CN105525044A - Method for preparing reducing sugar from cellulose and hemicellulose raw materials through ultralow acid catalytic hydrolysis in polar aprotic system - Google Patents
Method for preparing reducing sugar from cellulose and hemicellulose raw materials through ultralow acid catalytic hydrolysis in polar aprotic system Download PDFInfo
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- 239000001913 cellulose Substances 0.000 title claims abstract description 36
- 229920002678 cellulose Polymers 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 36
- 235000000346 sugar Nutrition 0.000 title claims abstract description 32
- 229920002488 Hemicellulose Polymers 0.000 title claims abstract description 25
- 239000002994 raw material Substances 0.000 title claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 title abstract description 19
- 230000007062 hydrolysis Effects 0.000 title abstract description 18
- 239000002253 acid Substances 0.000 title abstract description 6
- 230000003197 catalytic effect Effects 0.000 title abstract 2
- 239000012046 mixed solvent Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000000967 suction filtration Methods 0.000 claims abstract description 18
- 239000012074 organic phase Substances 0.000 claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 15
- 238000000605 extraction Methods 0.000 claims abstract description 14
- 239000012071 phase Substances 0.000 claims abstract description 11
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 28
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 240000008042 Zea mays Species 0.000 claims description 12
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 9
- 239000010902 straw Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002028 Biomass Substances 0.000 claims description 7
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims description 7
- 235000009973 maize Nutrition 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 5
- 235000005822 corn Nutrition 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 241000609240 Ambelania acida Species 0.000 claims description 3
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 239000010905 bagasse Substances 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- ZNRSXPDDVNZGEN-UHFFFAOYSA-K trisodium;chloride;sulfate Chemical compound [Na+].[Na+].[Na+].[Cl-].[O-]S([O-])(=O)=O ZNRSXPDDVNZGEN-UHFFFAOYSA-K 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000000413 hydrolysate Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000000194 supercritical-fluid extraction Methods 0.000 abstract 1
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 10
- 229960003487 xylose Drugs 0.000 description 9
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000004064 recycling Methods 0.000 description 7
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 6
- 238000000855 fermentation Methods 0.000 description 6
- 230000004151 fermentation Effects 0.000 description 6
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 6
- 229940040102 levulinic acid Drugs 0.000 description 6
- 150000002772 monosaccharides Chemical class 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 5
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 5
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 230000008595 infiltration Effects 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- 150000008163 sugars Chemical class 0.000 description 5
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 150000004804 polysaccharides Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- PLZNPHDJGFDNRM-UHFFFAOYSA-M O.[Na+].[O-][PH2]=O Chemical compound O.[Na+].[O-][PH2]=O PLZNPHDJGFDNRM-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 229940041514 candida albicans extract Drugs 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011218 seed culture Methods 0.000 description 2
- 229920001221 xylan Polymers 0.000 description 2
- 150000004823 xylans Chemical class 0.000 description 2
- 239000012138 yeast extract Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 241000196324 Embryophyta 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
- 229920001410 Microfiber Polymers 0.000 description 1
- KVCWSJZUKMSPLM-UHFFFAOYSA-N O.O[PH2]=O Chemical compound O.O[PH2]=O KVCWSJZUKMSPLM-UHFFFAOYSA-N 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- SRBFZHDQGSBBOR-QMKXCQHVSA-N alpha-L-arabinopyranose Chemical compound O[C@H]1CO[C@@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-QMKXCQHVSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- -1 hypophosphite monohydrate disodium hydrogen Chemical class 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000003658 microfiber Substances 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
- 235000019319 peptone Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009923 sugaring Methods 0.000 description 1
- OGWLTJRQYVEDMR-UHFFFAOYSA-F tetramagnesium;tetracarbonate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O OGWLTJRQYVEDMR-UHFFFAOYSA-F 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
- C13K13/002—Xylose
-
- 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
- C13K1/04—Purifying
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for preparing reducing sugar from cellulose and hemicellulose through ultralow acid catalytic hydrolysis in a polar aprotic system. Water, a polar aprotic solvent and concentrated sulfuric acid are uniformly mixed, and a mixed solvent is obtained; the cellulose and hemicellulose raw materials are added to the mixed solvent to be soaked, the temperature is raised linearly from 110-130 DEG C to 150-220 DEG C, the mixture is heated to react for 30-60 minutes, suction filtration is performed while the mixture is hot after the reaction ends, and filtrate and filter residues are obtained; the filter residues are added to the mixed solvent, the soaking and heating reaction and suction filtration are performed twice, filtrate is collected and is subjected to supercritical extraction through carbon dioxide, alternatively, an inorganic salt extraction agent is added, a water phase and an organic phase are separated, and the water phase is a solvent containing the reducing sugar. The concentration of the reducing sugar in hydrolysate obtained ultimately with the method can be higher than 180 g/L, and the yield of the reducing sugar obtained through hydrolysis can be higher than 91%. According to the method, the consumption of sulfuric acid is extremely low, the conversion rate is higher, and the cost is lower.
Description
Technical field
The invention belongs to technical field of biochemical industry, be specifically related to a kind of in aprotic, polar system ultralow acid-catalyzed hydrolysis Mierocrystalline cellulose, hemicellulosic material prepare the method for reducing sugar.
Background technology
The macromolecular polysaccharide that Mierocrystalline cellulose (cellulose) is made up of glucose.Water insoluble and common organic solvents.It is the main component of plant cell wall.Mierocrystalline cellulose is a kind of polysaccharide that occurring in nature distribution is the widest, content is maximum, accounts for more than 50% of vegitabilia's carbon content.Hemicellulose (hemicellulose) is the heteromultimer be made up of several dissimilar monose, and these sugar are five-carbon sugar and hexose, comprises wood sugar, pectinose and semi-lactosi etc.Hemicellulose xylan accounts for 50% of total amount in lignum, and it is combined in the surface of cellulose micro-fibers, and is interconnected, and these fibers constitute the interconnective network of hard cell.
Traditional biochemical industry relies on grain raw material, but provision price is in rise situation all the time causes production cost to remain high, and finding alternate resources is the task of top priority.Be renewable resources the abundantest on the earth with the lignocellulose-like biomass that Mierocrystalline cellulose, hemicellulose are representative, there is the advantages such as cheapness, regeneration period be short and pollution-free.Therefore, Mierocrystalline cellulose, hemicellulose being converted into the energy, industrial raw material, fine chemicals, is the study hotspot of biomass recycling use.But, Mierocrystalline cellulose, hemicellulose complex structure, there is a large amount of crystalline region, amorphous silicon carbonfilms and hydrogen bond in inside, cause the lignocellulose percent hydrolysis under native state very low, lignocellulose must be made loosely organized by preconditioning technique, more Mierocrystalline cellulose and hemicellulose are exposed to surface, promote the hydrolysis and saccharification in later stage.Lignocellulose raw material pretreatment process comprises Physical, chemical method, physical-chemical method and biological process etc., but these pretreatment process ubiquities environmental pollution, economy deficiency and the shortcoming of amplifying the aspects such as difficulty.
Pretreated lignocellulose forms the monose hydrolyzed solution based on glucose and xylose after further hydrolysis and saccharification, at present many employing acid hydrolysiss and enzymic hydrolysis two kinds of approach.
In dilute acid hydrolysis process, most hemicellulose and a small amount of Mierocrystalline cellulose are degraded to soluble saccharide, form the hydrolyzed solution based on wood sugar, and this is also the method for hydrolysis generally adopted in current Mierocrystalline cellulose xylose production process.AguilarR etc. utilize 2% dilute sulphuric acid to process 24min at 122 DEG C, and 92% xylan hydrolysis in bagasse can be made to be wood sugar; 2% dilute sulphuric acid 122 DEG C process 71min, the wood sugar output of sorghum stalk is 18.17g/100g (raw material).Improving the concentration of acid or treatment temp can the hydrolysis of accelerating fibers element, improves glucose yield.As jute stalk with 70% sulfuric acid, 40 ~ 50 DEG C process 10 ~ 20min, total sugar yield is close to 100%; The people such as Zhou Lanlan use Concentrated acid hydrolysis wood chip, and monose yield reaches more than 90%.In order to alleviate the harm of concentrated acid on equipment and the impact on product quality, investigator is also had to propose two step dilute acid hydrolysis methods: first to adopt low temperature by hydrolysis of hemicellulose at high temperature hydrocellulose again.As Wang Chenxia etc. adopts 72% vitriol oil, the lower 30 DEG C of process 2h of normal pressure, then use the dilute sulphuric acid of 4%, at 0.1MPa hydrolyzed under pressure 1h, the mass transitions rate of corn cob reducing sugar and five-carbon sugar is respectively 81% and 46%; Wang Huan etc. first adopt 60% sulfuric acid, and acid is admittedly than 12: Isosorbide-5-Nitrae 5 DEG C hydrolysis 30min, then under water-solid ratio 220: 1 condition, 100 DEG C of hydrolysis 120min, maize straw total reducing sugar yield can reach 93.81%.But, though be adopt which kind of technique, all exist acid recovery difficulty, by product mainly with and must the shortcomings such as corrosion resistant apparatus be selected.
Enzymatic hydrolysis refers to that lignocellulose generates the process of corresponding kind monose after pretreatment again under the effect of enzyme.Be hydrolyzed through various pretreated lignocellulosic material can obtain reducing sugar by adding the biological catalyst such as cellulase, but the preparation cost of hydrolysis enzyme is high at present, causes that cost does not have competitive power.
In order to solve above drawback, JeremyS.Luterbacher, γ-valerolactone is applied in cellulosic hydrolysis reaction by the multidigit scholars such as JacquelineM.Rand, obtain higher yield, but the method solvent load is large, equipment is complicated, and the polysaccharide and the oligosaccharide content that are not easy to microorganism utilization in gained reducing sugar reach more than 50%, if also needed further by traditional technology acid hydrolysis for fermentation.
Therefore, urgently development is a kind of easy to operate, easily separated, and cost is low, and eco-friendly Mierocrystalline cellulose, hydrolysis of hemicellulose prepare the method for monose, improves the economy that lignocellulose biomass utilizes, and reduces environmental pressure.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that is simple, economic, efficient, environmental protection and produces reducing sugar by Mierocrystalline cellulose, hemicellulosic material.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
In polar aprotic solvent, ultralow acid-catalyzed hydrolysis Mierocrystalline cellulose, hemicellulosic material prepare a method for reducing sugar, and it comprises the steps:
(1) water, polar aprotic solvent and the vitriol oil are mixed and obtain mixed solvent in 1:4 ~ 9:0.0025 ~ 0.005 in mass ratio;
(2) Mierocrystalline cellulose, hemicellulosic material are added in the mixed solvent that step (1) obtains and infiltrate, from 110 DEG C ~ 130 DEG C linear temperature increase to 150 ~ 220 DEG C, reacting by heating 30 ~ 60 minutes altogether, after reaction terminates, suction filtration obtains filtrate and filter residue while hot;
(3) filter residue is added in the mixed solvent that step (1) obtains and infiltrate, from 110 DEG C ~ 130 DEG C linear temperature increase to 150 ~ 220 DEG C, reacting by heating 30 ~ 60 minutes altogether, after reaction terminates, suction filtration obtains filtrate and filter residue while hot;
(4) by the filter residue repeating step (3) that obtains after step (3) suction filtration once;
(5) filtrate of combining step (2), (3), (4) gained is collected, filtrate is by carbon dioxide upercritical fluid extraction water phase separated and organic phase, or add inorganic salt behind filtrate adjust ph to 5 ~ 6 and be stirred to the rear hold over night of dissolving completely, water phase separated and organic phase, gained aqueous phase is the solution containing reducing sugar.
In step (1), described polar aprotic solvent is gamma-butyrolactone, γ-valerolactone, tetrahydrofuran (THF) or dimethyl formamide polar aprotic solvent, preferred gamma-butyrolactone.
In step (1), the described vitriol oil is the vitriol oil of 95wt%.
In step (1), preferably by water, polar aprotic solvent and the vitriol oil in mass ratio 1:4:0.0025 mix and obtain mixed solvent.
In step (2), described Mierocrystalline cellulose, hemicellulosic material are any one or a few the mixture in the cheap lignocellulose-like biomass raw materials such as maize straw, corn cob, wheat stalk, bagasse and straw, or are stripped of the above raw material of wherein hemicellulose through pre-treatment.
In step (2), the solid-liquid mass ratio of Mierocrystalline cellulose, hemicellulosic material and mixed solvent is 1:15 ~ 30, preferred 1:20.
In step (3), the functional quality of mixed solvent is identical with the functional quality of mixed solvent in step (2).
In step (5), carbon dioxide upercritical fluid extraction, actual conditions is: pressure 72.9 ~ 92.9atm, temperature 31.26 ~ 51.26 DEG C, and extraction time is 20 ~ 60 minutes, and optimum condition is: pressure 73atm, temperature 40 DEG C, and extraction time is 60 minutes.
In step (5), filtrate uses calcium carbonate or calcium hydroxide adjust ph to 5 ~ 6.
In step (5), add that quality is the total mass of water in reaction system to be added 0.5 ~ 12% of inorganic salt, preferably 1%.Because whole reaction is carried out in encloses container, therefore, in reaction system to be added the total mass of water with the Mass Calculation of water in the mixed solvent to add for three times.
In step (5), described inorganic salt are any one or a few in sodium-chlor, sodium sulfate, Repone K and potassium sulfate, preferred sodium-chlor.
In step (5), be separated the organic phase obtained and recycle and reuse, be reused for the cheap biomass-making of degraded and prepare glucose for mixing sugar or degraded cellulose.
In step (5), be separated in the aqueous phase obtained, total reducing sugars content can reach more than 180g/L, and hydrolysis sugaring yield can reach more than 91%.The liquid glucose obtained can be used as the fermenting carbon source of industrial microorganism.
Beneficial effect: the present invention compared with prior art, has the following advantages:
1. polar aprotic solvent can recycling use, cost-saving, environmental friendliness.
2. bio-toxicity substances content low (wherein the content of levulinic acid, furfural, hydroxymethylfurfural is not all higher than 1g/L) in this law gained reduction liquid glucose, is easy to be utilized by microorganism.
3. acid catalyst levels is extremely low, and environmental pollution is little, without the need to reclaiming, cost-saving.Overcome the problem such as equipment complexity or separation difficulty, High Temperature High Pressure, equipment corrosion in background technology, belong to environmentally friendly technology route.
4. when polar aprotic solvent selects gamma-butyrolactone, water, polar aprotic solvent and vitriol oil mass ratio select 1:4:0.0025, during inorganic salt selective chlorination sodium, finally hydrolysis sugar liquid is obtained by the inventive method, reductive monosaccharide concentration can reach more than 180g/L, yield reaches more than 91%, can reduce the later stage to concentrate energy consumption.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1:
Added by 10g maize straw in 200g mixed solvent, mixed solvent component is: water: gamma-butyrolactone: the 98wt% vitriol oil (mass ratio)=1:4:0.0025.Stirring is placed in homogeneous reactor, from 120 DEG C of linear temperature increases to 220 DEG C, and altogether reacting by heating 60 minutes, suction filtration while hot after reaction terminates.Filter residue takes out and continues to add 200g mixed solvent, infiltrates, from 120 DEG C of linear temperature increases to 220 DEG C, and altogether reacting by heating 60 minutes, suction filtration while hot after reaction terminates.Filter residue takes out and continues to add the infiltration of 200g mixed solvent, and from 120 DEG C of linear temperature increases to 220 DEG C, reacting by heating 60 minutes altogether, reaction terminates, and Mierocrystalline cellulose, hemicellulose dissolve completely.Collect gained filtrate, filtrate is by the sodium-chlor water phase separated and the organic phase that add aqueous phase quality 1% after calcium carbonate adjust ph to 5.5.Organic phase recycling, after aqueous phase analyzes each component by HPLC, wherein, Mierocrystalline cellulose, hemicellulose transformation efficiency 100%, reductive monosaccharide yield 92%, total reducing sugars concentration 181g/L, glucose concn 86g/L, xylose concentration 60g/L, levulinic acid 0.45g/L, furfural 0.35g/L, hydroxymethylfurfural 0.6g/L.
Embodiment 2:
Added by 10g wheat stalk in 200g mixed solvent, mixed solvent component is: water: gamma-butyrolactone: the 98wt% vitriol oil (mass ratio)=1:4:0.0025.Stirring is placed in homogeneous reactor, from 120 DEG C of linear temperature increases to 220 DEG C, and altogether reacting by heating 60 minutes, suction filtration while hot after reaction terminates.Filter residue takes out, and adds 200g mixed solvent and infiltrates, from 120 DEG C of linear temperature increases to 220 DEG C, and altogether reacting by heating 60 minutes, suction filtration while hot after reaction terminates.Filter residue takes out and continues to add the infiltration of 200g mixed solvent, and from 120 DEG C of linear temperature increases to 220 DEG C, reacting by heating 60 minutes altogether, reaction terminates, and Mierocrystalline cellulose, hemicellulose dissolve completely.Collect gained filtrate, filtrate uses calcium hydroxide adjust ph to 6, adds sodium-chlor water phase separated and the organic phase of aqueous phase quality 2% subsequently.Organic phase recycling, after aqueous phase analyzes each component by HPLC, for fermentation production of succinic acid, synthetic gamma butyrolactone.Gained gamma-butyrolactone makes in the solvent next time reacted.Wherein, Mierocrystalline cellulose, hemicellulose transformation efficiency 100%, reductive monosaccharide yield 91.5%, total reducing sugars concentration 176g/L, glucose concn 81g/L, xylose concentration 60g/L, levulinic acid 0.35g/L, furfural 0.45g/L, hydroxymethylfurfural 0.55g/L.
Embodiment 3:
10g corncob powder added in 200g mixed solvent, mixed solvent component is: water: gamma-butyrolactone: the 98wt% vitriol oil (mass ratio)=1:4:0.0025.Stirring is placed in homogeneous reactor, from 120 DEG C of linear temperature increases to 220 DEG C, and altogether reacting by heating 60 minutes, suction filtration while hot after reaction terminates.Filter residue takes out, and adds 200g mixed solvent and infiltrates, from 120 DEG C of linear temperature increases to 220 DEG C, and altogether reacting by heating 60 minutes, suction filtration while hot after reaction terminates.Filter residue takes out and continues to add the infiltration of 200g mixed solvent, and from 120 DEG C of linear temperature increases to 220 DEG C, reacting by heating 60 minutes altogether, reaction terminates, and Mierocrystalline cellulose, hemicellulose dissolve completely.Collect gained filtrate, after filtrate calcium carbonate adjust ph to 5.5, add sodium-chlor water phase separated and the organic phase of aqueous phase quality 1%.Organic phase recycling, after aqueous phase analyzes each component by HPLC, for fermentation production of succinic acid, synthetic gamma butyrolactone.Gained gamma-butyrolactone makes in the solvent next time reacted.Wherein, Mierocrystalline cellulose, hemicellulose transformation efficiency 100%, reductive monosaccharide yield 92.9%, total reducing sugars concentration 182g/L, glucose concn 81g/L, xylose concentration 62g/L, levulinic acid 0.37g/L, furfural 0.47g/L, hydroxymethylfurfural 0.75g/L.
Embodiment 4:
150g maize straw end is added 600g to be contained in the mixed solvent of 150mM sulfuric acid, and mixed solvent component is: water: gamma-butyrolactone (mass ratio)=1:4.Stirring is placed in homogeneous reactor, and 120 DEG C are reacted 60 minutes, filter the maize straw residue obtaining xylogen and hemicellulose.Add in 200g mixed solvent by above-mentioned for 10g residue, mixed solvent component is: water: gamma-butyrolactone: the 98wt% vitriol oil (mass ratio)=1:4:0.0025.Stirring is placed in homogeneous reactor, from 120 DEG C of linear temperature increases to 150 DEG C, and altogether reacting by heating 30 minutes, suction filtration while hot after reaction terminates.Filter residue takes out, and adds 200g mixed solvent and infiltrates, from 120 DEG C of linear temperature increases to 150 DEG C, and altogether reacting by heating 30 minutes, suction filtration while hot after reaction terminates.Filter residue takes out and continues to add the infiltration of 200g mixed solvent, and from 120 DEG C of linear temperature increases to 150 DEG C, reacting by heating 30 minutes altogether, reaction terminates, and residue dissolves completely.Collect gained filtrate, adopt carbon dioxide upercritical fluid extraction water phase separated and organic phase, actual conditions is: pressure 73atm, temperature 40 DEG C, and extraction time is 60 minutes.After extraction, organic phase recycling, after aqueous phase analyzes each component by HPLC, for fermentation.Wherein, cellulose conversion rate 100%, reductive monosaccharide yield 96%, glucose concn 210g/L, levulinic acid 0.25g/L, hydroxymethylfurfural 0.86g/L.
Embodiment 5:
Be 5% at the massfraction of NaOH solution, under temperature of reaction is 55 DEG C, the reaction times is 1.5h condition, remove hemicellulose; At NaClO
2strength of solution is under 9.5g/L, treatment temp 75 DEG C of conditions, and the reaction times is remove xylogen under 2h condition.Filter the maize straw residue obtaining xylogen and hemicellulose.Add in 200g mixed solvent by above-mentioned for 10g residue, mixed solvent component is: water: gamma-butyrolactone: the 98wt% vitriol oil (mass ratio)=1:4:0.0025.Stirring is placed in homogeneous reactor, from 120 DEG C of linear temperature increases to 150 DEG C, and altogether reacting by heating 30 minutes, suction filtration while hot after reaction terminates.Filter residue takes out, and adds 200g mixed solvent and infiltrates, from 120 DEG C of linear temperature increases to 150 DEG C, and altogether reacting by heating 30 minutes, suction filtration while hot after reaction terminates.Filter residue takes out and continues to add the infiltration of 200g mixed solvent, and from 120 DEG C of linear temperature increases to 150 DEG C, reacting by heating 30 minutes altogether, reaction terminates, and residue dissolves completely.Collect gained filtrate, adopt carbon dioxide upercritical fluid extraction water phase separated and organic phase, actual conditions is: pressure 73atm, temperature 40 DEG C, and extraction time is 60 minutes.After extraction, organic phase recycling, after aqueous phase analyzes each component by HPLC, for fermentation.Wherein, cellulose conversion rate 100%, reductive monosaccharide yield 95.5%, glucose concn 189g/L, levulinic acid 0.29g/L, hydroxymethylfurfural 0.9g/L.
Embodiment 6 ~ 10:
Other reactions steps is with example 1, but the non-edible cheap biomass material used and consumption difference thereof, selected polar aprotic solvent is different from Inorganic Salts, and wherein under all reaction conditionss, inorganic salt consumption is all 1% of aqueous phase quality in reaction system.Detailed reaction condition is in table 1.
Table 1
Embodiment 11:
Configuration seed culture medium, composition is: glucose 10g/L (separately sterilizing), yeast extract paste 5g/L, Dried Corn Steep Liquor Powder 2.5g/L, sodium bicarbonate 10g/L, two hypophosphite monohydrate sodium dihydrogen 9.6g/L, three hypophosphite monohydrate hydrogen dipotassium 15.5g/L, sodium-chlor 1g/L, 121 DEG C of sterilizing 15min.
By the frozen bacterial classification (ActinobacillussuccinogenesNJ113 in-70 DEG C of refrigerators, CGMCCNo.11716) be inoculated in 100ml to be equipped with in the serum bottle of seed culture medium and to cultivate, liquid amount 50ml, inoculum size 3%, in 37 DEG C, cultivate 10h as seed liquor in 200r/min shaking table.
Configuration fermention medium: yeast extract paste 10g/L, peptone 4g/L, Dried Corn Steep Liquor Powder 7.5g/L, sodium acetate 1.36g/L, dipotassium hydrogen phosphate 3g/L, sodium-chlor 1g/L, calcium chloride 0.2g/L, two hypophosphite monohydrate sodium dihydrogen 1.6g/L, three hypophosphite monohydrate disodium hydrogen 0.31g/L, bicarbonate of ammonia 1.57g/L, magnesium basic carbonate 56g/L, 121 DEG C of sterilizing 15min.Aseptic working platform adds the hydrolysis sugar liquid (separately sterilizing) of preparation in example 1 ~ 9 respectively, makes the total reducing sugars concentration in substratum reach 70g/L.
Fermentation inoculum size 6% (volume fraction), logical carbonic acid gas 2min, sealed fermenting 72h, shaking speed 200r/min at 37 DEG C.The results are shown in Table 2.
Table 2
Can be found out by above embodiment: the present invention be a kind of in the mixed system of polar aprotic solvent and water, with the vitriol oil of ultra-low volume for catalyzer, achieve a kind of method being prepared reducing sugar under relatively mild conditions by cheap lignocellulose-like biomass.The present invention has significant advantage: reaction conditions is gentle, and simple to operate, environmental friendliness, acid catalyst levels is low, and Reducing sugar is high, and the liquid glucose of acquisition can be utilized by microorganism, and its leavening property is close to glucose.The present invention is Mierocrystalline cellulose, hemicellulose biolobic material utilizes and provides a feasible efficient approach, and gained reducing sugar is as biochemical industry raw material, of many uses, has good industrial applications and is worth.
Claims (10)
1. in polar aprotic solvent, ultralow acid-catalyzed hydrolysis Mierocrystalline cellulose, hemicellulosic material prepare a method for reducing sugar, it is characterized in that it comprises the steps:
(1) water, polar aprotic solvent and the vitriol oil are mixed and obtain mixed solvent in 1:4 ~ 9:0.0025 ~ 0.005 in mass ratio;
(2) Mierocrystalline cellulose, hemicellulosic material are added in the mixed solvent that step (1) obtains and infiltrate, from 110 DEG C ~ 130 DEG C linear temperature increase to 150 ~ 220 DEG C, reacting by heating 30 ~ 60 minutes altogether, after reaction terminates, suction filtration obtains filtrate and filter residue while hot;
(3) filter residue is added in the mixed solvent that step (1) obtains and infiltrate, from 110 DEG C ~ 130 DEG C linear temperature increase to 150 ~ 220 DEG C, reacting by heating 30 ~ 60 minutes altogether, after reaction terminates, suction filtration obtains filtrate and filter residue while hot;
(4) by the filter residue repeating step (3) that obtains after step (3) suction filtration once;
(5) filtrate of combining step (2), (3), (4) gained is collected, filtrate is by carbon dioxide upercritical fluid extraction water phase separated and organic phase, or filtrate adds inorganic salt behind adjust ph to 5 ~ 6, water phase separated and organic phase, gained aqueous phase is the solution containing reducing sugar.
2. method according to claim 1, is characterized in that, in step (1), described polar aprotic solvent is gamma-butyrolactone, γ-valerolactone, tetrahydrofuran (THF) or dimethyl formamide polar aprotic solvent.
3. method according to claim 1, is characterized in that, in step (1), the described vitriol oil is the vitriol oil of 95wt%.
4. method according to claim 1, it is characterized in that, in step (2), described Mierocrystalline cellulose, hemicellulosic material are any one or a few the mixture in the cheap lignocellulose-like biomass raw material of maize straw, corn cob, wheat stalk, bagasse and straw class, or are stripped of the above raw material of wherein hemicellulose through pre-treatment.
5. method according to claim 1, is characterized in that, in step (2), the solid-liquid mass ratio of Mierocrystalline cellulose, hemicellulosic material and mixed solvent is 1:15 ~ 30.
6. method according to claim 1, is characterized in that, in step (5), carbon dioxide upercritical fluid extraction, actual conditions is: pressure 72.9 ~ 92.9atm, temperature 31.26 ~ 51.26 DEG C, and extraction time is 20 ~ 60 minutes.
7. method according to claim 1, is characterized in that, in step (5), filtrate uses calcium carbonate or calcium hydroxide adjust ph to 5 ~ 6.
8. method according to claim 1, is characterized in that, in step (5), and add that quality is the total mass of water in reaction system to be added 0.5 ~ 12% of inorganic salt.
9. method according to claim 1, is characterized in that, in step (5), described inorganic salt are any one or a few in sodium-chlor, sodium sulfate, Repone K and potassium sulfate.
10. the method according to claim 1 or 9, is characterized in that, in step (5), the organic phase that separation obtains is reused for the cheap biomass-making of degraded and prepares glucose for mixing sugar or degraded cellulose.
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| CN105907896A (en) * | 2016-05-16 | 2016-08-31 | 中国科学院广州能源研究所 | Method for co-producing high-concentration xylose and xylooligosaccharide by utilizing wood fiber raw materials |
| CN108863770A (en) * | 2018-08-23 | 2018-11-23 | 天津科技大学 | A kind of technique of levulic acid preparation and its solvent and catalyst recycling |
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| WO2014110084A1 (en) * | 2013-01-08 | 2014-07-17 | Wisconsin Alumni Research Foundation | Method to produce water-soluble sugars from biomass using solvents containing lactones |
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| WO2014110084A1 (en) * | 2013-01-08 | 2014-07-17 | Wisconsin Alumni Research Foundation | Method to produce water-soluble sugars from biomass using solvents containing lactones |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105907896A (en) * | 2016-05-16 | 2016-08-31 | 中国科学院广州能源研究所 | Method for co-producing high-concentration xylose and xylooligosaccharide by utilizing wood fiber raw materials |
| CN105907896B (en) * | 2016-05-16 | 2019-11-12 | 中国科学院广州能源研究所 | A method of utilizing lignocellulose raw material coproduction high concentration xylose and xylo-oligosaccharide |
| CN108863770A (en) * | 2018-08-23 | 2018-11-23 | 天津科技大学 | A kind of technique of levulic acid preparation and its solvent and catalyst recycling |
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