid catalyst examples include carbon materials and transition metals. These can be used alone or in combination of two or more.
- Examples of the carbon material include activated carbon, carbon black, and graphite. These carbon materials may be used alone or in combination of two or more.
- the shape of the carbon material is preferably porous and / or fine particles in terms of improving reactivity by expanding the contact area with the substrate, and in terms of promoting acid hydrolysis by expressing acid sites.
- the surface preferably has a functional group such as a phenolic hydroxyl group, a carboxyl group, a sulfo group, or a phosphoric acid group.
- porous carbon materials having functional groups on the surface woody materials such as palm, bamboo, pine, walnut, and bagasse, coke, phenol, etc., are treated at high temperatures using gases such as water vapor, carbon dioxide, and air.
- activated carbon prepared by a chemical method such as a chemical method of treating at a high temperature using a chemical such as alkali or zinc chloride.
- transition metal examples include ruthenium, platinum, rhodium, palladium, iridium, nickel, cobalt, iron, copper, silver, and gold. These transition metals may be used alone or in combination of two or more. From the viewpoint of high catalytic activity, those selected from the platinum group metals of ruthenium, platinum, rhodium, palladium, and iridium are preferred, and from the viewpoint of high cellulose conversion and glucose selectivity, selected from ruthenium, platinum, palladium, and rhodium. Are particularly preferred.
- [Crushing plant biomass] Cellulose, which is the main component of plant biomass, exhibits crystallinity by binding two or more cellulose molecules by hydrogen bonding.
- cellulose having such crystallinity can be used as a raw material, but cellulose having crystallinity lowered by a treatment for lowering crystallinity can also be used.
- Cellulose with reduced crystallinity may be partially reduced in crystallinity or completely or almost completely lost.
- the type of the crystallinity reduction treatment is not particularly limited, but is preferably a crystallinity reduction treatment that can break the hydrogen bond and at least partially generate a single-chain cellulose molecule.
- Examples of a method for physically breaking hydrogen bonds between cellulose molecules include pulverization.
- the pulverizing means is not particularly limited as long as it has a function capable of being pulverized.
- the system of the apparatus may be either dry type or wet type, and the pulverization system of the apparatus may be either batch type or continuous type.
- the crushing force of the apparatus can be any of impact, compression, shear, friction and the like.
- Equipment that can be used for pulverization includes rolling ball mills such as pot mills, tube mills, and conical mills, vibration ball mills such as circular vibration type vibration mills, swivel type vibration mills, and centrifugal mills, stirring tank mills, annular mills, and distribution type mills.
- rolling ball mills such as pot mills, tube mills, and conical mills
- vibration ball mills such as circular vibration type vibration mills, swivel type vibration mills, and centrifugal mills
- stirring tank mills stirring tank mills, annular mills, and distribution type mills.
- Agitating mills such as tower crushers, swirling flow jet mills, impingement type jet mills, fluidized bed type jet mills, wet type jet mills, and other jet crushers, shearing machines (crushers), shears such as ong mills Collision mills such as mills, mortars, and stone mills, hammer mills, cage mills, pin mills, disintegrators, impact mills such as screen mills, turbo mills, centrifugal classifiers, and other types of milling that employ rotation and revolving motions.
- An example is a planetary ball mill.
- Hydrolysis is a reaction between the solid substrate and the solid catalyst, and the contact between the substrate and the catalyst is rate-limiting. Therefore, it is also effective to mix the solid substrate and the solid catalyst in advance and perform simultaneous pulverization as a method to improve the reactivity. It is.
- the simultaneous pulverization treatment can also serve as a pretreatment for reducing the crystallinity of the substrate in addition to the mixing.
- the pulverizer used is preferably a rolling ball mill, a vibrating ball mill, a stirring mill, or a planetary ball mill used for pretreatment for reducing the crystallinity of the substrate, and is classified as a pot mill or a stirring mill classified as a rolling ball mill.
- a stirred tank mill and a planetary ball mill are more preferable. Furthermore, since the higher the bulk density of the raw material subjected to the simultaneous pulverization of the solid catalyst and the solid substrate, the higher the tendency of the reactivity, it is possible to compress the pulverized solid catalyst and the pulverized solid substrate. It is more preferable to use a rolling ball mill, a stirring mill, or a planetary ball mill to which a strong force is applied.
- the ratio of the solid catalyst and the solid substrate to be simultaneously pulverized is not particularly limited, but in terms of hydrolysis efficiency during the reaction, reduction of the substrate residue after the reaction, and recovery rate of the produced sugar,
- the solid catalyst is preferably 1 to 100 parts by mass, more preferably 1 to 10 parts by mass.
- the raw material obtained by individually pulverizing the substrate and the raw material obtained by simultaneously pulverizing the substrate and the catalyst are both determined as the average particle diameter after pulverization (cumulative median diameter (median diameter))
- the particle diameter (D50) at which the cumulative curve is 50% is 1 to 100 ⁇ m, and is preferably 1 to 30 ⁇ m and more preferably 1 to 20 ⁇ m from the viewpoint of further improving the reactivity.
- Preliminary pulverization treatment can be carried out using a coarse pulverizer and a medium pulverizer such as a stamp mill, an edge runner, a cutting / shearing mill, a rod mill, an autogenous pulverizer, and a roller mill.
- the processing time of a raw material will not be limited if the raw material after a process is pulverized uniformly.
- the inorganic acid is preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or boric acid, and these can be used in combination.
- hydrochloric acid is particularly preferred because it has a high effect of increasing the glucose selectivity.
- the inorganic acid can be added using the pH after the addition as an index.
- the pH of the mixture containing plant biomass after addition of the inorganic acid, solid catalyst and water is preferably 1.0 to 4.0, and the pH is 2 in terms of achieving both high saccharification yield and suppression of excessive decomposition.
- pH 0.0 to 4.0 is more preferable, and pH 2.0 to 3.0 is most preferable.
- the pH was measured at 25 ° C. in a glass bottle using a pH meter D-51 (manufactured by Horiba, Ltd.) calibrated at three points using HORIBA, Ltd. pH STANDARD 100-4, 100-7, and 100-9. Then, after immersing the glass electrode of the device, the mixture was lightly stirred and then left to stand (about 1 minute) until it was stabilized.
- Hydrolysis using a polysaccharide derived from plant biomass as a substrate is performed by heating the substrate in the presence of a catalyst, an inorganic acid, and water, preferably at a temperature at which the substrate is pressurized.
- the heating temperature at which the pressure is applied is suitably in the range of 110 to 380 ° C., for example.
- a relatively high temperature is preferable from the viewpoint of rapidly performing the hydrolysis and suppressing the conversion of the product glucose to other sugars.
- maximum heating (reaction) The temperature is suitably in the range of 170 to 320 ° C, more preferably 170 to 200 ° C, and even more preferably 170 to 190 ° C.
- the holding time at the temperature is preferably 0 to 120 minutes.
- the area of the portion exceeding 160 ° C. (hereinafter referred to as “temperature-time product exceeding 160 ° C.”) in the figure where the vertical axis represents the reaction temperature and the horizontal axis represents time is 200 to 800 ° C./min. Is preferred.
- the temperature-time product exceeding 160 ° C. can be obtained by integrating the difference between the processing temperature and 160 ° C. (processing temperature ⁇ 160 ° C.) over time at a portion exceeding 160 ° C. Is linear and the figure is a mountain or trapezoid, it is expressed by the following equation.
- the hydrolysis is usually carried out in a closed container such as an autoclave, so even at normal pressure at the start of the reaction, at the above temperature.
- a closed container such as an autoclave
- the reaction system When the reaction system is heated, it enters a pressurized state.
- the reaction can be carried out by pressurizing the inside of the sealed container before or during the reaction.
- the pressure to be applied is, for example, 0.1 to 30 MPa, preferably 1 to 20 MPa, and more preferably 2 to 10 MPa.
- the reaction can also be carried out by heating and pressurizing the reaction solution with a high-pressure pump.
- the amount of water present for hydrolysis is an amount capable of hydrolyzing at least the total amount of cellulose, taking into consideration the fluidity and agitation of the reaction mixture, an amount 1 to 500 times the mass of cellulose, The amount is preferably 2 to 200 times.
- the atmosphere for the hydrolysis is not particularly limited. Industrially, it is preferably performed in an air atmosphere, but may be performed in an atmosphere of a gas other than air, for example, oxygen, nitrogen, hydrogen, or a mixture thereof.
- the heating for the hydrolysis is terminated when the conversion rate by hydrolysis of cellulose is between 10 and 100% and the selectivity of glucose is between 20 and 90%. It is preferable in terms of enhancement.
- the heating time is, for example, in the range of 5 to 60 minutes, preferably in the range of 5 to 30 minutes from the start of heating for the hydrolysis reaction under normal conditions, but is not limited to this range. .
- the heating for hydrolysis is such that the conversion by hydrolysis of cellulose is preferably in the range of 30 to 100%, more preferably in the range of 40 to 100%, still more preferably in the range of 50 to 100%, most preferably. Is in the range of 55-100% and ends when the glucose selectivity is preferably in the range of 25-90%, more preferably in the range of 30-90%, most preferably in the range of 40-90%. Is appropriate.
- the form of the hydrolysis reaction may be either a batch type or a continuous type.
- the reaction is preferably carried out while stirring the reaction mixture.
- the reaction solution After completion of the heating, it is preferable to cool the reaction solution from the viewpoint of suppressing the conversion of glucose to other sugars and increasing the glucose yield.
- the reaction solution is preferably cooled under the condition that the selectivity of glucose is maintained in the range of 20 to 90%, more preferably in the range of 25 to 90%, and 30 to 90%. Is more preferable, and the range of 40 to 90% is most preferable.
- the reaction solution is preferably cooled as quickly as possible to a temperature at which the conversion of glucose into other sugars does not occur, for example, at a rate in the range of 1 to 200 ° C./min. The rate is preferably in the range of 10 to 150 ° C./min.
- the temperature at which the conversion of glucose into other sugars does not occur is, for example, 150 ° C. or lower, preferably 110 ° C. or lower. That is, the reaction solution is suitably cooled to a temperature of 150 ° C. or lower in the range of 1 to 200 ° C./min, preferably in the range of 10 to 150 ° C./min. It is more appropriate to carry out in the range of ⁇ 200 ° C./min, preferably in the range of 10 to 150 ° C./min.
- the obtained raw material is referred to as a mixed pulverized raw material.
- reaction temperature When the reaction temperature was reached, the temperature was maintained for the time shown in Table 1, and then the heating was stopped, and the reactor was air-cooled at an average cooling rate of 16.7 ° C / min. After cooling, the reaction solution is separated into liquid and solid using a centrifuge, and the product in the liquid phase is a high performance liquid chromatograph manufactured by Shimadzu Corporation (Condition 1 Column: Shodex (registered trademark) SH-10111, mobile phase).
- Example 1 to 8 using an inorganic acid the cellulose conversion rate and the glucose yield were improved as compared with Comparative Example 1 not using an inorganic acid, and the glucose yield was higher as the pH was lower regardless of the type of acid. It was.
- the conditions that gave the best results among Examples 1 to 8 were Example 8 in which hydrochloric acid was added to adjust the pH to 2.5.
- the cellulose conversion was 93% and the glucose yield was 72%.
- the glucose selectivity was 77%.
- the result of Example 8 is expressed as a relative ratio to the result of Comparative Example 1 in which no inorganic acid is used, the cellulose conversion is 200%, the glucose yield is 900%, and the glucose selectivity is 460%, both of which are greatly improved. I understand that.
- Example 9 When comparing the types of acids, hydrochloric acid was superior to sulfuric acid, and a significant difference was observed particularly in glucose yield. Moreover, in Example 9 in which the heating time was extended in Example 8 where good results were obtained, it can be seen that the cellulose conversion rate, glucose yield, and glucose selectivity were further improved.
- Example 11 when the reaction temperature and the reaction temperature holding time were changed under the same hydrochloric acid conditions as in Example 8 with a pre-reaction pH of 2.5, the reaction temperature was changed to 190 ° C. for 5 minutes (Example 10) and 7 minutes (implementation).
- Example 11 at 180 ° C. for 10 minutes (Example 12), 20 minutes (Example 13), 25 minutes (Example 14), at 170 ° C. for 60 minutes (Example 15), 75 minutes (Example 16)
- the cellulose conversion rate, glucose yield, and glucose selectivity were all improved from Example 8, and even if the reaction temperature was lowered from 200 ° C., the result was the highest level exceeding Example 8 if the retention time was increased. Was found to be obtained.
- Example 13 The glucose yield of Example 13 was 88%, the cellulose conversion was 99%, and the glucose selectivity of Example 14 was 90%.
- Example 12 shows 74% below the highest level of performance, glucose is an intermediate product of cellulose hydrolysis, which is a sequential reaction, so if the retention time at the same reaction temperature is too short, it degrades. If the amount is too short or too long, the glucose yield decreases due to excessive decomposition, so that the conditions for obtaining the highest level of performance are within the range of a moderately heated heat history.
- Examples 8 to 16 that obtained good results were used as heat history parameters indicating reaction temperature and holding time conditions, with 160 ° C. being the temperature near the upper limit at which no decomposition of cellulose occurs at a holding time of 0 minutes.
- Example 9 and Example 13 the results of Comparative Example 2 and Comparative Example 3 in which hydrochloric acid was simply changed to no addition were all over 90% conversion.
- the glucose yield and selectivity are both about 20% at a level slightly lower than that of the examples, which is less than 1 ⁇ 4 of each example, and the yield of other sugars is about 70%, which is 10 times that of each example.
- the effect of adding hydrochloric acid is to hydrolyze most of the other oligosaccharides, and to decompose only monosaccharides to glucose, without excessively degrading them, and to improve yield and selectivity. It was.
- the suspension was suspended in 40 mL of water, set in a high pressure reactor (internal volume 100 mL, autoclave manufactured by Nitto Koatsu Co., Ltd., SUS316), and then heated from room temperature to a reaction temperature of 240 ° C. for about 15 minutes while stirring at 600 rpm. As soon as the reaction temperature was reached, heating was stopped and the reactor was placed in a water bath and cooled.
- the reaction solution After cooling, the reaction solution is separated into a liquid and a solid by a centrifugal separator, and the product in the liquid phase is a high performance liquid chromatograph (device: Shodex high performance liquid chromatography manufactured by Showa Denko KK, column: Shodex (registered trademark)).
- KS801 mobile phase: water 0.6 mL / min, 75 ° C., detection: differential refractive index).
- the cellulose conversion rate was calculated
- the present invention can improve glucose yield and glucose selectivity by a simple method of adjusting the pH by adding an inorganic acid, thereby effectively utilizing biomass resources. Very useful.
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Abstract
Description
例えば、固体-固体反応の系で反応性を向上させる方法として、特開2008-297229号公報(特許文献1)には粉砕した基質と触媒と予備蒸気とをミキシング予熱する方法が記載され、特開2010-98994号公報(特許文献2)には触媒と基質をマイクロ波の照射下で反応させる方法が記載されている。
しかしながら、特許文献1には、セルロースが70%程度分解されることを開示しているものの、分解生成物である糖収率について具体的記載がなく、その効果は不明である。また、特許文献2も、グルコース収率が約30%であり、高い反応収率は得られておらず、さらに高価なマイクロ波照射装置の導入が必要である点で実用性にも課題がある。
すなわち、本発明は以下の[1]~[10]の植物性バイオマスの加水分解方法、及び[11]のグルコースの製造方法を含む。
[2]植物性バイオマス、固体触媒、無機酸及び水を含む混合物のpHが1.0~4.0である前項1に記載の植物性バイオマスの加水分解方法。
[3]植物性バイオマス、固体触媒、無機酸及び水を含む混合物のpHが2.0~3.0である前項2に記載の植物性バイオマスの加水分解方法。
[4]無機酸が、塩酸、硫酸、硝酸、リン酸及びホウ酸から選ばれる少なくとも1種である前項1~3のいずれか1項に記載の植物性バイオマスの加水分解方法。
[5]無機酸が、塩酸である前項1~3のいずれか1項に記載の植物性バイオマスの加水分解方法。
[6]最高加熱(反応)温度が170℃~200℃であり、当該温度における保持時間が0~120分である前項1~5のいずれか1項に記載の植物性バイオマスの加水分解方法。
[7]縦軸に反応温度、横軸に時間を表した図における160℃を超える部分の温度時間積((処理温度-160℃)×時間)が200~800℃・分である前項1~6のいずれか1項に記載の植物性バイオマスの加水分解方法。
[8]固体触媒が炭素材料である前項1~7のいずれか1項に記載の植物性バイオマスの加水分解方法。
[9]炭素材料がアルカリ賦活活性炭、水蒸気賦活活性炭、またはメソポーラスカーボンである前項8に記載の植物性バイオマスの加水分解方法。
[10]植物性バイオマスがセルロースである前項1~9のいずれか1項に記載の植物性バイオマスの加水分解方法。
[11]前項1~10のいずれか1項に記載の加水分解方法を行うことを特徴とするグルコースの製造方法。
[植物性バイオマス(固体基質)]
本明細書において「植物性バイオマス」(以下、固体基質ということがある。)とは、例えば、稲わら、麦わら、サトウキビわら、籾殻、バガス、広葉樹、竹、針葉樹、ケナフ、家具廃材、建築廃材、古紙、食品残渣等の主にセルロースやヘミセルロースを含むバイオマスである。なお、「バイオマス」とは一般的には「再生可能な生物由来の有機性資源で化石資源を除いたもの」を指す。
植物性バイオマスは、精製処理してあるものでも、精製処理してないものでも用いることができる。精製処理してあるものは、アルカリ蒸煮、アルカリ性亜硫酸塩蒸煮、中性亜硫酸塩蒸煮、アルカリ性硫化ソーダ蒸煮、アンモニア蒸煮などの処理をした後に固液分離し水洗することにより脱リグニン処理を行い、セルロース、ヘミセルロース及びリグニンのうち2つ以上を含有するものが挙げられる。さらに、工業的に調製したセルロース、キシラン、セロオリゴ糖、キシロオリゴ糖などでも良い。不純物としては、植物性バイオマス由来の珪素、アルミニウム、カルシウム、マグネシウム、カリウム、ナトリウムなどの灰分を含有してもかまわない。
固体触媒は、植物性バイオマスの加水分解を触媒できるものであれば特に限定されるものではないが、主成分であるセルロースを形成しているグルコース間のβ-1,4グリコシド結合に代表されるような、グリコシド結合を加水分解する活性を有することが好ましい。
植物性バイオマスの主成分であるセルロースは、2本またはそれ以上のセルロース分子が水素結合により結合して結晶性を示す。本発明では、そのような結晶性を有するセルロースを原料として使用することもできるが、結晶性低下のための処理を施して結晶性を低下させたセルロースも用いることができる。結晶性を低下させたセルロースは、結晶性を部分的に低下させたものでも、完全にまたはほぼ完全に消失させたものでもよい。結晶性低下処理の種類には特に制限はないが、上記水素結合を切断して、1本鎖のセルロース分子を少なくとも部分的に生成できる結晶性低下処理であることが好ましい。少なくとも部分的に1本鎖のセルロース分子を含むセルロースを原料とすることで、加水分解の効率を大幅に向上することができる。
同時粉砕処理は、混合に加え、基質の結晶性を低下させる前処理を兼ねることができる。その観点から、用いる粉砕装置は、基質の結晶性を低下させる前処理に用いられる、転動ボールミル、振動ボールミル、撹拌ミル、遊星ボールミルが好ましく、転動ボールミルに分類されるポットミル、撹拌ミルに分類される撹拌槽ミル、遊星ボールミルがより好ましい。さらに、固体触媒と固体基質との同時粉砕処理された原料の嵩密度が大きい方が反応性が高い傾向が認められることから、固体触媒の粉砕物と固体基質の粉砕物とが食い込むような圧縮力が強く加わる転動ボールミル、撹拌ミル、遊星ボールミルを用いることがより好ましい。
処理する原料の粒径が大きい場合などは、微粉砕を効率的に行うために、微粉砕の前に、例えば、シュレッダー、ジョークラッシャー、ジャイレトリクラッシャー、コーンクラッシャー、ハンマークラッシャー、ロールクラッシャー、ロールミルなどの粗粉砕機、並びにスタンプミル、エッジランナ、切断・せん断ミル、ロッドミル、自生粉砕機、ローラミルなどの中粉砕機を用いて、予備的な粉砕処理を実施することができる。原料の処理時間は、処理後原料が均一に微粉化されるのであれば限定されるものではない。
無機酸は、塩酸、硫酸、硝酸、リン酸またはホウ酸が好ましく、これらを併用することも可能である。これらの無機酸を添加することにより、固体触媒による植物性バイオマスの加水分解反応における糖化率とグルコース選択率を高めることができる。グルコース選択率を高める効果が高いという点で、塩酸は特に好ましい。
無機酸の添加は、添加後のpHを指標にして行うことができる。無機酸を添加した後の植物性バイオマス、固体触媒及び水を含む混合物のpHはpH1.0~4.0が好ましく、高い糖化収率と過分解生成の抑制を両立するという点でpHが2.0~4.0がより好ましく、pH2.0~3.0が最も好ましい。
pHは、堀場製作所pH STANDARD100-4、100-7、及び100-9を用いて3点校正したpH計D-51(株式会社堀場製作所製)を用いて、ガラス瓶に入れた25℃の試料溶液に、機器のガラス電極を浸した後、軽く撹拌してから静置し安定するまで(1分程度)待ち計測した。
植物性バイオマス由来の多糖類を基質とする加水分解は、基質を触媒と無機酸と水の存在下、好ましくは加圧状態となる温度で加熱して行う。加圧状態となる加熱の温度は、例えば、110~380℃の範囲が適当である。植物性バイオマスがセルロースの場合、その加水分解を迅速に行い、かつ生成物であるグルコースの他の糖への転化を抑制するという観点から、比較的高い温度が好ましく、例えば、最高加熱(反応)温度は、170~320℃、より好ましくは170~200℃、さらに好ましくは170~190℃の範囲とすることが適当である。また、当該温度における保持時間は、0~120分であることが好ましい。
また、縦軸に反応温度、横軸に時間を表した図における160℃を超える部分の面積(以下、「160℃超の温度時間積」という。)が、200~800℃・分であることが好ましい。なお、160℃超の温度時間積は、160℃を超える部分において、処理温度と160℃との差(処理温度-160℃)を時間で積分することにより求めることができるが、昇温及び降温が直線的で、図が山型や台形となる場合、以下の式で表される。
グルコース収率を高めるという観点から、前記反応液の冷却は、グルコースの他の糖への転化が事実上生じない温度までできるだけ速く行うことが好ましく、例えば、1~200℃/分の範囲の速度で行うことができ、好ましくは10~150℃/分の範囲の速度である。グルコースの他の糖への転化が事実上生じない温度は、例えば、150℃以下、好ましくは110℃以下である。すなわち、反応液の冷却は、150℃以下の温度まで、1~200℃/分の範囲、好ましくは10~150℃/分の範囲で行うことが適当であり、110℃以下の温度まで、1~200℃/分の範囲、好ましくは10~150℃/分の範囲で行うことがより適当である。
[固体触媒]
コークスを700℃で加熱処理し、ジェットミルにて微粉砕した後、水酸化カリウムを添加し再度700℃で加熱処理して賦活化した。得られた賦活化コークスを、水洗後、塩酸で中和し、さらに熱水で煮沸した後、乾燥したものを篩分し、粒径1μm以上30μm以下のアルカリ賦活多孔質炭素材料(メジアン径13μm)を得た。得られた固体触媒を、以下、炭素触媒と称する。
固体基質としてのAvicel(Merck社製結晶性微粉セルロース)10.00gと、炭素触媒1.54g(基質と触媒の質量比6.5:1.0)を、容量3600mLのセラミックポットミルの中に直径1.5cmのアルミナ球2000gと共に入れた。このセラミックポットミルを卓上ポットミル回転台(日陶科学(株)製,卓上ポットミル型式ANZ-51S)にセットし、60rpmで48時間ボールミル処理して混合同時粉砕した。得られた原料を、以下、混合粉砕原料と称する。
固体基質としてのAvicel(Merck社製結晶性微粉セルロース)3.00gを、容量500mLのセラミックポットミルの中に直径1.5cmのジルコニア球300gと共に入れた。このセラミックポットミルを卓上ポットミル回転台((株)入江商会製,卓上ポットミル型式V-1M)にセットし、60rpmで48時間ボールミル処理して粉砕した。得られた原料を、以下、個別粉砕原料と称する。
混合粉砕原料0.374g(C6H10O5単位で2.00mmol)と、表1に記載の無機酸を用いて、表1に記載のpHに調整した水分散液40mLを、高圧反応器(内容積100mL,オーエムラボテック(株)製オートクレーブ,ハステロイC22製)に入れた後、600rpmで撹拌しながら室温から表1に記載の反応温度まで平均昇温速度11.3℃/分で加熱した。反応温度に到達するとその温度で表1に記載の時間保持して後に加熱を止め、反応器を平均降温速度16.7℃/分で風冷した。冷却後、反応液を遠心分離装置により液体と固体に分離し、液相の生成物は、(株)島津製作所製高速液体クロマトグラフ(条件1 カラム:Shodex(登録商標)SH-1011,移動相:水0.5mL/min,50℃,検出:示差屈折率、条件2 カラム:Phenomenex Rezex RPM-Monosaccharide Pb++(8%),移動相:水0.6mL/min,70℃,検出:示差屈折率)によりグルコース、その他糖類及び過分解物を定量分析した。また、固体残渣を110℃で24時間乾燥したものを未反応セルロースと炭素触媒とし、その質量からセルロース転化率を求めた。結果を表1~2及び図1に示す。なお、表2における値は、比較例1の値を100とした場合の相対値である。
以下に収率及びセルロース転化率、グルコース選択率の計算式を示す。
酸の種類を比較すると、硫酸より塩酸の方が優れた結果が得られ、特にグルコース収率において有意な差が見られた。
また、良好な結果が得られた実施例8において加熱時間を長くした実施例9では、セルロース転化率、グルコース収率、グルコース選択率共にさらに向上していることが分かる。
実施例12が最高レベルの成績より低い74%になったことが示すように、グルコースは逐次反応であるセルロースの加水分解の中間生成物であるため、同じ反応温度における保持時間は短すぎると分解不足で、また長すぎると過分解でグルコース収率は低下することになるので、最高レベルの成績が得られる条件は、過不足なく適度な加熱された熱履歴の範囲に入ることになる。
良好な結果を得た実施例8~16を、反応温度と保持時間の条件を示す熱履歴パラメータとして、保持時間0分でセルロースの分解が起こらない上限付近の温度である160℃を基準とした、昇温から降温までの液温160℃以上における温度時間積(=(処理温度-160℃)×時間)のデータを表3に示す。実施例8~16の温度時間積は200~800℃・分の範囲入ることが分かった。
個別粉砕原料0.324g(C6H10O5単位で2.00mmol)、炭素触媒0.050g及び表4に記載した塩濃度(N=規定度)にするための必要量を秤量した塩を40mLの水で懸濁し、高圧反応器(内容積100mL,日東高圧社製オートクレーブ,SUS316製)にセットした後、600rpmで撹拌しながら室温から反応温度240℃まで約15分で加熱した。反応温度に到達すると同時に加熱を止め、反応器を水槽に入れ冷却した。冷却後、反応液を遠心分離装置により液体と固体に分離し、液相の生成物は、高速液体クロマトグラフ(装置:昭和電工(株)製Shodex高速液体クロマトグラフィー,カラム:Shodex(登録商標)KS801,移動相:水0.6mL/min,75℃,検出:示差屈折率)により定量分析した。また、水洗した固体残渣を110℃で24時間乾燥した後、未反応セルロースの質量からセルロース転化率を求めた。結果を表4~5及び図2に示す。
このことにより、SO4 2-やCl-のようなアニオンが存在すれば良いという訳ではなく、pHが重要であるということが示唆される。
Claims (11)
- 植物性バイオマスを加水分解する方法であって、植物性バイオマス、前記バイオマスの加水分解を触媒する固体触媒、無機酸及び水を含む混合物を加熱する工程を有することを特徴とする方法。
- 植物性バイオマス、固体触媒、無機酸及び水を含む混合物のpHが1.0~4.0である請求項1に記載の植物性バイオマスの加水分解方法。
- 植物性バイオマス、固体触媒、無機酸及び水を含む混合物のpHが2.0~3.0である請求項2に記載の植物性バイオマスの加水分解方法。
- 無機酸が、塩酸、硫酸、硝酸、リン酸及びホウ酸から選ばれる少なくとも1種である請求項1~3のいずれか1項に記載の植物性バイオマスの加水分解方法。
- 無機酸が、塩酸である請求項1~3のいずれか1項に記載の植物性バイオマスの加水分解方法。
- 最高加熱(反応)温度が170℃~200℃であり、当該温度における保持時間が0~120分である請求項1~5のいずれか1項に記載の植物性バイオマスの加水分解方法。
- 縦軸に反応温度、横軸に時間を表した図における160℃を超える部分の温度時間積((処理温度-160℃)×時間)が200~800℃・分である請求項1~6のいずれか1項に記載の植物性バイオマスの加水分解方法。
- 固体触媒が炭素材料である請求項1~7のいずれか1項に記載の植物性バイオマスの加水分解方法。
- 炭素材料がアルカリ賦活活性炭、水蒸気賦活活性炭、またはメソポーラスカーボンである請求項8に記載の植物性バイオマスの加水分解方法。
- 植物性バイオマスがセルロースである請求項1~9のいずれか1項に記載の植物性バイオマスの加水分解方法。
- 請求項1~10のいずれか1項に記載の加水分解方法を行うことを特徴とするグルコースの製造方法。
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WO2018131711A1 (ja) * | 2017-01-16 | 2018-07-19 | 国立大学法人北海道大学 | 糖類含有セルロース加水分解物の製造方法 |
WO2019208594A1 (ja) * | 2018-04-24 | 2019-10-31 | 日立化成株式会社 | 炭素触媒、及び水溶性糖類の製造方法 |
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