CN114763680A - Method for removing lignin from lignocellulosic feedstocks - Google Patents
Method for removing lignin from lignocellulosic feedstocks Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 150
- 238000011282 treatment Methods 0.000 claims abstract description 64
- 238000010411 cooking Methods 0.000 claims abstract description 52
- 239000007787 solid Substances 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 238000005406 washing Methods 0.000 claims abstract description 35
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 23
- 239000010452 phosphate Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 19
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 19
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims abstract description 19
- 235000019801 trisodium phosphate Nutrition 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 18
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims abstract description 4
- 235000019798 tripotassium phosphate Nutrition 0.000 claims abstract description 4
- 239000010902 straw Substances 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 240000008042 Zea mays Species 0.000 claims description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 6
- 235000005822 corn Nutrition 0.000 claims description 6
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 239000010907 stover Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 30
- 239000002699 waste material Substances 0.000 description 27
- 108010059892 Cellulase Proteins 0.000 description 26
- 229940106157 cellulase Drugs 0.000 description 26
- 229920002678 cellulose Polymers 0.000 description 26
- 239000001913 cellulose Substances 0.000 description 26
- 238000001816 cooling Methods 0.000 description 18
- 235000021317 phosphate Nutrition 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 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 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 15
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 15
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 15
- 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 15
- 239000008103 glucose Substances 0.000 description 15
- 238000005070 sampling Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 159000000011 group IA salts Chemical class 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229920002522 Wood fibre Polymers 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000002025 wood fiber Substances 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
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Abstract
The present invention provides a method for removing lignin from a lignocellulosic feedstock. The method comprises the steps of S1, carrying out cooking treatment on a lignocellulose raw material by using pretreatment liquid containing phosphate to obtain cooking treated liquid; step S2, carrying out solid-liquid separation on the liquid after the cooking treatment to obtain liquid and solid; step S3, washing the solid to obtain a washing liquid; and step S4, mixing the liquid and the washing liquid to obtain a mixed liquid, enabling the pH value of the mixed liquid to be more than or equal to 9.0, using the mixed liquid as a new pretreatment liquid, and repeatedly carrying out the treatments from the step S1 to the step S3 on the lignocellulose raw material, wherein the phosphate is trisodium phosphate or tripotassium phosphate. According to the method, the pH value of the mixed liquid obtained by mixing the liquid and the washing liquid is controlled to be more than or equal to 9.0, and the mixed liquid is used as a new pretreatment liquid to treat the lignocellulose raw material, so that the comprehensive utilization rate of the lignocellulose raw material is improved, the cost is reduced, and the environmental pollution is reduced.
Description
Technical Field
The invention relates to the technical field of lignocellulose treatment, in particular to a method for removing lignin from a lignocellulose raw material.
Background
In biomass feedstock pretreatment, alkaline salts can effectively break ester and glycosidic bonds in the cell wall matrix, causing structural changes in lignin, swelling cellulose, and removing lignin. Meanwhile, along with the separation and degradation of the components, the concentration of inhibitors such as lignin and the like in the pretreatment liquid is gradually increased, so that the difficulty is increased for the recovery and regeneration of the pretreatment liquid, and the method becomes the maximum application limit of the prior alkaline pretreatment. In addition, because the regeneration and circulation of the treated waste liquid cannot be realized, the waste lye generated in the process can cause serious environmental pollution, and the development and the scale application of the technology are hindered.
Acidic or basic salts may also be used for pre-treatment of ligno-cellulosic materials, such as sulfites, phosphates, carbonates, etc. Chinese patent application publication No. CN 105063100 a discloses a method for pretreating non-wood fiber raw materials by combining alkaline salt with hydrogen peroxide: soaking the non-wood fiber raw material in a mixed solvent, treating the non-wood fiber raw material at 50-120 ℃ for 1-6 h with a substrate concentration of 5-20 g/L, adding 0.5-2 times of deionized water after the reaction is finished, stirring the mixture at room temperature for 10-30 min to obtain a regenerated cellulose raw material, and washing solid residues with water to finish the pretreatment process. The solid recovery rate after pretreatment is 40-80%, the lignin removal rate is 20-90%, the cellulose retention rate is 75-95%, and the hemicellulose retention rate is 70-90%. The pretreatment method effectively removes lignin, and largely retains cellulose and hemicellulose, thereby improving the enzymatic hydrolysis saccharification efficiency. Although the method achieves a good treatment effect, the use amount of alkaline salt is large, the treatment time is long, the consumption amount of the pretreatment liquid in the treatment process is large, hydrogen peroxide with strong oxidizability is added, the complexity of the process is increased to a certain extent, a lot of problems are brought to the treatment of the pretreatment liquid, a large amount of waste water is generated, and the cost is greatly increased.
Disclosure of Invention
The invention mainly aims to provide a method for removing lignin from a lignocellulose raw material so as to solve the problem of high cost of removing the lignin from the lignocellulose raw material in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for removing lignin from a lignocellulosic feedstock, the method comprising the steps of S1, subjecting the lignocellulosic feedstock to a cooking treatment with a phosphate-containing pretreatment liquor to obtain a cooking-treated liquor; step S2, carrying out solid-liquid separation on the liquid after the cooking treatment to obtain liquid and solid; step S3, washing the solid to obtain a washing liquid; and step S4, mixing the liquid and the washing liquid to obtain a mixed liquid, enabling the pH value of the mixed liquid to be more than or equal to 9.0, using the mixed liquid as a new pretreatment liquid, and repeatedly carrying out the treatments from the step S1 to the step S3 on the lignocellulose raw material, wherein the phosphate is trisodium phosphate or tripotassium phosphate.
Further, the pH value of the mixed solution is adjusted by adopting phosphate, so that the pH value is more than or equal to 11, and the preferable pH value is 12-14.
Furthermore, the mass percent of the solute of the mixed solution is less than or equal to 23 percent, preferably less than or equal to 17 percent.
Further, step S4 is repeated 1 to 4 times, and preferably step S4 is repeated 2 to 3 times.
Further, the mass ratio of the phosphate to the lignocellulose raw material is 2.5-4.5: 10.
The pretreatment solution is a phosphate aqueous solution, and preferably the mass concentration of the solute of the pretreatment solution is 25-45 g/L.
Further, the temperature of the cooking treatment is 160-190 ℃.
Furthermore, the time of the cooking treatment is 0.2-1 h.
Further, the solid-liquid separation is centrifugal separation.
Further, the above lignocellulose raw material is derived from crop straws or forest residues, preferably, the lignocellulose raw material is selected from any one or more of corn straws, wheat straws and rice straw straws.
By applying the technical scheme of the invention, as the molecular structure of the lignin contains hydroxyl, the lignin is easily converted into lignin salt and dissolved in water under an alkaline condition, so that the lignin in the lignocellulose raw material is removed, but the lignin salt is also easily converted back into the lignin under an acidic condition, so that the pH value of the mixed solution obtained by mixing the liquid and the washing solution is controlled to be more than or equal to 9.0, the lignin and the like in the mixed solution are prevented from being separated out of the mixed solution and re-adsorbed in the lignocellulose raw material in the subsequent cooking treatment process, and the cyclic utilization of the mixed solution is further realized. Therefore, the mixed liquor is used as new pretreatment liquor to treat the lignocellulose raw material, so that the lignin in the mixed liquor can be enriched and recovered, the regeneration utilization rate of phosphate in the mixed liquor is improved, the using amount of the pretreatment liquor is greatly reduced, the practicability of alkaline pretreatment and the comprehensive utilization rate of the lignocellulose raw material are improved, the cost is greatly reduced, and the environmental pollution is reduced through the regeneration cycle of the mixed liquor.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art, there is a problem in the prior art that the cost of removing lignin from lignocellulosic feedstocks is high, and to solve this problem, the present invention provides a method for removing lignin from lignocellulosic feedstocks.
In an exemplary embodiment of the present application, there is provided a method of removing lignin from a lignocellulosic feedstock, the method comprising: step S1, cooking the lignocellulose raw material by using pretreatment liquid containing phosphate to obtain cooked liquid; step S2, carrying out solid-liquid separation on the liquid after the cooking treatment to obtain liquid and solid; step S3, washing the solid to obtain a washing liquid; and S4, mixing the liquid and the washing liquid to obtain a mixed liquid, enabling the pH value of the mixed liquid to be more than or equal to 9.0, taking the mixed liquid as a new pretreatment liquid, and repeatedly carrying out the treatments from S1 to S3 on the lignocellulose raw material, wherein the phosphate is trisodium phosphate or tripotassium phosphate.
Because the molecular structure of the lignin contains hydroxyl, the lignin is easily converted into lignin salt and dissolved in water under an alkaline condition, so that the lignin in the lignocellulose raw material is removed, but the lignin salt is also easily converted back into the lignin under an acidic condition, so that the pH value of a mixed solution obtained by mixing the liquid and the washing solution is controlled to be more than or equal to 9.0, the lignin and the like in the mixed solution are not separated out from the mixed solution and are adsorbed in the lignocellulose raw material again in the subsequent cooking treatment process, and the cyclic utilization of the mixed solution is further realized. Therefore, the mixed liquor is used as new pretreatment liquor to treat the lignocellulose raw material, so that the lignin in the mixed liquor can be enriched and recovered, the regeneration utilization rate of phosphate in the mixed liquor is improved, the using amount of the pretreatment liquor is greatly reduced, the practicability of alkaline pretreatment and the comprehensive utilization rate of the lignocellulose raw material are improved, the cost is greatly reduced, and the environmental pollution is reduced through the regeneration cycle of the mixed liquor.
In order to further ensure the removal efficiency of lignin in the lignocellulose raw material when the mixed solution is used as a new pretreatment solution and avoid introducing excessive other impurities, the pH value of the mixed solution is preferably adjusted by phosphate so that the pH value is more than or equal to 11, and the pH value is preferably 12-14.
In order to reduce the content of lignin in the mixed liquor as much as possible and reduce the probability of re-adsorption of lignin in the mixed liquor to the new lignocellulosic raw material, thereby ensuring the extraction efficiency of lignin in the new lignocellulosic raw material, the mass percentage of the solute in the mixed liquor is preferably less than or equal to 23%, and preferably less than or equal to 17%.
On the basis of reusing the treated waste liquid to reduce the cost, the lignin content in the treated waste liquid is not too high due to too many times of recycling the treated waste liquid, so that the extraction efficiency of the lignin in the new lignocellulose raw material is too low, and the step S4 is preferably repeatedly performed for 1 to 4 times, and the step S4 is preferably repeatedly performed for 2 to 3 times.
In order to make the phosphate in the phosphate-containing pretreatment solution have a sufficient amount of phosphate so that the pH value of the pretreatment solution is favorable for precipitation of lignin in the lignocellulose raw material, the mass ratio of the phosphate to the lignocellulose raw material is preferably 2.5-4.5: 10.
In order to enable the lignin to be better precipitated and dissolved in the pretreatment liquid, the pretreatment liquid is preferably a phosphate aqueous solution, and the solute mass concentration of the pretreatment liquid is preferably 25-45 g/L.
In order to further improve the destructive effect of the alkaline salt on ester bonds and glycosidic bonds in the cell wall matrix, thereby causing the structural change of the lignin and swelling the cellulose, thereby removing the lignin and part of the crystalline cellulose, the temperature of the cooking treatment is preferably 160-190 ℃.
The time for the above-mentioned steaming treatment is preferably 0.2 to 1 hour, in order to swell the cellulose in the lignocellulose raw material as sufficiently as possible and dissolve it in the treatment waste liquid.
In order to more sufficiently separate the liquid portion and the solid portion in the liquid after the cooking treatment, the solid-liquid separation is preferably centrifugal separation.
In one embodiment of the present application, the above mentioned lignocellulosic raw material is derived from crop stalks or forest residues, preferably the lignocellulosic raw material is selected from any one or more of corn stover, wheat straw, rice straw.
The lignocellulosic feedstock of the present application may be any of a variety of cellulose-containing feedstocks known in the art, and in order to further use the method of the present application for removing lignin from a lignocellulosic feedstock, it is preferred that the lignocellulosic feedstock be treated as described above.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Example 1
Taking corn straws with the water content of below 15%, crushing the straws to below 2.8mm by using a hammer mill, and screening and taking part of crushed straws with the diameter of 2.8-0.85 mm.
500mL of trisodium phosphate aqueous solution with solute mass concentration of 32.6g/L and 50g of straw crushed materials are placed in a small group tank of a digester, mixed and sealed, then placed in the digester for heating, heated to 160 ℃ within 40min, and then kept warm for 50min to perform cooking treatment on the straw crushed materials, so as to obtain a liquid after the cooking treatment. And then, deflating, cooling to below 100 ℃ after 40min, opening the digester, taking out the small tank, putting the small tank into a water bath, and cooling to room temperature. Wherein the mass ratio of the trisodium phosphate in the trisodium phosphate aqueous solution to the crushed straw is 3.3: 10. And (3) carrying out centrifugal separation on the liquid after the cooking treatment to obtain liquid and solid, washing the solid in the liquid to be neutral, and mixing the washing liquid and the liquid to obtain the once-recovered treatment waste liquid. And (3) carrying out enzymolysis saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, using cellulase R-10 (Shanghai Baoman Biotechnology Co., Ltd.), the using amount of the cellulase R-10 is 20 FPUg/substrate, periodically sampling, measuring components such as cellobiose, glucose, xylose and the like, and measuring the conversion rate of the cellulose after 72 hours to be 84.1%.
500mL of the above-mentioned once-recovered waste treatment solution (pH 10.6) was taken and its pH was adjusted to 12 with trisodium phosphate to obtain a mixed solution. And the mass percent of the solute in the mixed solution is 6.3%, then 50g of the straw crushed materials and the mixed solution are placed in a small group of digester, mixed and sealed, then placed in the digester for heating up, heated to 160 ℃ within 40min, and then kept warm for 50min to carry out cooking treatment on the straw crushed materials, so as to obtain a liquid after the cooking treatment. And then, deflating, cooling to below 100 ℃ after 40min, opening the cooking pot, taking out the small pot, putting the small pot into a water bath, and cooling to room temperature. And (3) carrying out centrifugal separation on the liquid after the cooking treatment to obtain liquid and solid, washing the solid in the liquid to be neutral, and mixing the washing liquid and the liquid to obtain the secondary treatment waste liquid. And (3) carrying out enzymolysis saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, the cellulase R-10 is used, the dosage of the cellulase R-10 is 20 FPUg/substrate, periodic sampling is carried out, components such as cellobiose, glucose, xylose and the like are measured, and the conversion rate of cellulose is 82.5% after 72 hours.
Example 2
Example 2 differs from example 1 in that 500mL of the above-mentioned recovered secondary waste liquid (pH 7.7) was taken and its pH was adjusted to 12 with trisodium phosphate to obtain a mixed solution. And the mass percent of the solute in the mixed solution is 10.6%, then 50g of the crushed straw and the mixed solution are placed in a small group of pots of a digester, mixed and sealed, then placed in the digester for heating up, the temperature is raised to 160 ℃ within 40min, and then the temperature is kept for 50min to perform cooking treatment on the crushed straw, so that the liquid after the cooking treatment is obtained. And then, deflating, cooling to below 100 ℃ after 40min, opening the cooking pot, taking out the small pot, putting the small pot into a water bath, and cooling to room temperature. And (3) carrying out centrifugal separation on the liquid after the cooking treatment to obtain liquid and solid, washing the solid in the liquid to be neutral, and mixing the washing liquid and the liquid to obtain the treated waste liquid recovered for three times. And (3) carrying out enzymolysis saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, the cellulase R-10 is used, the dosage of the cellulase R-10 is 20 FPUg/substrate, periodic sampling is carried out, components such as cellobiose, glucose, xylose and the like are measured, and the conversion rate of cellulose is 83.4% after 72 hours.
Example 3
Example 3 differs from example 1 in that 500mL of the above-mentioned three-time recovered waste treatment liquid (pH 6.6) was taken and pH thereof was adjusted to 12 with trisodium phosphate to obtain a mixed liquid. And the mass percent of the solute in the mixed solution is 14.4%, then 50g of the crushed straw and the mixed solution are placed in a small group of pots of a digester, mixed and sealed, then placed in the digester for heating up, the temperature is raised to 160 ℃ within 40min, and then the temperature is kept for 50min to perform cooking treatment on the crushed straw, so that the liquid after the cooking treatment is obtained. And then, deflating, cooling to below 100 ℃ after 40min, opening the cooking pot, taking out the small pot, putting the small pot into a water bath, and cooling to room temperature. And (3) carrying out centrifugal separation on the liquid after the cooking treatment to obtain liquid and solid, washing the solid in the liquid to be neutral, and mixing the washing liquid and the liquid to obtain the treated waste liquid recovered for four times. And (3) carrying out enzymolysis saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, the cellulase R-10 is used, the dosage of the cellulase R-10 is 20 FPUg/substrate, periodic sampling is carried out, components such as cellobiose, glucose, xylose and the like are measured, and the conversion rate of cellulose is 81.7% after 72 hours.
Example 4
Example 4 differs from example 1 in that 500mL of the above-mentioned four-time recovered waste treatment solution (pH 6.0) was taken and its pH was adjusted to 12 with trisodium phosphate to obtain a mixed solution. And the mass percent of the solute in the mixed solution is 18.6%, then 50g of the crushed straw and the mixed solution are placed in a small group of pots of a digester, mixed and sealed, then placed in the digester for heating up, the temperature is raised to 160 ℃ within 40min, and then the temperature is kept for 50min to perform cooking treatment on the crushed straw, so that the liquid after the cooking treatment is obtained. And then, deflating, cooling to below 100 ℃ after 40min, opening the cooking pot, taking out the small pot, putting the small pot into a water bath, and cooling to room temperature. And (3) centrifugally separating the liquid after the cooking treatment to obtain liquid and solid, washing the solid in the liquid to be neutral, and mixing the washing liquid and the liquid to obtain the treatment waste liquid which is recovered for five times. And (3) carrying out enzymolysis saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, the cellulase R-10 is used, the dosage of the cellulase R-10 is 20 FPUg/substrate, sampling is carried out periodically, components such as cellobiose, glucose, xylose and the like are measured, and the conversion rate of cellulose is 80.1% after 72 hours.
Example 5
Example 5 differs from example 2 in that trisodium phosphate was used to adjust the pH of the secondary recovered waste treatment solution (pH 7.7) to 13.5, resulting in a mixed solution with 11.8% solute by mass. And finally, performing enzymolysis and saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, the cellulase R-10 is used, the dosage of the cellulase R-10 is 20 FPUg/substrate, sampling is performed periodically, components such as cellobiose, glucose, xylose and the like are measured, and the conversion rate of cellulose is 86.1% after 72 hours.
Example 6
Example 6 is different from example 2 in that the pH of the secondary recovered waste treatment solution (pH 7.7) was adjusted to 10.0 with trisodium phosphate to obtain a mixed solution, and the mass percentage of the solute in the mixed solution was 10.1%. And finally, carrying out enzymolysis saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, using cellulase R-10, and the dosage of the cellulase R-10 is 20 FPUg/substrate, periodically sampling, measuring components such as cellobiose, glucose, xylose and the like, and measuring the conversion rate of cellulose after 72 hours to be 75.2%.
Example 7
Example 7 is different from example 3 in that the pH of the treatment waste liquid (pH 6.6) recovered three times was adjusted to 10.6 using trisodium phosphate to obtain a mixed liquid in which the solute content was 12.7% by mass. And finally, carrying out enzymolysis saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, using cellulase R-10, and the dosage of the cellulase R-10 is 20 FPUg/substrate, periodically sampling, measuring components such as cellobiose, glucose, xylose and the like, and measuring the conversion rate of the cellulose after 72 hours to be 76.7%.
Example 8
Example 8 differs from example 4 in that the pH of the treatment waste liquid (pH 5.1) recovered five times was adjusted to 13.5 with trisodium phosphate to obtain a mixed liquid in which the solute content was 25% by mass. And finally, carrying out enzymolysis saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, using cellulase R-10, and the dosage of the cellulase R-10 is 20 FPUg/substrate, periodically sampling, measuring components such as cellobiose, glucose, xylose and the like, and measuring the conversion rate of the cellulose to be 70.4% after 72 hours.
Example 9
Taking corn straws with the water content of below 15%, crushing the straws to be below 2.8mm by using a hammer mill, screening, and preprocessing a part of crushed straws with the size of 2.8-0.85 mm.
Placing a trisodium phosphate aqueous solution with solute mass concentration of 30g/L and 50g of straw crushed materials into a small group of pots of a digester, mixing, sealing, placing into the digester, heating to 160 ℃ within 40min, and keeping the temperature for 50min to perform cooking treatment on the straw crushed materials to obtain a liquid after the cooking treatment. And then, deflating, cooling to below 100 ℃ after 40min, opening the cooking pot, taking out the small pot, putting the small pot into a water bath, and cooling to room temperature. And (3) carrying out centrifugal separation on the liquid after the cooking treatment to obtain liquid and solid, washing the solid in the liquid to be neutral, and mixing the washing liquid and the liquid to obtain the once-recovered treatment waste liquid. And (3) carrying out enzymolysis saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, the cellulase R-10 is used, the dosage of the cellulase R-10 is 20 FPUg/substrate, sampling is carried out periodically, components such as cellobiose, glucose, xylose and the like are measured, and the conversion rate of cellulose is 69.8% after 72 hours.
500mL of the treated waste liquid (pH 9.0) collected once was collected as a mixed liquid. And 4.6% of solute in the mixed solution, then placing 50g of the crushed straw and the mixed solution into a small group of digester, mixing, sealing, placing into the digester, heating to 160 ℃ within 40min, and keeping the temperature for 50min to perform cooking treatment on the crushed straw, thus obtaining the liquid after the cooking treatment. And then, deflating, cooling to below 100 ℃ after 40min, opening the cooking pot, taking out the small pot, putting the small pot into a water bath, and cooling to room temperature. And (3) carrying out centrifugal separation on the liquid after the cooking treatment to obtain liquid and solid, washing the solid in the liquid to be neutral, and mixing the washing liquid and the liquid to obtain the secondary treatment waste liquid. And (3) carrying out enzymolysis saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, the cellulase R-10 is used, the dosage of the cellulase R-10 is 20 FPUg/substrate, sampling is carried out periodically, components such as cellobiose, glucose, xylose and the like are measured, and the conversion rate of cellulose is 72.1% after 72 hours.
Comparative example 1
The difference between the comparative example 1 and the example 2 is that 500mL of the secondary recovered waste treatment liquid (pH 7.7) is directly used as a mixed liquid, the mass percent of the solute in the mixed liquid is 9.4%, finally, the pretreated solid is subjected to enzymolysis saccharification, the mass concentration of the system is 20g/L, the cellulose R-10 is used, the dosage of the cellulose R-10 is 20 FPUg/substrate, samples are periodically taken, the components such as cellobiose, glucose, xylose and the like are measured, and the conversion rate of cellulose is 52.7% after 72 hours.
Comparative example 2
The difference between the comparative example 2 and the example 3 is that 500mL of the three-time recovered treated waste liquid (pH 6.6) is directly used as a mixed liquid, the mass percent of the solute in the mixed liquid is 11.3%, the pretreated solid is finally subjected to enzymatic saccharification, the mass concentration of the system is 20g/L, the cellulose R-10 is used, the dosage of the cellulose R-10 is 20 FPUg/substrate, samples are periodically taken, the components such as cellobiose, glucose, xylose and the like are measured, and the conversion rate of cellulose is 42.5% after 72 hours.
Comparative example 3
Taking corn straws with the water content of below 15%, crushing the straws to below 2.8mm by using a hammer mill, and screening and preprocessing a part of crushed straws with the size of 2.8-0.85 mm.
Placing a trisodium phosphate aqueous solution with a solute mass concentration of 23g/L and 50g of straw crushed materials into a small group of cooking pots, wherein the mass ratio of trisodium phosphate in the trisodium phosphate aqueous solution to the straw crushed materials is 2.3: 10. Mixing, sealing, heating to 160 deg.C within 40min, and keeping the temperature for 50min to obtain a decoction. And then, deflating, cooling to below 100 ℃ after 40min, opening the cooking pot, taking out the small pot, putting the small pot into a water bath, and cooling to room temperature. And (3) carrying out centrifugal separation on the liquid after the cooking treatment to obtain liquid and solid, washing the solid in the liquid to be neutral, and mixing the washing liquid and the liquid to obtain the once-recovered treatment waste liquid. And (3) carrying out enzymolysis saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, the cellulase R-10 is used, the dosage of the cellulase R-10 is 20 FPUg/substrate, periodic sampling is carried out, components such as cellobiose, glucose, xylose and the like are measured, and the conversion rate of cellulose is 69.4% after 72 hours.
500mL of the treated waste liquid (pH 8.5) collected once was collected as a mixed liquid. And 5.3% of solute in the mixed solution, then placing 50g of the crushed straw and the mixed solution into a small group of digester, mixing, sealing, placing into the digester, heating to 160 ℃ within 40min, and keeping the temperature for 50min to perform cooking treatment on the crushed straw to obtain a cooked liquid. And then, deflating, cooling to below 100 ℃ after 40min, opening the cooking pot, taking out the small pot, putting the small pot into a water bath, and cooling to room temperature. And (3) carrying out centrifugal separation on the liquid after the cooking treatment to obtain liquid and solid, washing the solid in the liquid to be neutral, and mixing the washing liquid and the liquid to obtain the secondary treatment waste liquid. And (3) carrying out enzymolysis saccharification on the pretreated solid, wherein the mass concentration of the system is 20g/L, the cellulase R-10 is used, the dosage of the cellulase R-10 is 20 FPUg/substrate, sampling is carried out periodically, components such as cellobiose, glucose, xylose and the like are measured, and the conversion rate of cellulose is 58.2% after 72 hours.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
because the molecular structure of the lignin contains hydroxyl, the lignin is easily converted into lignin salt and dissolved in water under an alkaline condition, so that the lignin in the lignocellulose raw material is removed, but the lignin salt is also easily converted back into the lignin under an acidic condition, so that the pH value of a mixed solution obtained by mixing the liquid and the washing solution is controlled to be more than or equal to 9.0, the lignin and the like in the mixed solution are not separated out from the mixed solution and are adsorbed in the lignocellulose raw material again in the subsequent cooking treatment process, and the cyclic utilization of the mixed solution is further realized. Therefore, the mixed liquor is used as new pretreatment liquor to treat the lignocellulose raw material, so that the lignin in the mixed liquor can be enriched and recovered, the regeneration utilization rate of phosphate in the mixed liquor is improved, the using amount of the pretreatment liquor is greatly reduced, the practicability of alkaline pretreatment and the comprehensive utilization rate of the lignocellulose raw material are improved, the cost is greatly reduced, and the environmental pollution is reduced through the regeneration cycle of the mixed liquor.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for removing lignin from a lignocellulosic feedstock, said method comprising:
step S1, cooking the lignocellulose raw material by using pretreatment liquid containing phosphate to obtain cooked liquid;
step S2, carrying out solid-liquid separation on the liquid after the cooking treatment to obtain liquid and solid;
step S3, washing the solid to obtain a washing liquid; and
and S4, mixing the liquid and the washing liquid to obtain a mixed liquid, enabling the pH value of the mixed liquid to be more than or equal to 9.0, taking the mixed liquid as a new pretreatment liquid, and repeatedly performing the treatments of the steps S1 to S3 on the lignocellulose raw material, wherein the phosphate is trisodium phosphate or tripotassium phosphate.
2. The method according to claim 1, wherein the phosphate is used to adjust the pH of the mixed solution so that the pH is not less than 11, preferably the pH is 12 to 14.
3. The method according to claim 1 or 2, characterized in that the mixed liquor has a solute mass percent of 23% or less, preferably 17% or less.
4. A method according to any of claims 1 to 3, wherein step S4 is repeated 1-4 times, preferably step S4 is repeated 2-3 times.
5. The method according to any one of claims 1 to 3, wherein the mass ratio of the phosphate to the lignocellulosic feedstock is 2.5-4.5: 10.
6. The method according to claim 1, wherein the pretreatment solution is a phosphate aqueous solution, and preferably the solute mass concentration of the pretreatment solution is 25-45 g/L.
7. The method according to claim 1, wherein the temperature of the cooking treatment is 160 to 190 ℃.
8. The method according to claim 1, wherein the cooking time is 0.2-1 h.
9. The method of claim 1, wherein the solid-liquid separation is centrifugation.
10. The method according to claim 1, wherein the lignocellulosic feedstock is derived from crop stalks or forest residues, preferably the lignocellulosic feedstock is selected from any one or more of corn stover, wheat straw, rice straw.
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