CN110257453B - Pretreatment method for preparing fermentable sugar by improving biological enzymolysis conversion rate of fiber raw material - Google Patents
Pretreatment method for preparing fermentable sugar by improving biological enzymolysis conversion rate of fiber raw material Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 43
- 239000002994 raw material Substances 0.000 title claims abstract description 34
- 239000000835 fiber Substances 0.000 title claims abstract description 18
- 238000002203 pretreatment Methods 0.000 title claims abstract description 13
- 235000000346 sugar Nutrition 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 13
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 13
- 241001330002 Bambuseae Species 0.000 claims abstract description 13
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 13
- 239000011425 bamboo Substances 0.000 claims abstract description 13
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 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 abstract description 44
- 239000008103 glucose Substances 0.000 abstract description 44
- 238000011084 recovery Methods 0.000 abstract description 20
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 108090000790 Enzymes Proteins 0.000 abstract description 5
- 102000004190 Enzymes Human genes 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229940088598 enzyme Drugs 0.000 abstract description 5
- 108010059892 Cellulase Proteins 0.000 abstract description 3
- 229940106157 cellulase Drugs 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 230000008485 antagonism Effects 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 229920002678 cellulose Polymers 0.000 description 21
- 239000001913 cellulose Substances 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 5
- 239000010902 straw Substances 0.000 description 5
- 241000209140 Triticum Species 0.000 description 4
- 235000021307 Triticum Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000007071 enzymatic hydrolysis Effects 0.000 description 4
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- AIDFJGKWTOULTC-UHFFFAOYSA-N 1-butylsulfonylbutane Chemical compound CCCCS(=O)(=O)CCCC AIDFJGKWTOULTC-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- 244000166124 Eucalyptus globulus Species 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- 244000302661 Phyllostachys pubescens Species 0.000 description 3
- 235000003570 Phyllostachys pubescens Nutrition 0.000 description 3
- 241000219000 Populus Species 0.000 description 3
- 229920002522 Wood fibre Polymers 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000002025 wood fiber Substances 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000013401 experimental design Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 241001424413 Lucia Species 0.000 description 1
- 241000218982 Populus nigra Species 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/02—Monosaccharides
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention provides a pretreatment method for preparing fermentable sugar by improving the biological enzymolysis conversion rate of a fiber raw material, which adopts a low-temperature pretreatment technology to pretreat a lignocellulose raw material, and effectively removes an inhibiting factor which restricts the hydrolysis of cellulase of the raw material. The method comprises the following steps: (1) disintegrating the fiber raw material; (2) pretreatment of fine materials: the pretreatment procedure is repeated for a plurality of times, and the dosage of chemicals added each time is as follows: the method comprises the following steps of (1) using 3-20% of hydrogen peroxide, 3-20% of sodium hydroxide, 1-5% of sodium silicate and 0.3-5% of DTPA, wherein the chemical consumption is in mass percent relative to absolutely dry materials, the mass concentration of solids in the whole pretreatment system is 5-30%, the solvent is water and an organic solvent miscible with water, the reaction temperature is 70-150 ℃, and the reaction time is 30-180 minutes. For bamboo raw materials with larger enzyme hydrolysis antagonism, the pretreatment temperature is not more than 95 ℃, and the glucose conversion rate of an enzyme hydrolysis section is 90 percent, and the total glucose recovery rate is close to 90 percent.
Description
Technical Field
The invention belongs to the field of preparation of fermentable sugars, and particularly relates to a pretreatment method for preparing fermentable sugars by improving the biological enzymolysis conversion rate of fiber raw materials.
Background
The wood fiber raw material mainly comprises cellulose, hemicellulose and lignin, wherein the hemicellulose and the lignin tightly wrap the cellulose to form a compact physical and chemical structure of wood fiber biomass. Thus, biorefineries utilizing lignocellulosic feedstocks require first a pretreatment to break the physicochemical structure of the feedstock, to facilitate cellulase contact with the cellulose in the cell wall lining, for enzymatic hydrolysis (Tekin K, hao N, karagoz S, ragauskas A J. Ethanol: A formulating Green Solvent for the neutralization of Lignocellulose. ChemsChemsChemsChemsChemsChem, 2018,11 3559-3575.Min D, li Q, chiang V, jameel H, chang H M, lucia L. The underflue of lignin-carbohydrate complexes on the cell-catalyzed purification II: transgenic hydropoplasers (Populus nigra L. And Populus maxima A. 56, 2014116).
The conventional pretreatment method comprises dilute acid pretreatment, hydrothermal pretreatment, alkaline pretreatment, steam explosion pretreatment and the like, which can effectively destroy the structure of the raw material, thereby achieving higher cellulose enzyme hydrolysis yield. Wherein, for the conventional wood raw material, the dilute acid pretreatment reaction temperature needs at least 160 ℃, the acid dosage is 1 percent, the glucose yield of the enzymolysis section is not more than 80 percent, and the total glucose recovery rate is not more than 60 percent (Lvjiaqing, biyanjin, seiki, et al. The influence of dilute sulfuric acid hydrolysis pretreatment on the hydrolytic saccharification of the waste residue enzyme of wheat straw pulping material preparation [ J ]. Nanjing university of forestry (Nature science edition), 2015 (4): 137-141.); the hydrothermal pretreatment reaction temperature needs at least 180 ℃, the glucose yield of the enzymolysis section does not exceed 80%, and the total glucose recovery rate does not exceed 90% [ Huang C, wu X, huang Y, lai C, li X, yong Q.Premoving enhancement of the liquid hot water pretreatment of water high strand with high free content Technology,2016,219 583-588]; the reaction temperature of alkaline pretreatment needs to be at least 120 ℃, the alkali dosage is 2-4%, the glucose yield of an enzymolysis section is not more than 70%, and the total glucose recovery rate is not more than 70% (Denghui, lichun, lifei, et al. Optimization of pretreatment conditions of cotton straw saccharification alkali [ J ]. Agricultural engineering report, 2009 (1): 208-212.); the temperature of the steam explosion pretreatment reaction is at least 220 ℃, the glucose yield of the enzymolysis section is not more than 80%, and the total glucose recovery rate is not more than 70% (Ropeng, liu Zhong, yan Dynasty, et al. Research on the synchronous saccharification, fermentation and conversion of wheat straw by steam explosion [ J ]. Chemical engineering, 2007,35 (12): 42-45.).
Compared with the conventional wood fiber raw material, the lignification degree of the bamboo wood is higher, and the utilization difficulty is higher. The method has the advantages that the method is used for pretreating bamboo wood by scholars, and the acid pretreatment can remove most of hemicellulose in the bamboo wood, but the lignin content of the pretreated material is still high, so that the enzyme hydrolysis yield of the pretreated material is low; the pretreatment method of delignification can effectively improve the enzymatic hydrolysis yield of the pretreated materials. In spite of the current mainstream bamboo pretreatment methods, it is not difficult to find that the current pretreatment of bamboo is performed at a higher temperature (more than 140 ℃) and a larger alkali consumption (more than 4%), and cellulose is partially dissolved by the peeling reaction during the pretreatment, resulting in low glucose recovery (less than 50%) and the like [ Huang C, ma J, liang C, li X, yong Q. Underflue of sulfuric dioxide-ethanol-water pretreatment on the physical properties and enzymatic chemistry Technology,2018,263 17-24].
Disclosure of Invention
The invention aims to: the existing fiber raw material pretreatment technology has the advantages of higher reaction temperature, high requirement on equipment, high operating cost, low glucose recovery rate in a pretreatment section and low total glucose recovery rate, and in order to solve the problems, the invention provides a pretreatment method for preparing fermentable sugar by improving the biological enzymolysis conversion rate of fiber raw materials.
The technical scheme is as follows: in order to achieve the technical purpose, the pretreatment method for preparing the fermentable sugar by improving the biological enzymolysis conversion rate of the fiber raw material comprises the following steps:
(1) Crushing the fiber raw material: washing, soaking and processing fiber raw materials by mechanical extrusion equipment to form a filament dough, and then carrying out disc grinding treatment under normal pressure to obtain fine materials;
(2) Pretreatment of fine materials: the pretreatment procedure is repeated for several times, preferably 1 to 5 times, although the more the pretreatment procedure is repeated, the better the pretreatment procedure is, the amount of chemicals added each time is: the method comprises the following steps of (1) using 3-20% of hydrogen peroxide, 3-20% of sodium hydroxide, 1-5% of sodium silicate and 0.3-5% of DTPA, wherein the chemical consumption is in mass percent relative to absolutely dry materials, the mass concentration of solids in the whole pretreatment system is 5-30%, the solvent is water and an organic solvent miscible with water, the reaction temperature is 70-150 ℃, and the reaction time is 30-180 minutes.
Preferably, after being soaked for 12 hours at normal temperature in the step (1), the mixture is processed into a filament dough by a mechanical extrusion device, and the fine material with the size of 1-10mm is obtained after being processed by a normal pressure disc mill.
Specifically, the solvent is any one or a mixture of several of methanol, ethanol, acetone, tetrahydrofuran, butyl sulfone, dioxane, ethylene glycol and 1, 3-dioxolane in any proportion.
In the step (2), all chemicals and solvents are put into a reactor at one time, mixed with the fine materials uniformly, heated to a set temperature, then subjected to heat preservation reaction, taken out after the designed reaction time is reached, and washed by distilled water until the pH value of the filtrate is 7.
Specifically, the fiber raw material is any one of bamboo, poplar, wheat straw, eucalyptus, moso bamboo, cotton stalk and corncob.
In particular, the treatment method of the invention has excellent treatment effect on bamboo wood.
Has the advantages that: compared with the prior art, the method has the advantages that under the condition of lower temperature (not lower than 70 ℃ and excellent effect at 95 ℃), a physicochemical barrier restricting the efficient saccharification of cellulose can be broken through, higher glucose yield (90%) of an enzymatic hydrolysis section is realized, higher cellulose conversion rate (total glucose recovery rate exceeds 80%) is kept in a pretreatment section, and the method has excellent effect on traditional treatment methods particularly for fiber raw materials with high lignin content, and particularly for bamboo wood, the total sugar conversion rate of the traditional method is only about 50%, the method can reach 90%, the reaction conditions of the method are relatively mild, the requirements on equipment are not high, the used chemicals are conventional agents, and the operation cost is low.
Detailed Description
The invention provides a pretreatment method for preparing fermentable sugar by improving the biological enzymolysis conversion rate of a fiber raw material, which comprises the following steps:
(1) Crushing the fiber raw material: the fiber raw material is washed, soaked and processed by mechanical extrusion equipment to form a filament dough, and then ground by a disc mill under normal pressure to obtain fine materials;
(2) Pretreatment of fine materials: the pretreatment procedure is repeated for a plurality of times, and the dosage of chemicals added each time is as follows: 3-20% of hydrogen peroxide, 3-20% of sodium hydroxide, 1-5% of sodium silicate and 0.3-5% of DTPA, wherein the chemical dosages are all in percentage by mass relative to absolutely dry materials, the mass concentration of the solid of the whole pretreatment system is 5-30%, the solvent is water and an organic solvent which can be mixed and dissolved with water, such as methanol, ethanol, acetone, tetrahydrofuran, butyl sulfone, dioxane, ethylene glycol and 1, 3-dioxolane, and the reaction temperature is 70-150 ℃, and the reaction time is 30-180 minutes. All chemicals and solvents are put into a reactor at one time, are uniformly mixed with the fine materials, are heated to a set temperature, are subjected to heat preservation reaction, and are taken out after the designed reaction time is reached, and are washed in a Buchner funnel by distilled water until the pH value of the filtrate is 7.
The present invention is described in detail below with reference to specific examples.
Wherein, the step of saccharifying the cellulose in the following examples is:
weighing a processed material with the absolute dry weight of 2.5g, putting the processed material into a 150mL enzymolysis bottle, adding 2.5mL of 1mol/L citric acid buffer solution, adding cellulase according to the dosage of 25FPU/g cellulose, and finally supplementing distilled water to ensure that the volume of an enzymolysis system is 50mL; and (3) placing the enzymolysis bottle in a constant-temperature shaking table at 150rpm and 50 ℃ for enzymolysis for 72 hours, taking an enzymolysis sample after the enzymolysis is finished, centrifuging at 10000rpm, taking supernate to determine the glucose concentration and the cellobiose concentration in the supernate, and calculating the enzymatic hydrolysis yield.
Wherein, the yield (%) of glucose in the enzymolysis segment is = [ (glucose concentration g/L0.9 in the hydrolysate + cellobiose concentration g/L0.95 in the hydrolysate) × 0.05/(absolute dry weight g of substrate) × 100%), wherein 0.9 is the conversion coefficient of glucose and cellulose, 0.95 is the conversion coefficient of cellobiose and cellulose, and 0.05 is the volume of the hydrolysis system;
the total glucose yield (%) = [ (glucose concentration g/L0.9 + cellobiose concentration g/L0.95 in the hydrolysate) × 0.05/(absolute dry weight g of the raw material) × 100%), wherein 0.9 is the conversion coefficient of glucose and cellulose, 0.95 is the conversion coefficient of cellobiose and cellulose, and 0.05 is the volume of the hydrolysis system.
Example 1 effect of different pretreatment processes on the glucose conversion of fibrous material.
The following example uses bamboo as raw material, with cellulose content 43.14%, and comprises the following steps: after the raw materials are conventionally crushed, fine materials with the weight equivalent to 10g of absolute dry weight are weighed, various chemicals and the fine materials are uniformly mixed according to the dosage of the following table 1, the mixture is put into a closed reactor after the system concentration is adjusted to be 20% by using distilled water, the mixture is heated to 95 ℃, then the heat preservation reaction is carried out for 60min, and the obtained materials are cleaned for later use. If the experimental design requires multiple stages of treatment, the pretreatment reaction process described above is repeated. The obtained material is subjected to conventional saccharification reaction to obtain corresponding glucose conversion rate, and the recovery rate data is shown in the table below.
TABLE 1
As can be seen from the above table, the conversion rate of glucose in the material without pretreatment is only 13%, and the pretreatment is performed at 95 ℃ by using ethanol (1), hydrogen peroxide (2) and sodium hydroxide (3) alone, the glucose enzymolysis yield and the total glucose recovery rate are both low, the total glucose recovery rate is not more than 73% by using aqueous phase alkaline hydrogen peroxide for treatment (4, 5), the multi-stage ethanol-alkaline hydrogen peroxide pretreatment (7, 8, 9) is adopted, the enzymolysis glucose yield is more than 90%, and the total glucose recovery rate is about 90%. Namely, the technology has the best effect when organic solvent-hydrogen peroxide-sodium hydroxide is used.
Example 2 effect of different pretreatment processes on the glucose conversion of fibrous material.
The following examples adopt bamboo as raw material, the cellulose content of which is 43.14%, and the concrete steps are as follows: after the raw materials are conventionally disintegrated, fine materials with the weight equivalent to 10g of absolute dry weight are weighed, various chemicals and the fine materials are uniformly mixed according to the dosage shown in the table, the mixture is put into a closed reactor after the system concentration is adjusted to be 20% by using distilled water, the mixture is heated to the set value and then is subjected to heat preservation reaction for 60min, and the obtained materials are cleaned for later use. The pretreatment reaction process described above is repeated if the experimental design requires multiple stages of treatment. The obtained material is subjected to conventional saccharification reaction to obtain corresponding glucose conversion rate, and the recovery rate data is shown in table 2.
TABLE 2
Example 3
Poplar was used as the starting material, with a cellulose content of 45.43%, and the material was treated according to the procedure of example one, where the pretreatment conditions were: weighing materials which are equivalent to 10g of oven-dried weight, wherein the hydrogen peroxide amount is 8%, the sodium hydroxide amount is 9%, the sodium silicate amount is 2%, and the DTPA amount is 0.5%, adding the liquid medicine in three sections, wherein the dioxane amount is 7g in each section of treatment, the temperature is 95 ℃, the concentration of a reaction system is 20%, the yield of the glucose in the obtained enzymolysis section is 94.53%, and the total recovery rate of the glucose is 91.47%.
Example 4
Wheat straw, having a cellulose content of 35.64%, was used as the starting material and the material was processed according to the procedure of example one, wherein the pretreatment conditions were: weighing materials with the weight equivalent to 10g of oven-dried powder, wherein the dosage of hydrogen peroxide is 10%, the dosage of sodium hydroxide is 6%, the dosage of sodium silicate is 2%, and the dosage of DTPA is 0.5%, adding the liquid medicine in two sections, wherein the dosage of acetone is 4g in each section of treatment, the temperature is 95 ℃, the concentration of a reaction system is 30%, the yield of the glucose in the obtained enzymolysis section is 85.41%, and the total recovery rate of the glucose is 81.54%.
Example 5
Eucalyptus is used as a raw material, the cellulose content of the eucalyptus is 42.63 percent, the material is treated according to the operation steps of the example one, wherein the pretreatment conditions are as follows: weighing materials with the weight equivalent to 10g of oven-dried powder, wherein the dosage of hydrogen peroxide is 8 percent, the dosage of sodium hydroxide is 4.5 percent, the dosage of sodium silicate is 2 percent, the dosage of DTPA is 0.5 percent, the liquid medicine is added in one section, the dosage of methanol is 60 percent in each section of treatment, the temperature is 95 ℃, the concentration is 20 percent, the yield of the glucose in the enzymolysis section is 93.69 percent, and the total recovery rate of the glucose is 90.72 percent.
Example 6
Adopting moso bamboo as a raw material, wherein the cellulose content of the moso bamboo is 43.14%, and treating the material according to the operation steps of example one, wherein the pretreatment conditions are as follows: weighing materials with the weight equivalent to 10g of oven-dried powder, wherein the dosage of hydrogen peroxide is 15%, the dosage of sodium hydroxide is 10%, the dosage of sodium silicate is 2%, and the dosage of DTPA is 0.5%, adding the liquid medicine in three stages, wherein the dosage of butyl sulfone used in each stage of treatment is 90%, the temperature is 95 ℃, the concentration is 10%, the yield of the obtained glucose in the enzymolysis stage is 94.69%, and the total recovery rate of the glucose is 89.58%.
Example 7
The material was treated according to the procedure of example one, using cotton stalks as raw material, with a cellulose content of 31.69%, wherein the pretreatment conditions were: weighing materials with the weight equivalent to 10g of oven-dried materials, wherein the dosage of hydrogen peroxide is 9%, the dosage of sodium hydroxide is 6%, the dosage of sodium silicate is 2%, the dosage of DTPA is 0.5%, the liquid medicine is added in one section, the dosage of ethylene glycol used in each section of treatment is 80%, the temperature is 95 ℃, the concentration is 5%, the yield of glucose in the enzymolysis section is 88.53%, and the recovery rate of total glucose is 81.36%.
Example 8
Using corncobs as raw materials, the cellulose content of which is 28.57%, and processing the materials according to the operation steps of example one, wherein the pretreatment conditions are as follows: weighing materials with the weight equivalent to 10g of oven-dried powder, wherein the dosage of hydrogen peroxide is 9 percent, the dosage of sodium hydroxide is 5 percent, the dosage of sodium silicate is 2 percent, the dosage of DTPA is 0.5 percent, the liquid medicine is added in one section, the dosage of tetrahydrofuran is 50 percent in each section of treatment, the temperature is 95 ℃, the concentration is 20 percent, the yield of the glucose in the enzymolysis section is 89.87 percent, and the total recovery rate of the glucose is 84.69 percent.
Claims (3)
1. A pretreatment method for improving the biological enzymolysis conversion rate of a bamboo fiber raw material to prepare fermentable sugar is characterized by comprising the following steps:
(1) Crushing the fiber raw material: the bamboo fiber raw material is washed, soaked and processed by mechanical extrusion equipment to form a filament dough, and then ground by a normal pressure disc to obtain fine materials;
(2) Pretreatment of fine materials: the pretreatment procedure is repeated for a plurality of times, and the dosage of chemicals added each time is as follows: 3-20% of hydrogen peroxide, 3-20% of sodium hydroxide, 1-5% of sodium silicate and 0.3-5% of DTPA, and putting all chemicals and solvents into a closed reactor at one time; the chemical consumption is relative to the mass percentage of the absolutely dry material, the mass concentration of the solid of the whole pretreatment system is 5-30%, the solvent is water and ethanol, the reaction temperature is 70-120 ℃, and the reaction time is 30-180 minutes.
2. The pretreatment method according to claim 1, wherein in the step (1), the size of the fine material obtained after the millstone treatment is usually pressed is 1 to 10mm.
3. The pretreatment method according to claim 1, wherein in the step (2), all chemicals and solvents are put into the reactor at one time, mixed with the fine materials uniformly, heated to the set temperature, and then subjected to heat preservation reaction, and after the designed reaction time is reached, the materials are taken out and washed in a Buchner funnel by distilled water until the pH of the filtrate is 7.
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| CA1096559A (en) * | 1978-05-04 | 1981-03-03 | Jonas A. I. Lindahl | Process for pretreating particulate lignocellulosic material |
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