CN111441187A - Method for coproducing fiber sugar, corrugated paper pulp, lignin, biogas and organic fertilizer by comprehensively utilizing straws - Google Patents
Method for coproducing fiber sugar, corrugated paper pulp, lignin, biogas and organic fertilizer by comprehensively utilizing straws Download PDFInfo
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- CN111441187A CN111441187A CN202010325844.9A CN202010325844A CN111441187A CN 111441187 A CN111441187 A CN 111441187A CN 202010325844 A CN202010325844 A CN 202010325844A CN 111441187 A CN111441187 A CN 111441187A
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- water
- lignin
- fibers
- black liquor
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- 239000000835 fiber Substances 0.000 title claims abstract description 136
- 239000010902 straw Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 57
- 229920005610 lignin Polymers 0.000 title claims abstract description 53
- 239000003895 organic fertilizer Substances 0.000 title claims abstract description 28
- 229920001131 Pulp (paper) Polymers 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 89
- 239000007788 liquid Substances 0.000 claims abstract description 72
- 238000000926 separation method Methods 0.000 claims abstract description 62
- 239000002351 wastewater Substances 0.000 claims abstract description 43
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003337 fertilizer Substances 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- 238000012216 screening Methods 0.000 claims abstract description 17
- 108010059892 Cellulase Proteins 0.000 claims abstract description 6
- 229940106157 cellulase Drugs 0.000 claims abstract description 6
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
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- 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 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 241000209140 Triticum Species 0.000 description 5
- 235000021307 Triticum Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000010009 beating Methods 0.000 description 5
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- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000007667 floating Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 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
- 239000000446 fuel Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 241000219146 Gossypium Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
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- 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
- D21C1/00—Pretreatment of the finely-divided materials before digesting
- D21C1/06—Pretreatment of the finely-divided materials before digesting with alkaline reacting compounds
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- 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
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
- D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
- D21B1/14—Disintegrating in mills
- D21B1/16—Disintegrating in mills in the presence of chemical agents
-
- 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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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
-
- 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
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Zoology (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Mechanical Engineering (AREA)
- Fertilizers (AREA)
Abstract
The utility model discloses a method for comprehensively utilizing straws to co-produce fiber sugar, corrugated paper pulp, lignin, methane and organic fertilizer, which comprises the following steps: (1) pretreating straws, and carrying out solid-liquid separation to obtain fibers and black liquor; (2) separating and settling the black liquor to obtain lignin and an organic silicon fertilizer; (3) grinding the fibers into thick liquid, and grading and screening the ground materials to obtain long fibers and fine fibers respectively; dewatering the long fiber to be used as corrugated paper pulp; the fine fiber is saccharified to prepare the fibrous sugar; (4) and the wastewater generated in the process is used for preparing methane and organic fertilizer and is collected and reused. Has the advantages that: the invention provides a new economic and feasible idea of comprehensive utilization of straw biomass, and the profit capacity of straw sugar production can be improved. Meanwhile, the method is based on the lignin preferential separation pretreatment process, so that the ineffective adsorption of lignin to cellulase in the subsequent enzymolysis process is reduced, the enzymolysis effect is improved, and the enzyme dosage is reduced.
Description
Technical Field
The invention belongs to the field of biochemical engineering, and particularly relates to a method for coproducing fiber sugar, corrugated paper pulp, lignin, methane and organic fertilizer by comprehensively utilizing straws.
Background
With the increase of population and the development of social productivity, the shortage of energy and the deterioration of environment become important problems which face and need to be solved urgently for human beings in the twenty-first century, and are also main factors for restricting the sustainable development of society and economy in China. Lignocellulosic biomass resources, an important component of renewable resources, are carriers of green plants for the conversion of solar energy into chemical energy through photosynthesis. It can be converted into solid, liquid and gaseous fuels by physical, chemical or biological means, and also can be converted into various chemical raw materials. Meanwhile, the biomass is also the only renewable carbon source, the effective utilization of the biomass can realize the conversion from the petrochemical carbon economy to the photosynthetic carbon economy, and the biomass has positive significance for maintaining the carbon balance of the ecological environment.
China has abundant biomass resources, the quantity of the resources such as crop straws of corn, rice, wheat, cotton and the like is about 8.2 million tons (about 4 million tons of standard coal) every year, and the quantity of the collectable resources is about 6.9 million tons every year. However, straw utilization has remained a worldwide problem to date. In China, the straw burning phenomenon is still very serious at present, and about more than 3 hundred million tons of crop straws are burnt or discarded every year. The straw recycling and commercialization degree is low, and the task is still quite difficult to realize the aim that the comprehensive utilization rate of the straw is over 80% in 2020 of China.
Lignocellulose constitutes the cell wall of the plant and protects the cells, and it is composed mainly of cellulose, hemicellulose and lignin 3 parts. At present, the utilization of cellulose, hemicellulose and lignin has been intensively studied and achieved many industrialized achievements. But the current utilization mode is only to separate and efficiently utilize single components of lignocellulose. For example, in a typical cellulosic ethanol industry, patents CN101509018 and CN101525636 adopt steam explosion to pretreat a lignocellulose raw material, so that the enzymolysis efficiency of cellulose and hemicellulose is improved, but neglecting separation and extraction of lignin is more favorable for enzymolysis and saccharification of cellulose, and lignin is not efficiently utilized. Patent CN103898788A adopts single screw rod steam explosion equipment to carry out lignocellulose's preliminary treatment, for the pot-type steam explosion, very big improvement the efficiency and the enzymolysis saccharification efficiency of preliminary treatment, but this technique is only to destroy plant fiber structure and hydrolyze hemicellulose simultaneously, still does not have effective separation lignin. Patent CN103790056A adopts double screw extruder preliminary treatment lignocellulose, is only the single component of separation lignocellulose, has improved enzymolysis saccharification efficiency, but under the condition that cellulose and hemicellulose coexist, cellulase enzymolysis efficiency descends, and the enzymolysis time is prolonged. Patent CN107208120A discloses a rapid pretreatment method and apparatus, which have a promising application prospect, but does not emphasize the importance of lignin utilization and the separation and extraction method thereof. The separation technology of the pretreatment components in the above patents is mainly applied to the bioenergy industry represented by cellulosic ethanol, but the industry is currently faced with the general problems: the large ineffective investment results in losses and has not formed a large scale industry worldwide for a long time. The investment for producing the main product alcohol is only 1/3, and in addition, 2/3 is respectively used for solid slag power generation and wastewater treatment, and the main reasons are that: 1) the route design is unreasonable, and corresponding high value-added products cannot be designed according to the structural characteristics of the raw materials; 2) the three major components are not fully and effectively utilized, the utilization efficiency of the pentose in the sugar platform is low, and the lignin is used as low-value fuel; 3) the product is single, only the ethanol and the electric energy of cogeneration are produced, and the industrial chain cannot be effectively extended.
Therefore, the utilization mode of only using lignocellulose for preparing sugar and lignin as combustion fuel is not reasonable, the existing utilization mode of straw lignocellulose must be broken through, the potential application value of each component is deeply analyzed, grading and segmentation separation of each component is realized, and great significance is generated for full-value utilization of lignocellulose.
Disclosure of Invention
The purpose of the invention is as follows: the technical problem to be solved by the invention is to provide a process flow for comprehensive utilization of straw biomass aiming at the defects of the prior art, so as to solve the problem that the industry promotion of the biorefinery industry (biological energy and bio-based chemicals) which takes the lignocellulose such as the straw as the raw material is difficult.
In order to solve the problems, the invention provides a method for comprehensively utilizing straws to coproduce fiber sugar, corrugated paper pulp, lignin, methane and organic fertilizer, which comprises the following steps:
(1) pretreating straws, and carrying out solid-liquid separation to obtain fibers and black liquor;
(2) separating and settling the black liquor obtained in the step (1) to obtain lignin and an organic silicon fertilizer;
wherein the purity of the lignin is more than 85%; the silicon element in the organic silicon fertilizer accounts for more than 50 percent;
(3) grinding the fibers obtained in the step (1) into thick liquid, and grading and screening the ground materials to obtain long fibers and fine fibers respectively; dewatering the long fiber to be used as corrugated paper pulp; the fine fiber is saccharified to prepare the fibrous sugar;
wherein the length of the long fiber is 0.6-5 mm, the beating degree is 30-60 DEG SR, and the wet weight is 1-10 g; the length of the fine fiber is less than 0.6 mm;
(4) and (3) using the wastewater generated in the steps (1) to (3) for preparing methane and organic fertilizer and collecting return water for reuse, wherein the COD of the return water is not more than 500 mg/L.
In the step (1), the pretreatment comprises the following steps:
(i) cutting off raw materials: putting the straws into a continuous straw cutting machine for cutting;
(ii) and (3) dry dedusting: putting the cut straws in the step (i) into dry dedusting equipment, loosening and rolling the cut straws in the dry dedusting equipment, pumping the raised sand dust and straw scraps into a water film dedusting device through a draught fan, and performing water film dedusting;
the water film dedusting is to settle sand dust and straw scraps in the air flow of the sand dust and the straw scraps pumped by the draught fan under the action of spray water and a swirler, remove clean air, separate the straw scraps in the upper layer of the sprayed suspension, and use the straw scraps (mainly leaves and piths of the surface skin of the straw) as organic fertilizer; then carrying out solid-liquid separation on the suspension from which the straw scraps are removed, removing sand dust, and recycling water as spray water;
wherein, when the COD of the water is enriched to 5000 mg/L, the water is sent to a wastewater collection tank;
(iii) washing with hot water: (iii) soaking and washing the material subjected to dry dedusting in the step (ii) in hot water to remove soluble substances, and performing solid-liquid separation on the hot water subjected to material washing to remove sand and dust; the filtrate is used as washing water again for recycling;
wherein, when the COD enrichment of the water reaches 4000 mg/L, the water is sent into a water film spraying system to be used as spraying water;
wherein, if the COD of the water after soaking and washing reaches 5000 mg/L, the water is sent into a wastewater collection tank;
(iv) double-screw alkaline pretreatment: conveying the material washed by the hot water in the step (iii) into a double-screw extrusion thread rolling machine, and spraying alkali liquor while carrying out double-screw extrusion thread rolling on the material so as to fully mix the alkali liquor and the material to obtain an alkali material subjected to extrusion thread rolling;
meanwhile, sending the waste liquid (COD is not less than 10000 mg/L) discharged from the material passing through the twin-screw process into a waste liquid collecting tank;
(v) and (3) heat preservation of a heat preservation bin: heating and insulating the alkaline material treated in the step (iv) in an insulating bin;
(vi) multi-stage displacement washing: and (v) placing the alkaline material heated and insulated in the heat-insulating bin in a multistage displacement washing device for washing, and performing solid-liquid separation on washing water to obtain black liquor and fibers.
In the step (i), the length of the cut straw is 3-5 cm.
In the step (ii), the temperature of the spray water is 30-70 ℃.
In the step (iii), the temperature of the hot water is 70-95 ℃, and the soaking and washing time is 4-30 min.
In the step (iv), the dosage of the alkali liquor is 1-6 times of that of the straws, and the concentration of the alkali in the alkali liquor is 5-50 g/L, wherein the alkali is any one or a combination of more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia water, n-propylamine, isopropylamine, n-butylamine, isobutylamine, diethylamine, triethylamine and ethylenediamine.
In the step (v), the temperature of the heat preservation bin is 50-95 ℃, and the heat preservation time is 10-90 min.
And (vi) adding water to dilute the alkaline material heated and insulated in the heat-insulating bin in the step (v) until the concentration is 40-90 g/L, then placing the alkaline material in 2-5-stage displacement washing equipment for washing, and performing solid-liquid separation on washing water until the concentration of solid matters in the black liquor reaches 100 g/L or above, wherein the main components of the solid matters in the black liquor are sodium silicate, hemicellulose, inorganic salt and sodium lignin.
In the step (2), the step of separating and settling the black liquor to obtain the lignin and the organic silicon fertilizer is specifically to perform primary solid-liquid separation on the black liquor to obtain residue containing fine fibers (namely a small amount of fine fibers, and the fine fibers are added into the fine fibers obtained in the step of fiber grading and screening) and filtrate, perform secondary solid-liquid separation after the filtrate is acidified to the pH value of 8.5-9.5 for the first time to obtain acidified black liquor and residue, wherein the obtained residue is the organic silicon fertilizer, and extract the lignin after the acidified black liquor is concentrated until the concentration of solid matters reaches 200 g/L.
The method for extracting lignin from the concentrated acidified black liquor is any one of the following methods:
the method comprises the following steps: carrying out solid-liquid separation for three times after the acidified black liquor is acidified for the second time to obtain residue and filtrate; the obtained residue is lignin, and the filtrate is directly or after desalination treatment, sent into an aerobic treatment tank for treatment and recycled; wherein the secondary acidification is carried out until the pH value is 2-5, and the temperature in the acidification process is room temperature-90 ℃.
The second method comprises the following steps: membrane concentrating the acidified black liquor to obtain concentrated solution, i.e. lignin solution, and sending the permeate (alkali liquor) to the double-screw alkaline pretreatment for recycling; wherein the membrane is any one or a combination of a ceramic microfiltration membrane with the molecular weight of 40-100 nm, a stainless steel membrane with the molecular weight of 40-100 nm and a nanofiltration membrane with the molecular weight of 300-5000 Da.
Wherein, the concentration of the acid used in the first acidification and the second acidification is 3 to 25 percent (mass fraction); the acid is any one or combination of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, sulfurous acid, formic acid, acetic acid, citric acid, oxalic acid, carbon dioxide and sulfur dioxide.
And (3) grinding the fibers obtained in the step (1) into pulp with the concentration of 150-300 g/L (water is not necessarily added, the dryness of the obtained material is met in a certain range in the previous replacement washing step, if the dryness of the obtained material is not met, certain water is supplemented, the ground material is diluted to the concentration of 10-100 g/L by adding water, and then grading and screening are carried out by adopting a screen with the aperture of 18-60 meshes (grading and screening are carried out according to the required size, and long fibers and fine fibers are respectively obtained).
In the step (3), the classifying screen is used for screening the ground materials by using a screen to obtain long fibers and a solution containing fine fibers; and then carrying out solid-liquid separation on the solution containing the fine fibers to obtain the fine fibers and filtrate, wherein the filtrate is used as dilution water to dilute and recycle the ground materials.
And (3) dewatering the long fibers, namely feeding the long fibers into a fiber concentration device for dewatering until the concentration of the long fibers is 350-500 g/L, using the dewatered long fibers as corrugated paper pulp, and recycling the removed water as return water.
In the step (3), the specific steps of preparing the fibrous sugar by hydrolyzing and saccharifying the fine fibers comprise the steps of adding water into the fine fibers to prepare slurry with the concentration of 50-250 g/L, adding 5-50U/g cellulose, performing enzymolysis and saccharification for 24-72 hours at the temperature of 25-35 ℃, and separating solid and liquid of reaction liquid after the reaction is finished to obtain sugar liquid and enzymolysis residues, wherein the enzymolysis residues are decomposed to be used as organic fertilizers, or directly used as raw materials for synthesizing phenolic resin adhesives, or doped with long fiber components to be used for producing corrugated paper pulp.
The cellulase is commercial Novoxil cellulase, the enzyme activity value is 200U/m L, the enzyme activity is defined as that the amount of 1m L enzyme hydrolyzed to generate 1 microgram of glucose per minute at 50 ℃ and pH value of 4.8 is defined as an activity unit.
In the step (4), the wastewater is used for preparing methane and organic fertilizer, and the return water is collected and reused, specifically, the wastewater collection tank is subjected to anaerobic treatment to obtain methane; and then carrying out aerobic treatment on the wastewater after the anaerobic treatment, carrying out solid-liquid separation, wherein the obtained filtrate is backwater, and the obtained filter residue is used for preparing an organic fertilizer (sludge concentration, plant debris, enzymolysis residues and an organic silicon fertilizer obtained by the anaerobic and aerobic treatment are mixed and fermented).
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the invention provides a new economic and feasible idea of comprehensive utilization of straw biomass, and the profit capacity of straw sugar production can be improved.
2. The method is based on the lignin preferential separation pretreatment process, so that the ineffective adsorption of lignin to cellulase in the subsequent enzymolysis process is reduced, the enzymolysis effect is improved, and the enzyme dosage is reduced.
3. The lignin of different types can be obtained by multi-stage separation of the lignin, the refining of the lignin is realized, and simultaneously the separation efficiency and the utilization value of carbohydrates such as cellulose are improved.
4. The invention conforms to the natural law, separates and extracts natural biomass long fibers, solves the problems of slow enzymolysis speed and low efficiency of the long fibers, and improves the economic value of the long fibers.
Drawings
FIG. 1 is a process flow diagram corresponding to example 1.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
Example 1
A method for comprehensively co-producing fiber sugar, corrugated paper pulp, lignin, methane and organic fertilizer by straws based on alkaline pretreatment specifically comprises the following steps:
the method comprises the following steps of feeding wheat straws into a continuous straw cutting machine through a conveyor belt for cutting, wherein the length of the cut straws is 3-5 cm, feeding the cut straws into dry dust removal equipment, loosely rolling the straws in the dry dust removal equipment, raising sand dust and debris into water film dust removal equipment through a draught fan, settling plant debris and sand dust under the action of air flow containing the sand dust and the debris under the action of spraying water flow and a cyclone, removing clean air, separating the straw debris floating in the suspension obtained after spraying (the obtained plant debris is used as an organic fertilizer) (refer to CN201110315722.2), carrying out solid-liquid separation on the suspension from which the straw debris is removed, discharging silt out of a system, using a circulating water tank as spraying water for recycling, feeding the water into a waste water collecting tank when COD of the water is enriched to 5000 mg/L, carrying out anaerobic treatment for producing biogas, wherein the plant debris mainly comprises leaves and pithes on the surface of the straws, and the spraying water is sprayed at a temperature of 40 ℃, and the silt attached to the material sheet is removed out of the system.
And (3) putting the dedusted materials into hot water washing equipment, soaking and washing the materials in hot water at 80 ℃ for 15min for washing, washing to remove soluble substances, then putting the materials into a double screw for alkaline pretreatment, carrying out solid-liquid separation on the washed hot water of the materials, removing the obtained sand dust out of a system, recycling the filtrate until COD is enriched to 4000 mg/L, putting the filtrate into a water film dedusting system to be used as spray water, and putting the filtrate into a waste water collecting tank if the COD is enriched to 5000 mg/L.
The materials washed by hot water are extruded and thread-rolled by a double screw rod, and simultaneously 2 times of alkali liquor corresponding to the dry weight of the straws is sprayed by a pump in the extrusion thread-rolling process, so that the alkali liquor is fully mixed with the materials, the alkali concentration in the alkali liquor is 50 g/L, the obtained alkali materials are sent into a heat-preserving bin for heat-preserving reaction, the materials are sent into a waste liquor collecting tank through waste liquor with the COD (chemical oxygen demand) of 10000 mg/L discharged in the double screw rod process for anaerobic treatment to produce methane, wherein the alkali used in the prepared alkali liquor is sodium hydroxide, then the alkali materials are sent into the heat-preserving bin at 85 ℃ for heating and heat preserving for 30min, and then the alkali materials are sent;
adding water to dilute the alkaline material subjected to the heating reaction in the heat-preservation bin to the concentration of 80 g/L before entering a multi-stage displacement washing device, performing solid-liquid separation on washing water by adopting 3-stage displacement washing to obtain black liquor and fibers, wherein the concentration of solid matters in the black liquor reaches 100 g/L, and the main components of the black liquor are sodium silicate, hemicellulose, inorganic salt and lignin sodium;
the washed material is mixed with 200 g/L pulp and enters a high-concentration mill for pulping, the grinded material is diluted to 50 g/L pulp according to a proportion, the pulp is sent to a fiber screening device with a screen mesh with the aperture of 30 meshes to obtain long fibers and solution containing the fine fibers, then the solution containing the fine fibers is subjected to solid-liquid separation to obtain the fine fibers and filtrate, wherein the filtrate is used as dilution water to dilute and recycle the grinded material, the average length of the long fibers is 0.8mm, the average length of the fine fibers is 0.2mm, the long fibers are sent to a fiber concentration device for dehydration, the concentration of the dehydrated long fibers is concentrated to 400 g/L from 70 g/L and used as corrugated paper pulp, the beating degree is 35 DEG SR, the obtained filtrate is used as backwater again, and the fine fibers are sent to an enzymolysis tank.
Preparing fine fibers into slurry with the concentration of 180 g/L, adding 15U/g cellulose into the slurry, carrying out enzymolysis saccharification in an enzymolysis tank, wherein the enzymolysis temperature is 30 ℃, the enzymolysis time is 60 hours, the total sugar yield is 80%, and after the reaction is finished, carrying out solid-liquid separation on feed liquid to obtain sugar liquid and enzymolysis residues, wherein the enzymolysis residues are used as organic fertilizers after being thoroughly decomposed;
carrying out solid-liquid separation on the obtained black liquor, merging a small amount of the obtained fine fibers into the fine fibers obtained in the fiber grading and screening step, carrying out primary acidification on the filtrate until the pH value is 8.7, carrying out solid-liquid separation to obtain a precipitate and acidified black liquor, wherein the precipitate is an organic silicon fertilizer, the silicon element content in the organic silicon fertilizer is 55%, concentrating the acidified black liquor until the solid concentration reaches 200 g/L, carrying out secondary acidification on the concentrated black liquor until the pH value is 3.5, carrying out solid-liquid separation at the acidification process temperature of 50 ℃, obtaining solid lignin with the lignin purity of 90%, directly feeding the waste liquor into an aerobic treatment tank or carrying out desalination treatment and then feeding into the aerobic treatment tank for treatment, and recycling the waste liquor again, wherein the used acid is 20% sulfuric acid (mass fraction).
The method comprises the steps of carrying out anaerobic treatment on high-concentration wastewater (COD of the high-concentration wastewater is more than 5000 mg/L) generated in the process to prepare methane, carrying out aerobic treatment on the wastewater after the anaerobic treatment, mixing the wastewater with part of low-concentration wastewater in a system to enter the system to be used as backwater, wherein the COD of the backwater is 500 mg/L, and carrying out mixed fermentation on sludge concentration, plant debris, enzymolysis residues and organic silicon fertilizers obtained by the anaerobic and aerobic treatment to produce the organic fertilizer.
The anaerobic treatment is to feed high-concentration wastewater into an anaerobic tower containing anaerobic granular sludge and carry out anaerobic treatment for 24 hours at 35 ℃, the aerobic treatment is to feed the wastewater into an aerobic tank, DO dissolved oxygen value is 3 mg/L and the wastewater is treated for 24 hours, and the mixed fermentation is as in the following examples with reference to CN201110315722.2.
Example 2
A method for comprehensively co-producing fiber sugar, corrugated paper pulp, lignin, methane and organic fertilizer by straws based on alkaline pretreatment specifically comprises the following steps:
the raw material cutting method comprises the steps of feeding wheat straws into a continuous straw cutting machine through a conveying belt for cutting, wherein the length of the cut straws is 3-5 cm, feeding the cut straws into dry dust removal equipment, loosening and rolling the cut straws in the dry dust removal equipment, raising sand dust and debris, pumping the raised sand dust and debris into water film dust removal equipment through a draught fan, settling plant debris and sand dust under the action of air flow containing the sand dust and the debris under the action of spraying water flow and a cyclone, removing clean air, separating straw debris floating in suspension obtained after spraying (the obtained plant debris is used as organic fertilizer), carrying out solid-liquid separation on the suspension from which the straw debris is removed, removing silt out of a system, recycling the water from a circulating water tank for spraying water, feeding the water into a waste water collecting tank when COD (chemical oxygen demand) of the water is enriched to 5000 mg/L, carrying out anaerobic treatment for producing biogas, wherein the plant debris mainly comprises leaves and pithes on the surface of the straws, the spraying water temperature is 40 ℃, and removing silt attached to the outside.
And (3) putting the dedusted materials into hot water washing equipment, soaking and washing the materials in hot water at 80 ℃ for 15min for washing, washing to remove soluble substances, then putting the materials into a double screw for alkaline pretreatment, carrying out solid-liquid separation on the washed hot water of the materials, removing the obtained sand dust out of a system, recycling the filtrate until COD is enriched to 4000 mg/L, putting the filtrate into a water film dedusting system to be used as spray water, and putting the filtrate into a waste water collecting tank if the COD is enriched to 5000 mg/L.
The materials washed by hot water are extruded and thread-rolled by a double screw rod, and simultaneously 2 times of alkali liquor corresponding to the dry weight of the straws is sprayed by a pump in the extrusion thread-rolling process, so that the alkali liquor is fully mixed with the materials, the alkali concentration in the alkali liquor is 50 g/L, the obtained alkali materials are sent into a heat-preserving bin for heat-preserving reaction, the materials are sent into a waste liquor collecting tank through waste liquor with the COD (chemical oxygen demand) of 10000 mg/L discharged in the double screw rod process for anaerobic treatment to produce methane, wherein the alkali used in the prepared alkali liquor is sodium hydroxide, then the alkali materials are sent into the heat-preserving bin at 85 ℃ for heating and heat preserving for 30min, and then the alkali materials are sent;
adding water to dilute the alkaline material subjected to the heating reaction in the heat-preservation bin to the concentration of 80 g/L before entering a multi-stage displacement washing device, performing solid-liquid separation on washing water by adopting 3-stage displacement washing to obtain black liquor and fibers, wherein the concentration of solid matters in the black liquor reaches 100 g/L, and the main components of the black liquor are sodium silicate, hemicellulose, inorganic salt and lignin sodium;
the washed material is mixed with 200 g/L pulp and enters a high-concentration mill for pulping, the grinded material is diluted to 50 g/L pulp according to a proportion, the pulp is sent to a fiber screening device with a screen mesh with the aperture of 50 meshes to obtain long fibers and solution containing the fine fibers, then the solution containing the fine fibers is subjected to solid-liquid separation to obtain the fine fibers and filtrate, wherein the filtrate is used as dilution water to dilute and recycle the grinded material, the average length of the long fibers is 0.7mm, the average length of the fine fibers is 0.1mm, the long fibers are sent to a fiber concentration device for dehydration, the concentration of the dehydrated long fibers is concentrated to 400 g/L from 70 g/L and used as corrugated paper pulp, the beating degree is 35 DEG SR, the obtained filtrate is used as backwater again, and the fine fibers are sent to an enzymolysis tank.
Preparing fine fibers into slurry with the concentration of 180 g/L, adding 15U/g cellulose into the slurry, carrying out enzymolysis saccharification in an enzymolysis tank, wherein the enzymolysis temperature is 30 ℃, the enzymolysis time is 60 hours, the total sugar yield is 85 percent, and after the reaction is finished, carrying out solid-liquid separation on feed liquid to obtain sugar liquid and enzymolysis residues, wherein the enzymolysis residues are used as organic fertilizers after being thoroughly decomposed;
carrying out solid-liquid separation on the obtained black liquor, merging a small amount of the obtained fine fibers into the fine fibers obtained in the fiber grading and screening step, carrying out primary acidification on the filtrate until the pH value is 9, carrying out solid-liquid separation to obtain a precipitate and acidified black liquor, wherein the precipitate is an organic silicon fertilizer, the silicon element content in the organic silicon fertilizer is 50%, concentrating the acidified black liquor until the solid concentration reaches 200 g/L, carrying out secondary acidification on the concentrated black liquor until the pH value is 3.5, the acidification process temperature is 50 ℃, then carrying out solid-liquid separation to obtain solid lignin, the lignin purity is 87%, and directly feeding the waste liquor into an aerobic treatment tank or carrying out desalination treatment and then feeding into the aerobic treatment tank for treatment, and recycling the waste liquor again, wherein the used acid is 20% sulfuric acid (mass fraction).
The method comprises the steps of carrying out anaerobic treatment on high-concentration wastewater (COD of the high-concentration wastewater is more than 5000 mg/L) generated in the process to prepare methane, carrying out aerobic treatment on the wastewater after the anaerobic treatment, mixing the wastewater with part of low-concentration wastewater in a system to enter the system to be used as backwater, wherein the COD of the backwater is 500 mg/L, and carrying out mixed fermentation on sludge concentration, plant debris, enzymolysis residues and organic silicon fertilizers obtained by the anaerobic and aerobic treatment to produce the organic fertilizer.
Example 3
A method for comprehensively co-producing fiber sugar, corrugated paper pulp, lignin, methane and organic fertilizer by straws based on alkaline pretreatment specifically comprises the following steps:
the raw material cutting method comprises the steps of feeding wheat straws into a continuous straw cutting machine through a conveying belt for cutting, wherein the length of the cut straws is 3-5 cm, feeding the cut straws into dry dust removal equipment, loosening and rolling the cut straws in the dry dust removal equipment, raising sand dust and debris, pumping the raised sand dust and debris into water film dust removal equipment through a draught fan, settling plant debris and sand dust under the action of air flow containing the sand dust and the debris under the action of spraying water flow and a cyclone, removing clean air, separating straw debris floating in suspension obtained after spraying (the obtained plant debris is used as organic fertilizer), carrying out solid-liquid separation on the suspension from which the straw debris is removed, removing silt out of a system, recycling the water from a circulating water tank for spraying water, feeding the water into a waste water collecting tank when COD (chemical oxygen demand) of the water is enriched to 5000 mg/L, carrying out anaerobic treatment for producing biogas, wherein the plant debris mainly comprises leaves and pithes on the surface of the straws, the spraying water temperature is 40 ℃, and removing silt attached to the outside.
And (3) putting the dedusted materials into hot water washing equipment, soaking and washing the materials in hot water at 80 ℃ for 15min for washing, washing to remove soluble substances, then putting the materials into a double screw for alkaline pretreatment, carrying out solid-liquid separation on the washed hot water of the materials, removing the obtained sand dust out of a system, recycling the filtrate until COD is enriched to 4000 mg/L, putting the filtrate into a water film dedusting system to be used as spray water, and putting the filtrate into a waste water collecting tank if the COD is enriched to 5000 mg/L.
The materials washed by hot water are extruded and thread-rolled by a double screw rod, and simultaneously 2 times of alkali liquor corresponding to the dry weight of the straws is sprayed by a pump in the extrusion thread-rolling process, so that the alkali liquor is fully mixed with the materials, the alkali concentration in the alkali liquor is 50 g/L, the obtained alkali materials are sent into a heat-preserving bin for heat-preserving reaction, the materials are sent into a waste liquor collecting tank through waste liquor with the COD (chemical oxygen demand) of 10000 mg/L discharged in the double screw rod process for anaerobic treatment to produce methane, wherein the alkali used in the prepared alkali liquor is sodium hydroxide, then the alkali materials are sent into the heat-preserving bin at 85 ℃ for heating and heat preserving for 30min, and then the alkali materials are sent;
adding water to dilute the alkaline material subjected to the heating reaction in the heat-preservation bin to the concentration of 80 g/L before entering a multi-stage displacement washing device, performing solid-liquid separation on washing water by adopting 3-stage displacement washing to obtain black liquor and fibers, wherein the concentration of solid matters in the black liquor reaches 100 g/L, and the main components of the black liquor are sodium silicate, hemicellulose, inorganic salt and lignin sodium;
the washed material is mixed with 200 g/L pulp and enters a high-concentration mill for pulping, the grinded material is diluted to 50 g/L pulp according to a proportion, the pulp is sent to a fiber screening device with a screen mesh with the aperture of 50 meshes to obtain long fibers and solution containing the fine fibers, then the solution containing the fine fibers is subjected to solid-liquid separation to obtain the fine fibers and filtrate, wherein the filtrate is used as dilution water to dilute and recycle the grinded material, the average length of the long fibers is 0.7mm, the average length of the fine fibers is 0.1mm, the long fibers are sent to a fiber concentration device for dehydration, the concentration of the dehydrated long fibers is concentrated to 400 g/L from 70 g/L and used as corrugated paper pulp, the beating degree is 35 DEG SR, the obtained filtrate is used as backwater again, and the fine fibers are sent to an enzymolysis tank.
Preparing fine fibers into slurry with the concentration of 180 g/L, adding 15U/g cellulose into the slurry, carrying out enzymolysis saccharification in an enzymolysis tank, wherein the enzymolysis temperature is 30 ℃, the enzymolysis time is 60 hours, the total sugar yield is 85 percent, and after the reaction is finished, carrying out solid-liquid separation on feed liquid to obtain sugar liquid and enzymolysis residues, wherein the enzymolysis residues are used as organic fertilizers after being thoroughly decomposed;
and (3) carrying out solid-liquid separation on the obtained black liquor, and merging a small amount of obtained fine fibers into the fine fibers obtained in the fiber grading and screening step. And (3) carrying out primary acidification on the filtrate until the pH value is 9, carrying out solid-liquid separation to obtain a precipitate and acidified black liquor, wherein the precipitate is the organic silicon fertilizer, and the silicon element in the organic silicon fertilizer accounts for 50%. And (3) introducing the acidified black liquor into a 400Da nanofiltration membrane for concentration, recovering alkali liquor, concentrating the lignin black liquor by 6 times, and spray-drying the concentrated black liquor to obtain lignin powder with the purity of 88%. The pH value of the obtained alkali liquor is 9.5, and the part of the alkali liquor is used for preparing the alkali liquor used for the alkali method double-screw pretreatment.
The method comprises the steps of carrying out anaerobic treatment on high-concentration wastewater (COD of the high-concentration wastewater is more than 5000 mg/L) generated in the process to prepare methane, carrying out aerobic treatment on the wastewater after the anaerobic treatment, mixing the wastewater with part of low-concentration wastewater in a system to enter the system to be used as backwater, wherein the COD of the backwater is 500 mg/L, and carrying out mixed fermentation on sludge concentration, plant debris, enzymolysis residues and organic silicon fertilizers obtained by the anaerobic and aerobic treatment to produce the organic fertilizer.
Example 4
A method for comprehensively co-producing fiber sugar, corrugated paper pulp, lignin, methane and organic fertilizer by straws based on alkaline pretreatment specifically comprises the following steps:
the raw material cutting method comprises the steps of feeding wheat straws into a continuous straw cutting machine through a conveying belt for cutting, wherein the length of the cut straws is 3-5 cm, feeding the cut straws into dry dust removal equipment, loosening and rolling the cut straws in the dry dust removal equipment, raising sand dust and debris, pumping the raised sand dust and debris into water film dust removal equipment through a draught fan, settling plant debris and sand dust under the action of air flow containing the sand dust and the debris under the action of spraying water flow and a cyclone, removing clean air, separating straw debris floating in suspension obtained after spraying (the obtained plant debris is used as organic fertilizer), carrying out solid-liquid separation on the suspension from which the straw debris is removed, removing silt out of a system, recycling the water from a circulating water tank for spraying water, feeding the water into a waste water collecting tank when COD (chemical oxygen demand) of the water is enriched to 5000 mg/L, carrying out anaerobic treatment for producing biogas, wherein the plant debris mainly comprises leaves and pithes on the surface of the straws, the spraying water temperature is 40 ℃, and removing silt attached to the outside.
And (3) putting the dedusted materials into hot water washing equipment, soaking and washing the materials in hot water at 80 ℃ for 15min for washing, washing to remove soluble substances, then putting the materials into a double screw for alkaline pretreatment, carrying out solid-liquid separation on the washed hot water of the materials, removing the obtained sand dust out of a system, recycling the filtrate until COD is enriched to 4000 mg/L, putting the filtrate into a water film dedusting system to be used as spray water, and putting the filtrate into a waste water collecting tank if the COD is enriched to 5000 mg/L.
The materials washed by hot water are extruded and thread-rolled by a double screw rod, and simultaneously 2 times of alkali liquor corresponding to the dry weight of the straws is sprayed by a pump in the extrusion thread-rolling process, so that the alkali liquor is fully mixed with the materials, the alkali concentration in the alkali liquor is 20 g/L, the obtained alkali materials are sent into a heat-preserving bin for heat-preserving reaction, the materials are sent into a waste liquor collecting tank through waste liquor with the COD (chemical oxygen demand) of 10000 mg/L discharged in the double screw rod process for anaerobic treatment to produce methane, wherein the alkali used in the prepared alkali liquor is sodium hydroxide, then the alkali materials are sent into the heat-preserving bin at 85 ℃ for heating and heat preserving for 30min, and then the alkali materials are sent;
adding water to dilute the alkaline material subjected to the heating reaction in the heat-preservation bin to the concentration of 50 g/L before entering a multi-stage displacement washing device, performing solid-liquid separation on washing water by adopting 3-stage displacement washing to obtain black liquor and fibers, wherein the concentration of solid matters in the black liquor reaches 100 g/L, and the main components of the black liquor are sodium silicate, hemicellulose, inorganic salt and lignin sodium;
the washed material is mixed with 200 g/L pulp and enters a high-concentration mill for pulping, the grinded material is diluted to 50 g/L pulp according to a proportion, the pulp is sent to a fiber screening device with a screen mesh with the aperture of 30 meshes to obtain long fibers and solution containing the fine fibers, then the solution containing the fine fibers is subjected to solid-liquid separation to obtain the fine fibers and filtrate, wherein the filtrate is used as dilution water to dilute and recycle the grinded material, the average length of the long fibers is 0.8mm, the average length of the fine fibers is 0.2mm, the long fibers are sent to a fiber concentration device for dehydration, the concentration of the dehydrated long fibers is concentrated to 400 g/L from 70 g/L and used as corrugated paper pulp, the beating degree is 35 DEG SR, the obtained filtrate is used as backwater again, and the fine fibers are sent to an enzymolysis tank.
Preparing fine fibers into slurry with the concentration of 180 g/L, adding 15U/g cellulose into the slurry, carrying out enzymolysis saccharification in an enzymolysis tank, wherein the enzymolysis temperature is 30 ℃, the enzymolysis time is 60 hours, the total sugar yield is 75%, carrying out solid-liquid separation on feed liquid after the reaction is finished to obtain sugar liquid and enzymolysis residues, and decomposing the enzymolysis residues to be used as organic fertilizer;
carrying out solid-liquid separation on the obtained black liquor, merging a small amount of the obtained fine fibers into the fine fibers obtained in the fiber grading and screening step, carrying out primary acidification on the filtrate until the pH value is 9, carrying out solid-liquid separation to obtain a precipitate and acidified black liquor, wherein the precipitate is an organic silicon fertilizer, the silicon element content in the organic silicon fertilizer is 50%, concentrating the acidified black liquor until the solid concentration reaches 200 g/L, carrying out secondary acidification on the concentrated black liquor until the pH value is 3.5, the acidification process temperature is 50 ℃, then carrying out solid-liquid separation to obtain solid lignin, the lignin purity is 87%, and directly feeding the waste liquor into an aerobic treatment tank or carrying out desalination treatment and then feeding into the aerobic treatment tank for treatment, and recycling the waste liquor again, wherein the used acid is 20% sulfuric acid (mass fraction).
The method comprises the steps of carrying out anaerobic treatment on high-concentration wastewater (COD of the high-concentration wastewater is more than 5000 mg/L) generated in the process to prepare methane, carrying out aerobic treatment on the wastewater after the anaerobic treatment, mixing the wastewater with part of low-concentration wastewater in a system to enter the system to be used as backwater, wherein the COD of the backwater is 500 mg/L, and carrying out mixed fermentation on sludge concentration, plant debris, enzymolysis residues and organic silicon fertilizers obtained by the anaerobic and aerobic treatment to produce the organic fertilizer.
Claims (10)
1. A method for comprehensively utilizing straws to coproduce fiber sugar, corrugated paper pulp, lignin, methane and organic fertilizer is characterized by comprising the following steps:
(1) pretreating straws, and carrying out solid-liquid separation to obtain fibers and black liquor;
(2) separating and settling the black liquor obtained in the step (1) to obtain lignin and an organic silicon fertilizer;
(3) grinding the fibers obtained in the step (1) into thick liquid, and grading and screening the ground materials to obtain long fibers and fine fibers; dewatering the long fiber to be used as corrugated paper pulp; the fine fiber is saccharified to prepare the fibrous sugar;
wherein the length of the long fiber is 0.6-5 mm; the length of the fine fiber is less than 0.6 mm;
(4) and (3) using the wastewater generated in the steps (1) to (3) for preparing methane and organic fertilizer and collecting return water for reuse, wherein the COD of the return water is not more than 500 mg/L.
2. The method of claim 1, wherein in step (1), the pre-treating comprises the steps of:
(i) cutting off raw materials: putting the straws into a continuous straw cutting machine for cutting;
(ii) and (3) dry dedusting: putting the cut straws in the step (i) into dry dedusting equipment, loosening and rolling the cut straws in the dry dedusting equipment, pumping the raised sand dust and straw scraps into a water film dedusting device through a draught fan, and performing water film dedusting;
the water film dedusting is to settle sand dust and straw scraps under the action of spray water and a swirler to obtain suspension; separating straw scraps in the upper layer of the suspension to be used as an organic fertilizer; then carrying out solid-liquid separation on the suspension from which the straw scraps are removed, removing sand dust, and recycling water as spray water;
wherein, when the COD of the water is enriched to 5000 mg/L, the water is sent to a wastewater collection tank;
(iii) washing with hot water: (iii) soaking and washing the materials subjected to dust removal in the step (ii) in hot water, and performing solid-liquid separation on the hot water subjected to material washing to remove dust; the filtrate is used as washing water again for recycling;
wherein, when the COD enrichment of the water reaches 4000 mg/L, the water is sent into a water film spraying system to be used as spraying water;
(iv) double-screw alkaline pretreatment: (iv) conveying the material washed by the hot water in the step (iii) into a double-screw extrusion thread rolling machine, and pumping alkali liquor into the double-screw extrusion thread rolling machine while the material is subjected to double-screw extrusion thread rolling to obtain an alkali material subjected to extrusion thread rolling;
meanwhile, sending waste liquid discharged in the process of passing the materials through the double screws into a waste liquid collecting tank;
(v) and (3) heat preservation of a heat preservation bin: heating and insulating the alkaline material treated in the step (iv) in an insulating bin;
(vi) multi-stage displacement washing: and (v) placing the alkaline material heated and insulated in the heat-insulating bin in a multistage displacement washing device for washing, and performing solid-liquid separation on washing water to obtain black liquor and fibers.
3. The method as claimed in claim 2, wherein in step (i), the cut straw has a length of 3-5 cm;
in the step (ii), the temperature of the spray water is 30-70 ℃;
in the step (iii), the temperature of hot water is 70-95 ℃, and the soaking and washing time is 4-30 min;
in the step (iv), the dosage of the alkali liquor is 1-6 times of that of the straws, and the alkali concentration in the alkali liquor is 5-50 g/L;
in the step (v), the temperature of the heat preservation bin is 50-95 ℃, and the heat preservation time is 10-90 min;
in the step (vi), the alkaline material heated and insulated in the heat-insulation bin in the step (v) is firstly diluted by adding water until the concentration is 40-90 g/L, then the alkaline material is placed in 2-5-stage replacement washing equipment for washing, and the washing water is subjected to solid-liquid separation, so that the concentration of solid matters in the black liquor reaches 100 g/L and above.
4. The method as claimed in claim 1, wherein the step (2) of separating and settling the black liquor to obtain lignin and the organic silicon fertilizer comprises the steps of carrying out primary solid-liquid separation on the black liquor to obtain residue containing fine fibers and filtrate, carrying out secondary solid-liquid separation on the filtrate after primary acidification is carried out until the pH value is 8.5-9.5 to obtain acidified black liquor and residue, wherein the residue is the organic silicon fertilizer, and concentrating the acidified black liquor until the concentration of solid matters reaches 200 g/L to extract the lignin.
5. The method according to claim 4, wherein the step of extracting lignin from the acidified black liquor after concentration comprises the steps of carrying out solid-liquid separation for three times after carrying out secondary acidification on the acidified black liquor to obtain residue and filtrate; the obtained residue is lignin, and the filtrate is directly or after desalination treatment, sent into an aerobic treatment tank for treatment and recycled;
wherein the secondary acidification is carried out until the pH value is 2-5, and the temperature in the acidification process is room temperature-90 ℃.
6. The method according to claim 4, wherein the step of extracting the lignin from the acidified black liquor after concentration is to concentrate the acidified black liquor by a membrane to obtain a concentrated solution, namely a lignin solution, and the permeate solution is sent to the twin-screw alkaline pretreatment for recycling;
wherein the membrane is any one or a combination of a ceramic microfiltration membrane with the molecular weight of 40-100 nm, a stainless steel membrane with the molecular weight of 40-100 nm and a nanofiltration membrane with the molecular weight of 300-5000 Da.
7. The method according to claim 1, wherein in the step (3), the fibers obtained in the step (1) are ground, the ground materials are diluted by adding water to the concentration of 10-100 g/L, and then a screen with the aperture of 18-60 meshes is used for classification and screening.
8. The method according to claim 1, wherein in the step (3), the classified screening is to screen the refined material by using a screen to obtain long fibers and a solution containing fine fibers; then carrying out solid-liquid separation on the solution containing the fine fibers to obtain fine fibers and filtrate, wherein the filtrate is used as dilution water to dilute and recycle the ground materials;
and the long fiber dewatering step is to send the long fibers into a fiber concentration device for dewatering until the concentration of the long fibers is 350-500 g/L, use the dewatered long fibers as corrugated paper pulp, and use the removed water as return water for recycling.
9. The method according to claim 1, wherein in the step (3), the specific steps of preparing the fibrous sugar by hydrolyzing and saccharifying the fine fibers comprise the steps of adding water into the fine fibers to prepare slurry with the concentration of 50-250 g/L, adding 5-50U/g cellulose of cellulase, performing enzymolysis and saccharification for 24-72 hours at 25-35 ℃, and separating solid and liquid in reaction liquid after the reaction is finished to obtain sugar liquid and enzymolysis residues, wherein the enzymolysis residues are decomposed to be used as organic fertilizers, or directly used as raw materials for synthesizing phenolic resin adhesives, or doped with long fiber components to be used for producing corrugated paper pulp.
10. The method according to claim 1, wherein in the step (4), the wastewater is used for preparing biogas and organic fertilizer, and the returned water is collected and reused, specifically, the wastewater collection tank is subjected to anaerobic treatment to obtain biogas; and carrying out aerobic treatment on the wastewater after the anaerobic treatment, carrying out solid-liquid separation, wherein the obtained filtrate is backwater, and the obtained filter residue is used for preparing the organic fertilizer.
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