CN106638089B - The method for preparing dissolving pulp and other high value added products using crop material - Google Patents
The method for preparing dissolving pulp and other high value added products using crop material Download PDFInfo
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- CN106638089B CN106638089B CN201610852062.4A CN201610852062A CN106638089B CN 106638089 B CN106638089 B CN 106638089B CN 201610852062 A CN201610852062 A CN 201610852062A CN 106638089 B CN106638089 B CN 106638089B
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- filter residue
- filtrate
- digester
- dissolving pulp
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- 229920000875 Dissolving pulp Polymers 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 57
- 239000003513 alkali Substances 0.000 claims abstract description 52
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011261 inert gas Substances 0.000 claims abstract description 46
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 40
- 229920005610 lignin Polymers 0.000 claims abstract description 37
- 239000003337 fertilizer Substances 0.000 claims abstract description 21
- 238000009835 boiling Methods 0.000 claims abstract description 19
- 229920002472 Starch Polymers 0.000 claims abstract description 12
- 239000008107 starch Substances 0.000 claims abstract description 12
- 235000019698 starch Nutrition 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 63
- 102000004139 alpha-Amylases Human genes 0.000 claims description 50
- 108090000637 alpha-Amylases Proteins 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 229940024171 alpha-amylase Drugs 0.000 claims description 47
- 238000004061 bleaching Methods 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 33
- 230000000694 effects Effects 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 108091005804 Peptidases Proteins 0.000 claims description 30
- 239000004365 Protease Substances 0.000 claims description 30
- 235000019419 proteases Nutrition 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 30
- 241000194108 Bacillus licheniformis Species 0.000 claims description 27
- 238000000926 separation method Methods 0.000 claims description 25
- 102000004190 Enzymes Human genes 0.000 claims description 20
- 108090000790 Enzymes Proteins 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229940088598 enzyme Drugs 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 235000015097 nutrients Nutrition 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 15
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 108010059378 Endopeptidases Proteins 0.000 claims description 10
- 102000005593 Endopeptidases Human genes 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 9
- 108010067770 Endopeptidase K Proteins 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 241000894006 Bacteria Species 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 230000009849 deactivation Effects 0.000 claims description 5
- 230000008030 elimination Effects 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 230000000937 inactivator Effects 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000028327 secretion Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 235000016709 nutrition Nutrition 0.000 claims description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims 6
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 11
- 239000000284 extract Substances 0.000 abstract description 10
- 230000007062 hydrolysis Effects 0.000 abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 9
- 230000032050 esterification Effects 0.000 abstract description 7
- 238000005886 esterification reaction Methods 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 102000004169 proteins and genes Human genes 0.000 abstract description 7
- 108090000623 proteins and genes Proteins 0.000 abstract description 7
- 230000018044 dehydration Effects 0.000 abstract description 5
- 238000006297 dehydration reaction Methods 0.000 abstract description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 4
- 230000008595 infiltration Effects 0.000 abstract description 4
- 238000001764 infiltration Methods 0.000 abstract description 4
- 210000004158 stalk cell Anatomy 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract 1
- 102000035195 Peptidases Human genes 0.000 description 24
- 229920002678 cellulose Polymers 0.000 description 21
- 239000001913 cellulose Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 14
- 239000000835 fiber Substances 0.000 description 12
- 239000012043 crude product Substances 0.000 description 9
- 239000010902 straw Substances 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 239000002956 ash Substances 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000004939 coking Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000035613 defoliation Effects 0.000 description 6
- 150000003384 small molecules Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004382 Amylase Substances 0.000 description 5
- 102000013142 Amylases Human genes 0.000 description 5
- 108010065511 Amylases Proteins 0.000 description 5
- 240000008042 Zea mays Species 0.000 description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- 235000019418 amylase Nutrition 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 241000209140 Triticum Species 0.000 description 4
- 235000021307 Triticum Nutrition 0.000 description 4
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 235000009973 maize Nutrition 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products 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-PICCSMPSSA-N 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 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 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010297 mechanical methods and process Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000008635 plant growth Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 102000004196 processed proteins & peptides Human genes 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 229920002955 Art silk Polymers 0.000 description 1
- 241001061264 Astragalus Species 0.000 description 1
- 235000010110 Astragalus glycyphyllos Nutrition 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 235000006533 astragalus Nutrition 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012549 training Methods 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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/22—Other features of pulping processes
- D21C3/26—Multistage processes
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/14—Hemicellulose; Derivatives thereof
-
- 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
-
- 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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
-
- 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
-
- 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
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microbiology (AREA)
- Paper (AREA)
Abstract
The invention discloses a kind of method for preparing dissolving pulp and other high value added products using crop material, belong to biological technical field.The present invention takes alkali lye preextraction hemicellulose and pre- extracting ash content inorganic salts；Zymyhydrolyzed protein matter and starch；Alkali soluble extracts lignin and remaining hemicellulose；Hydrogen peroxide removes remaining hemicellulose, lignin and dissolution lipoid material with organic solvent substep；Inert gas environment is kept to prevent the oxidation reaction of the components such as dissolving pulp, esterification of acetyl group etc. in digester；Relatively low boiling temperature is to avoid peeling reaction under the component high temperature such as dissolving pulp, dehydration, hydrolysis etc.；Inert gas provides elevated pressures and ensure that alkali lye the seven big technical measures such as effective infiltration stalk cell wall, has obtained very high-quality stalk dissolving pulp.The present invention farthest comprehensively utilizes to stalk, and dissolving pulp, hemicellulose, the recovery rate of lignin is high, integrality is good, quality is high, while can obtain liquid fertilizer.
Description
Technical field
It is more particularly to a kind of to prepare dissolving pulp using crop material and other high add the present invention relates to biological technical field
It is worth the method for product.
Background technology
Dissolving pulp is the refined cellulose slurry of high-purity, mainly for the production of high-end paper, viscose rayon（Artificial silk）Deng
Cellulose derivatives such as regenerated celulose fibre, nitrocellulose, acetate fiber, glassine paper, carboxymethyl cellulose etc..
At present, the raw material for preparing dissolving pulp is mainly cotton linter and timber.Because the price of cotton linter and supply are unstable
And the factor such as serious scarcity of China's Forest Resources, substitute timber using other cellulose resources and cotton linter prepares dissolving
Slurry, has been very urgent for China, and have obvious economic benefit, social benefit and environmental benefit.
China every year can more than 900,000,000 tons of harvesting crops stalk.The stalk include wheat, corn, rice, cotton, sorghum,
（It is sub-）Remaining stem after the herbage harvesting seed such as the crops such as crudefiber crop, soybean, peanut, potato class, melon and clover, prairie milk vetch, leaf,
Skin（Shell）, climing rattan（Seedling）Deng and sugarcane（Slag）, corncob, reed etc..According to surveying and determination, it is dry that the cellulose total amount that stalk contains accounts for it
The mass fraction of weight averagely reaches 30 ~ 49%, as the mass fraction of cellulose in straw reaches fiber in 39.12%, cotton stalk
The mass fraction that the mass fraction of element reaches cellulose in 43.74%, bagasse reaches 46%, etc..Stalk provides natural fibre
The abundant source of element is tieed up, thus is to prepare the potential excellent raw material of dissolving pulp.
In addition to cellulose, the stalk also hemicellulose containing 15 ~ 25% mass fractions and 12.5 ~ 28% mass fractions
Lignin.Therefore, the present invention can be carried preparing significantly outside dissolving pulp with coproduction hemicellulose, lignin and liquid fertilizer
The high utilization ratio of stalk；And production waste water is fully used, without any discharge.
Different from paper pulp, dissolving pulp is not required the form and intensity of fiber pulp, but to the degree of polymerization of fiber and
Chemical purity, particularly alpha-cellulose content and whiteness have higher requirement.Dissolving pulp rank is typically come with alpha-cellulose content
Division：Alpha-cellulose content is rudimentary dissolving pulp less than 90%, between 90% ~ 95% for intermediate dissolving pulp, and more than 95%
Be then advanced dissolving pulp.
Exactly see the abundant of crop material resource and its flood tide native cellulose contained, domestic and international different institutions
And technique, the method for professional person to preparing dissolving pulp using stalk cellulose etc. has carried out many researchs.
The A of Chinese patent CN 1143699 disclose a kind of method for preparing dissolved pulp of artificial wheat straw fibre.This method be by
Straw prehydrolysis under conditions of 0.8 ~ 1MPa of pressure, 175 DEG C of temperature, liquor ratio 1: 5, washing, concentration 30 ~ 35% after again boiling, wash
Choosing, bleaching etc., are made the staple fibre dissolving pulp containing alpha-cellulose 93 ~ 98%.Chinese patent CN101058953 A disclose one
The method that kind prepares bleached dissolving pulp using maize straw.Will be after the processing of maize straw soda-dip using once boiling, three times
The mode soda pulping process of heating, including material preparation, impregnate, feed intake, boiling, wash material, mashing, preceding selected, chlor-alkali, bleaching,
Finished product slurry etc. after acid treatment, washing, rear selected, papermaking.Two patents are simple slurrying, not by economic value added
The comprehensive utilizations such as higher hemicellulose, lignin are got up, thus fail efficiently to utilize stalk resource, and cause certain environment
Pollution.
The A of Chinese patent CN 102268833 disclose one kind and utilize agricultural crop straw steam blasting prehydrolytic sulfate process
The method for preparing dissolving pulp.Utilize half fine element of steam blasting and washing removing about 80% in advance, 10% lignin and 72%
Inorganic salts, and being separated high-quality long fibre and chopped fiber by machinery comb point, solve that crop branch fiber is short and small, heterogeneity
The prominent and high content of ashes problem of property.This method is distinguished by while preparing dissolving pulp and fully utilized in stalk
Lignin；But it is more the method for taking prehydrolysis removing rather than preextraction to utilize to hemicellulose, thus fails to fill
Divide using this precious resources of hemicellulose, and new pollution is brought to environment.In addition, prepared in the prior art using stalk
Dissolving pulp, has used acid medium or acid additive, and with lignin hydrolysis and peeling reaction can occur for dissolving pulp, it is impossible to protect
Demonstrate,prove the integrality and high quality of product.
The content of the invention
In order to make up the deficiencies in the prior art, dissolving pulp and other high is prepared using crop material the invention provides a kind of
The method of value-added product.
The technical scheme is that：
A kind of method for preparing dissolving pulp and other high value added products using crop material, including step：
1）Stalk through impurity elimination, dedusting, rub silk, segment, washing after insert digester；
2）The water of 1-20 times of stalk quality is added into digester, it is 1-10% to add alkali to alkali lye mass concentration；It is passed through steaming
60-100 DEG C is warming up in vapour to digester, inert gas is passed through into digester, by air emptying in digester；Then interval
Property is passed through steam and inert gas into digester, is 60-100 DEG C to maintain boiling kettle temperature, pressure 0.5-1MPa,
Heat-insulation pressure keeping 10-120 minutes；
3）Substance release in digester is come out, and is transferred in grinding mill and grinds；
4）Separation of solid and liquid, obtain filter residue one and filtrate one；
5）Filter residue one is inserted into digester, the water of 1-20 times of one mass of filter residue is added into digester and is passed through indifferent gas
Body, compound protease is added, interval 1-3 minutes, continues to be passed through inert gas, digests 10-80 minutes；Subsequent addition normal temperature type α-
Amylase, digest 10-80 minutes；Then pass to steam and be warming up to 60-70 DEG C, be incubated the activity of 2-20 minute inactivators；It is described
Compound protease is made up of the Proteinase K for possessing the alkali protease of endopeptidase activity and possessing peptide ending enzyme activity；The normal temperature
Type alpha-amylase alpha-amylase obtained by the variation bacillus licheniformis secretion of microwave induced gained, the normal temperature type alpha-amylase
Preference temperature is 22-35 DEG C；
6）After enzyme deactivation, it is 5-25% to add alkali to alkali lye mass concentration into digester, is passed through inert gas emptying digester
Interior air, it is passed through steam to boiling kettle temperature and rises to 80-120 DEG C, intermittence is passed through inert gas and steam, to maintain boiling
Kettle temperature is 80-120 DEG C, pressure 1-2MPa, heat-insulation pressure keeping 20-180 minutes；
7）Substance release in digester is come out, separation of solid and liquid, obtain filter residue two and filtrate two；
8）Filter residue two is inserted into bleaching tank, adds the water of 1-10 times of two mass of filter residue, adds hydrogen peroxide to the matter of hydrogen peroxide
Amount concentration is 0.1%-0.5%, is passed through air in inert gas emptying bleaching tank, is warming up to 50-80 DEG C, interval 1-3 minutes, continues
Inert gas 1-2 minutes are passed through, are incubated 10-120 minutes；
9）Continue to add hydrogen peroxide into bleaching tank, the mass concentration to hydrogen peroxide is 2%-5%, bleaching；
10）Substance release in bleaching tank is come out, separation of solid and liquid, and the filter residue obtained by the alkali liquid washing of gradient concentration,
Obtain filter residue three and filtrate three；
11）Filter residue three is placed in into progress alcohol in alcohol cleaning of evaporator to wash, finally with pure water, obtains filter residue four；
12）Filter residue four produces dissolving pulp finished product through drying, crushing；Wherein drying temperature is less than 120 DEG C；
13）The ethanol of 1-10 times of one volume of filtrate is added into the filtrate one, stable 1-3 hours, separate after stirring
Filter residue five and filtrate five；
14）Filter residue five is dissolved using sig water, then adds ethanol, and stable complete to Precipitation after stirring, separation is heavy
Shallow lake and clear liquid；
15）Step 14）Gained precipitates repeat step 14）Operation several times, be finally recovered to obtain filter residue six and filtrate six；
16）Filter residue the six channels drying and crushing obtains hemicellulose finished product；
17）The pH of diluted acid regulation filtrate two is used to separate out solid for 4-6, separation of solid and liquid, obtain filter residue seven and filtrate seven；Filter
Slag seven obtains lignin finished product through drying and crushing；
18）Filtrate three, filtrate four, filtrate seven mix, behind adjusted pH=6.5, as liquid fertilizer.
Preferably, step 5）In, the obtaining step of the microwave induced gained variation bacillus licheniformis is specific
For：The nutrient solution of bacillus licheniformis is placed in microwave generator, setting microwave power is 850-950W, and pulse frequency is
2300MHz, microwave treatment 20s, 20s is cooled down, it is reciprocal 25-35 times according to this；Nutrient solution after microwave treatment is coated on solid training
Support on base, cultivate 1-2 days under the conditions of 30 DEG C, by the high ground of alpha-amylase activity under four plants of normal temperature of screening in the bacterium colony that survives
The dissociant of clothing bacillus.
Further, the dissociant for selecting alpha-amylase activity highest bacillus licheniformis under normal temperature expands culture,
So as to obtain the normal temperature type alpha-amylase.The normal temperature type alpha-amylase obtained using this method, at normal temperatures can efficient enzyme
Starch is solved, energy consumption is both reduced, turn avoid the generation of side reaction.
Preferably, possess the alkali protease of endopeptidase activity in the compound protease and possess peptide ending enzyme work
Property Proteinase K ratio be 1:1-3；The addition of the compound protease meets every kilogram of butt stalk 400-800U, institute
The addition for stating normal temperature type alpha-amylase meets every kilogram of butt stalk 300-700U.
Preferably, step 10）In, the alkali lye of the gradient concentration is respectively 10%, 6%, 3% including mass concentration
And 1% alkali lye.
Preferably, step 18）After alkali lye adjusts pH=6.5, liquid fertilizer is used as after adjusted nutritional ingredient.
Preferably, the alkali is sodium hydroxide, potassium hydroxide, ammoniacal liquor or calcium hydroxide.
Preferably, the inert gas is nitrogen, helium or argon gas.Preferably nitrogen, nitrogen cost are low.
Beneficial effects of the present invention are：
The present invention farthest comprehensively utilizes to stalk, dissolving pulp, hemicellulose, the recovery rate of lignin be high,
Integrality is good, quality is high.Although the present invention also utilizes steam explosion isolation technics of the prior art, adopted in present invention process
With low temperature, condition of high voltage, and apply special biology enzyme, ensure that the present invention to the high efficiency of straw utilization, high quality,
High yield.
The present invention is separated by multi-layer, utilized at many levels, the protection of more components, has obtained very high-quality stalk dissolving
Slurry, and present invention, avoiding the use of acid medium or acid additive, so as to avoid dissolving pulp, hemicellulose, lignin
Hydrolysis, peeling reaction Deng product etc., further ensure the integrality and high quality of manufactured goods.
The present invention has not only widened the material range of dissolving pulp, and high-quality, abundant replacement is have found for the preparation of dissolving pulp
Raw material, and the stalk resource of agriculture field is taken full advantage of, avoid crop straw burning and seriously polluted to caused by environment, very
The high added value comprehensive utilization of stalk resource is just being realized, the added value of agricultural economy is being significantly improved, greatly advances agricultural
Industrialized production.
Embodiment
Embodiment 1
A kind of method for preparing dissolving pulp and other high value added products using crop material, including step：
1st, the preparation of dissolving pulp
1）Wheat stalk defoliation and fringe, stalk after defoliation and fringe through impurity elimination, dedusting, rub silk, segment（2-3cm）, washing
After insert digester；
2）The water of 10 times of stalk quality is added into digester, adds ammoniacal liquor, is 7% to alkali lye mass concentration；It is passed through steam
95 DEG C are warming up in digester, inert nitrogen gas is passed through into digester, by air emptying in digester；Then it is intermittent
Steam and inert gas are passed through into digester, to maintain boiling kettle temperature is 95 DEG C, pressure 0.8MPa, heat-insulation pressure keeping
60 minutes；
Most of hemicellulose can be extracted in the step and extracts the inorganic salts such as the major part in ash content is siliceous；Compared with
Under low boiling temperature, elevated pressures and inert gas environment, the decomposition reaction of the component such as hemicellulose, cellulose, lignin,
Oxidation reaction, dehydration（Coking）Reaction, peeling reaction, esterification etc. weaken significantly, it is ensured that the integrality of molecular radical, height
Yield and high quality；After testing, this step can extract 85% hemicellulose, extract 81% ash content inorganic salts.
3）Substance release in digester is come out, and is transferred in mill and grinds 15 minutes；Herein using Mechanical Method after
It is continuous to crack intermolecular part chemical bond.
4）Separation of solid and liquid, obtain filter residue one and filtrate one；The as slurry containing cellulose and lignin of filter residue one, filtrate one
For most of hemicellulose of extraction, inorganic salts etc. such as major part is siliceous of extracting.
5）Filter residue one is inserted into digester, the water of 10 times of one mass of filter residue is added into digester and is passed through inert gas,
Add compound protease（500U/ kilograms of butt stalk）, interval 1 minute, continue to be passed through inert gas, digest 40 minutes；Then
Add normal temperature type alpha-amylase（400U/ kilograms of butt stalk）, digest 30 minutes；Then pass to steam and be warming up to 65 DEG C, insulation
The activity of 12 minutes inactivators；Compound protease is by possessing the alkali protease of endopeptidase activity and possessing the egg of peptide ending enzyme activity
White enzyme K compositions；Possess the alkali protease of endopeptidase activity in compound protease and possess the ratio of the Proteinase K of peptide ending enzyme activity
Example is 1:1；Normal temperature type alpha-amylase alpha-amylase obtained by the variation bacillus licheniformis secretion of microwave induced gained, normal temperature type α-
The preference temperature of amylase is 22-35 DEG C；
The obtaining step of microwave induced gained variation bacillus licheniformis is specially：The nutrient solution of bacillus licheniformis is put
In microwave generator, setting microwave power is 900W, pulse frequency 2300MHz, microwave treatment 20s, cools down 20s, past according to this
It is multiple 30 times；Nutrient solution after microwave treatment is coated on solid medium, cultivated 2 days under the conditions of 30 DEG C, by what is survived
The dissociant of the bacillus licheniformis that alpha-amylase activity is high under four plants of normal temperature is screened in bacterium colony.Select alpha-amylase under normal temperature
The dissociant of active highest bacillus licheniformis（Numbering is B5184）Expand culture, so as to obtain normal temperature type alpha-amylase.
In the step, compound protease can effectively hydrolyzing protein at normal temperatures；And normal temperature type alpha-amylase is in 22-35
DEG C efficient hydrolysis starch, it is not necessary to as the thermal-stable α-amylase used in the prior art（Thermal-stable α-amylase needs 80-90
DEG C hot conditions；High temperature resistant type alpha-amylase of the amylase of industrial production from bacillus licheniformis at present, optimum temperature
For 80-90 DEG C, not only energy consumption is big, and side reaction is more）, energy consumption is not only reduced, while reduce the destruction to other materials；
Normal temperature type alpha-amylase used in the present invention, 22-35 DEG C of preference temperature, appropriate pH 6-8, vigor is reduced to zero when temperature reaches 60 DEG C；
Its enzymatic activity is 1.5 times of thermal-stable α-amylase.The other step can with it is soft by protein, Starch Hydrolysis into small molecule
Peptides, amino acid, maltose, glucose etc. enter in filtrate, so as to success deproteination matter and starch.
6）After enzyme deactivation, it is 16% that ammoniacal liquor to alkali lye mass concentration is added into digester, is passed through inert gas emptying digester
Interior air, it is passed through steam to boiling kettle temperature and rises to 110 DEG C, intermittence is passed through inert gas and steam, to maintain digester
Interior temperature is 110 DEG C, pressure 1.5MPa, heat-insulation pressure keeping 100 minutes；
In the step, relatively low boiling temperature is used to avoid the decomposition reaction of each component, dehydration（Coking）Reaction, peeling are anti-
It should wait, using elevated pressures（Realized by being passed through inert gas）It ensure that alkali lye to effective infiltration between stalk cell wall, is adopted
Use inert environments（It is passed through inert gas realization）Avoid oxidation reaction, the esterification of acetyl group of each component molecular radical
Deng so as to ensure that the integrality of each material, high yield pulp1 and high quality.
7）Substance release in digester is come out, separation of solid and liquid, obtain filter residue two and filtrate two；Filter residue two is with cellulose
For the dissolving pulp crude product of main component, filtrate two contains lignin.
8）Filter residue two is inserted into bleaching tank, adds the water of 5 times of two mass of filter residue, the quality for adding hydrogen peroxide to hydrogen peroxide is dense
Spend for 0.3%, be passed through air in inert gas emptying bleaching tank, be warming up to 60 DEG C, interval 1 minute, continue to be passed through inert gas 1
Minute, it is incubated 60 minutes；
The purpose of the step is to dissolve the hemicellulose for remaining in dissolving pulp crude product surface under the conditions of weak base with hydrogen peroxide
And lignin, to obtain purer dissolving pulp；Although the step is carried out in bleaching tank, its purpose is not bleaching.
9）Continue to add hydrogen peroxide into bleaching tank, the mass concentration to hydrogen peroxide is 3%, bleaching；
10）Substance release in bleaching tank is come out, separation of solid and liquid, and the filter residue obtained by the alkali liquid washing of gradient concentration,
Obtain filter residue three and filtrate three；With the alkali liquid washing of gradient concentration, to remove the lignin, the hemicellulose that are attached to dissolving pulp surface
Deng.Prepare sig water（NH4OH）To mass fraction（Alkali concn）Echelon is 10%, 6%, 3% and 1%.
11）Filter residue three is placed in alcohol cleaning of evaporator, carrying out alcohol using 95% ethanol for being five times in the mass of filter residue three washes 2 times, most
Pure water is used afterwards one time, obtain filter residue four；Ethanol is recycled, and the lignin on dissolving pulp surface is this time remained in ethanol removing
And dissolution lipoid material.
12）Filter residue four produces dissolving pulp finished product through heated-air drying, slight crushing；Wherein drying temperature is less than 120 DEG C, with
Ensure to dissolve the degree of polymerization of pulp fibres and the stability of cellulosic molecule；After testing, the dissolving pulp alpha fibre of gained wheat stalk
Cellulose content is 97.1%, whiteness 85%.
2nd, the preparation of hemicellulose
13）95% ethanol of filtrate one 4 times of volumes times is added into filtrate one, stirring is stablized 1.5 hours after 15 minutes,
Separate to obtain filter residue five and filtrate five；It is mainly hemicellulose crude product in filter residue five, is mainly second alcohol and water in filtrate five；
14）Filter residue five is dissolved using sig water, then adds 95% ethanol of 4 times of alkali lye volumes, stable to heavy after stirring
Precipitation goes out completely, precipitation and separation and clear liquid；
15）Step 14）Gained precipitates repeat step 14）Operation several times, be finally recovered to obtain filter residue six and filtrate six；
16）Filter residue the six channels heated-air drying, crush to obtain hemicellulose finished product；The equal recycling of ethanol used above.
3rd, the preparation of lignin
17）The pH of acetic acid,diluted regulation filtrate two is used to separate out solid for 4.5, separation of solid and liquid, obtain filter residue seven and filtrate seven；
Filter residue seven obtains lignin finished product through drying and crushing.
4th, the preparation of liquid fertilizer
18）Filtrate three merges with filtrate three or four, filtrate seven, behind adjusted pH=6.5, as liquid fertilizer.
Because above process uses ammoniacal liquor, acetic acid etc., therefore can be used for preparing liquid fertilizer, merging filtrate three, filtrate
Four（Certainly remaining liquid after ethanol reclaims can also be merged）, adjust pH to 6.5 or so, barrelling, as plant nutrient liquid
State fertilizer.Containing required for the plant growths such as a certain amount of N, P, K, mineral matter and small molecule organic material in gained liquid fertilizer
Nutrient.
Embodiment 2
A kind of method for preparing dissolving pulp and other high value added products using crop material, including step：
1st, the preparation of dissolving pulp
1）Maize straw defoliation and fringe, stalk after defoliation and fringe through impurity elimination, dedusting, rub silk, segment（4-5cm）, washing
After insert digester；
2）The water of 13 times of stalk quality is added into digester, adds potassium hydroxide, is 5% to alkali lye mass concentration；It is passed through
85 DEG C are warming up in steam to digester, inert nitrogen gas is passed through into digester, by air emptying in digester；Then between
Having a rest property is passed through steam and inert gas into digester, is 85 DEG C to maintain boiling kettle temperature, pressure 0.6MPa, insulation
Pressurize 80 minutes；
Most of hemicellulose can be extracted in the step and extracts the inorganic salts such as the major part in ash content is siliceous；
Under lower temperature, elevated pressures and inert environments, decomposition reaction, the oxidation of the component such as hemicellulose, cellulose, lignin are anti-
Should, it be dehydrated（Coking）Reaction, peeling reaction, esterification etc. weaken significantly, it is ensured that the integrality of molecular radical, high yield pulp1 with
And high quality；After testing, this step can extract 87% hemicellulose, extract 82% ash content inorganic salts.
3）Substance release in digester is come out, and is transferred in colloid mill and grinds 20 minutes；Mechanical Method is used herein
Continue to crack intermolecular part chemical bond.
4）Separation of solid and liquid, obtain filter residue one and filtrate one；The as slurry containing cellulose and lignin of filter residue one, filtrate one
For most of hemicellulose of extraction, inorganic salts etc. such as major part is siliceous of extracting.
5）Filter residue one is inserted into digester, the water of 13 times of one mass of filter residue is added into digester and is passed through inert gas,
Add compound protease（600U/ kilograms of butt stalk）, interval 2 minutes, continue to be passed through inert gas, digest 50 minutes；Then
Add normal temperature type alpha-amylase（500U/ kilograms of butt stalk）, digest 45 minutes；Then pass to steam and be warming up to 70 DEG C, insulation
The activity of 10 minutes inactivators；Compound protease is by possessing the alkali protease of endopeptidase activity and possessing the egg of peptide ending enzyme activity
White enzyme K compositions；Possess the alkali protease of endopeptidase activity in compound protease and possess the ratio of the Proteinase K of peptide ending enzyme activity
Example is 1:2；Normal temperature type alpha-amylase alpha-amylase obtained by the variation bacillus licheniformis secretion of microwave induced gained, normal temperature type α-
The preference temperature of amylase is 22-35 DEG C；
The obtaining step of microwave induced gained variation bacillus licheniformis is specially：The nutrient solution of bacillus licheniformis is put
In microwave generator, setting microwave power is 900W, pulse frequency 2300MHz, microwave treatment 20s, cools down 20s, past according to this
It is multiple 30 times；Nutrient solution after microwave treatment is coated on solid medium, cultivated 2 days under the conditions of 30 DEG C, by what is survived
The dissociant of the bacillus licheniformis that alpha-amylase activity is high under four plants of normal temperature is screened in bacterium colony.Select alpha-amylase under normal temperature
The dissociant of active highest bacillus licheniformis（Numbering is B5184）Expand culture, so as to obtain normal temperature type alpha-amylase.
In the step, compound protease can effectively hydrolyzing protein at normal temperatures；And normal temperature type alpha-amylase is in 22-35
DEG C efficient hydrolysis starch, it is not necessary to as the thermal-stable α-amylase used in the prior art（Thermal-stable α-amylase needs 80-90
DEG C hot conditions；High temperature resistant type alpha-amylase of the amylase of industrial production from bacillus licheniformis at present, optimum temperature
For 80-90 DEG C, not only energy consumption is big, and side reaction is more）, energy consumption is not only reduced, while reduce the destruction to other materials；
Normal temperature type alpha-amylase used in the present invention, 22-35 DEG C of preference temperature, appropriate pH 6-8, vigor is reduced to zero when temperature reaches 60 DEG C；
Its enzymatic activity is 1.5 times of thermal-stable α-amylase.The other step can with it is soft by protein, Starch Hydrolysis into small molecule
Peptides, amino acid, maltose, glucose etc. enter in filtrate, so as to success deproteination matter and starch.
6）After enzyme deactivation, it is 15% that potassium hydroxide to alkali lye mass concentration is added into digester, is passed through inert gas emptying steaming
Air in saucepan, it is passed through steam to boiling kettle temperature and rises to 105 DEG C, intermittence is passed through inert gas and steam, to maintain to steam
Boil kettle temperature be 105 DEG C, pressure 1.2MPa, heat-insulation pressure keeping 110 minutes；
In the step, relatively low boiling temperature is used to avoid the decomposition reaction of each component, dehydration（Coking）Reaction, peeling are anti-
It should wait, using elevated pressures（Realized by being passed through inert gas）It ensure that alkali lye to effective infiltration between stalk cell wall, is adopted
Use inert environments（It is passed through inert gas realization）Avoid oxidation reaction, the esterification of acetyl group of each component molecular radical
Deng so as to ensure that the integrality of each material, high yield pulp1 and high quality.
7）Substance release in digester is come out, separation of solid and liquid, obtain filter residue two and filtrate two；Filter residue two is with cellulose
For the dissolving pulp crude product of main component, filtrate two contains lignin.
8）Filter residue two is inserted into bleaching tank, adds the water of 7 times of two mass of filter residue, the quality for adding hydrogen peroxide to hydrogen peroxide is dense
Spend for 0.5%, be passed through air in inert gas emptying bleaching tank, be warming up to 70 DEG C, interval 2 minutes, continue to be passed through inert gas 2
Minute, it is incubated 80 minutes；
The purpose of the step is to dissolve the hemicellulose for remaining in dissolving pulp crude product surface under the conditions of weak base with hydrogen peroxide
And lignin, to obtain purer dissolving pulp；Although the step is carried out in bleaching tank, its purpose is not bleaching.
9）Continue to add hydrogen peroxide into bleaching tank, the mass concentration to hydrogen peroxide is 4%, bleaching；
10）Substance release in bleaching tank is come out, separation of solid and liquid, and the filter residue obtained by the alkali liquid washing of gradient concentration,
Obtain filter residue three and filtrate three；With the alkali liquid washing of gradient concentration, to remove the lignin, the hemicellulose that are attached to dissolving pulp surface
Deng.Prepare sig water（KOH）To mass fraction（Alkali concn）Echelon is 10%, 6%, 3% and 1%.
11）Filter residue three is placed in alcohol cleaning of evaporator, carrying out alcohol using 95% ethanol of six times of mass of filter residue three washes 2 times, most
Pure water is used afterwards one time, obtain filter residue four；Ethanol is recycled, and the lignin on dissolving pulp surface is this time remained in ethanol removing
And dissolution lipoid material.
12）Filter residue four produces dissolving pulp finished product through drying fluidized-bed drying, slight crushing；Wherein drying temperature is less than 120
DEG C, to ensure to dissolve the degree of polymerization of pulp fibres and the stability of cellulosic molecule；After testing, the dissolving pulp α of gained maize straw-
Content of cellulose is 97.4%, whiteness 86%.
2nd, the preparation of hemicellulose
13）95% ethanol of filtrate one 6 times of volumes times is added into filtrate one, stirring is stablized 1.5 hours after 15 minutes,
Separate to obtain filter residue five and filtrate five；It is mainly hemicellulose crude product in filter residue five, is mainly second alcohol and water in filtrate five；
14）Filter residue five is dissolved using sig water, then adds 95% ethanol of 6 times of alkali lye volumes, stable to heavy after stirring
Precipitation goes out completely, precipitation and separation and clear liquid；
15）Step 14）Gained precipitates repeat step 14）Operation several times, be finally recovered to obtain filter residue six and filtrate six；
16）Filter residue the six channels heated-air drying, crush to obtain hemicellulose finished product；The equal recycling of ethanol used above.
3rd, the preparation of lignin
17）The pH of dilute dust technology regulation filtrate two is used to separate out solid for 5, separation of solid and liquid, obtain filter residue seven and filtrate seven；
Filter residue seven obtains lignin finished product through drying and crushing.
4th, the preparation of liquid fertilizer
18）Filtrate three, filtrate four, filtrate seven merge, behind adjusted pH=6.5, as liquid fertilizer.
Because above process uses potassium hydroxide, nitric acid etc., therefore it can be used for preparing liquid fertilizer, merging filtrate three,
Filtrate four（Certainly remaining liquid after ethanol reclaims can also be merged）, adjust pH to 6.5 or so, barrelling, as plant nutrient
Use liquid fertilizer.Containing needed for the plant growths such as a certain amount of N, P, K, mineral matter and small molecule organic material in gained liquid fertilizer
The nutrient wanted.
Embodiment 3
A kind of method for preparing dissolving pulp and other high value added products using crop material, including step：
1st, the preparation of dissolving pulp
1）Cotton stalk defoliation, cot, cotton stalk after defoliation and cot through impurity elimination, dedusting, rub silk, segment（3-4cm）, water
Digester is inserted after washing；
2）The water of 12 times of stalk quality is added into digester, adds ammoniacal liquor, is 6% to alkali lye mass concentration；It is passed through steam
90 DEG C are warming up in digester, inert nitrogen gas is passed through into digester, by air emptying in digester；Then it is intermittent
Steam and inert gas are passed through into digester, to maintain boiling kettle temperature is 90 DEG C, pressure 0.7MPa, heat-insulation pressure keeping
70 minutes；
Most of hemicellulose can be extracted in the step and extracts the inorganic salts such as the major part in ash content is siliceous；
Under lower temperature, elevated pressures and inert environments, decomposition reaction, the oxidation of the component such as hemicellulose, cellulose, lignin are anti-
Should, it be dehydrated（Coking）Reaction, peeling reaction, esterification etc. weaken significantly, it is ensured that the integrality of molecular radical, high yield pulp1 with
And high quality；After testing, this step can extract 86% hemicellulose, extract 84% ash content inorganic salts.
3）Substance release in digester is come out, and ground 15 minutes in dense mill in being transferred to；Mechanical Method is used herein
Continue to crack intermolecular part chemical bond.
4）Separation of solid and liquid, obtain filter residue one and filtrate one；The as slurry containing cellulose and lignin of filter residue one, filtrate one
For most of hemicellulose of extraction, inorganic salts etc. such as major part is siliceous of extracting.
5）Filter residue one is inserted into digester, the water of 12 times of one mass of filter residue is added into digester and is passed through inert gas,
Add compound protease（550U/ kilograms of butt stalk）, interval 1.5 minutes, continue to be passed through inert gas, digest 45 minutes；With
Normal temperature type alpha-amylase is added afterwards（450U/ kilograms of butt stalk）, digest 45 minutes；Then pass to steam and be warming up to 70 DEG C, protect
The activity of warm 11 minutes inactivators；Compound protease is by possessing the alkali protease of endopeptidase activity and possessing peptide ending enzyme activity
Proteinase K forms；Possess the alkali protease of endopeptidase activity in compound protease and possess the Proteinase K of peptide ending enzyme activity
Ratio is 1:1.5；Normal temperature type alpha-amylase is by microwave induced gained variation bacillus licheniformis secretion gained alpha-amylase, normal temperature
The preference temperature of type alpha-amylase is 22-35 DEG C；
The obtaining step of microwave induced gained variation bacillus licheniformis is specially：The nutrient solution of bacillus licheniformis is put
In microwave generator, setting microwave power is 900W, pulse frequency 2300MHz, microwave treatment 20s, cools down 20s, past according to this
It is multiple 30 times；Nutrient solution after microwave treatment is coated on solid medium, cultivated 2 days under the conditions of 30 DEG C, by what is survived
The dissociant of the bacillus licheniformis that alpha-amylase activity is high under four plants of normal temperature is screened in bacterium colony.Select alpha-amylase under normal temperature
The dissociant of active highest bacillus licheniformis（Numbering is B5184）Expand culture, so as to obtain normal temperature type alpha-amylase.
In the step, compound protease can effectively hydrolyzing protein at normal temperatures；And normal temperature type alpha-amylase is in 22-35
DEG C efficient hydrolysis starch, it is not necessary to as the thermal-stable α-amylase used in the prior art（Thermal-stable α-amylase needs 80-90
DEG C hot conditions；High temperature resistant type alpha-amylase of the amylase of industrial production from bacillus licheniformis at present, optimum temperature
For 80-90 DEG C, not only energy consumption is big, and side reaction is more）, energy consumption is not only reduced, while reduce the destruction to other materials；
Normal temperature type alpha-amylase used in the present invention, 22-35 DEG C of preference temperature, appropriate pH 6-8, vigor is reduced to zero when temperature reaches 60 DEG C；
Its enzymatic activity is 1.5 times of thermal-stable α-amylase.The other step can with it is soft by protein, Starch Hydrolysis into small molecule
Peptides, amino acid, maltose, glucose etc. enter in filtrate, so as to success deproteination matter and starch.
6）After enzyme deactivation, it is 17% that ammoniacal liquor to alkali lye mass concentration is added into digester, is passed through inert gas emptying digester
Interior air, it is passed through steam to boiling kettle temperature and rises to 115 DEG C, intermittence is passed through inert gas and steam, to maintain digester
Interior temperature is 115 DEG C, pressure 1.6MPa, heat-insulation pressure keeping 90 minutes；
In the step, relatively low boiling temperature is used to avoid the decomposition reaction of each component, dehydration（Coking）Reaction, peeling are anti-
It should wait, using elevated pressures（Realized by being passed through inert gas）It ensure that alkali lye to effective infiltration between stalk cell wall, is adopted
Use inert environments（It is passed through inert gas realization）Avoid oxidation reaction, the esterification of acetyl group of each component molecular radical
Deng so as to ensure that the integrality of each material, high yield pulp1 and high quality.
7）Substance release in digester is come out, separation of solid and liquid, obtain filter residue two and filtrate two；Filter residue two is with cellulose
For the dissolving pulp crude product of main component, filtrate two contains lignin.
8）Filter residue two is inserted into bleaching tank, adds the water of 6 times of two mass of filter residue, the quality for adding hydrogen peroxide to hydrogen peroxide is dense
Spend for 0.45%, be passed through air in inert gas emptying bleaching tank, be warming up to 65 DEG C, interval 1.5 minutes, continue to be passed through indifferent gas
Body 1.5 minutes, it is incubated 70 minutes；
The purpose of the step is to dissolve the hemicellulose for remaining in dissolving pulp crude product surface under the conditions of weak base with hydrogen peroxide
And lignin, to obtain purer dissolving pulp；Although the step is carried out in bleaching tank, its purpose is not bleaching.
9）Continue to add hydrogen peroxide into bleaching tank, the mass concentration to hydrogen peroxide is 3.5%, bleaching；
10）Substance release in bleaching tank is come out, separation of solid and liquid, and the filter residue obtained by the alkali liquid washing of gradient concentration,
Obtain filter residue three and filtrate three；With the alkali liquid washing of gradient concentration, to remove the lignin, the hemicellulose that are attached to dissolving pulp surface
Deng.Weak aqua ammonia is prepared to mass fraction（Alkali concn）Echelon is 10%, 6%, 3% and 1%.
11）Filter residue three is placed in alcohol cleaning of evaporator, carrying out alcohol using 95% ethanol for being four times in the mass of filter residue three washes 2 times, most
Pure water is used afterwards one time, obtain filter residue four；Ethanol is recycled, and the lignin on dissolving pulp surface is this time remained in ethanol removing
And dissolution lipoid material.
12）Filter residue four slight crushing, produces dissolving pulp finished product through heated-air drying；Wherein drying temperature is less than 120 DEG C, with
Ensure to dissolve the degree of polymerization of pulp fibres and the stability of cellulosic molecule；After testing, the dissolving pulp alpha fibre of gained cotton stalk
Cellulose content is 97.7%, whiteness 86.5%.
2nd, the preparation of hemicellulose
13）95% ethanol of filtrate one 5 times of volumes times is added into filtrate one, stirring is stablized 1.5 hours after 15 minutes,
Separate to obtain filter residue five and filtrate five；It is mainly hemicellulose crude product in filter residue five, is mainly second alcohol and water in filtrate five；
14）Filter residue five is dissolved using sig water, then adds 95% ethanol of 5 times of alkali lye volumes, stable to heavy after stirring
Precipitation goes out completely, precipitation and separation and clear liquid；
15）Step 14）Gained precipitates repeat step 14）Operation several times, be finally recovered to obtain filter residue six and filtrate six；
16）Filter residue the six channels heated-air drying, crush to obtain hemicellulose finished product；The equal recycling of ethanol used above.
3rd, the preparation of lignin
17）The pH of dust technology regulation filtrate two is used to separate out solid for 4.8, separation of solid and liquid, obtain filter residue seven and filtrate seven；
Filter residue seven obtains lignin finished product through drying and crushing.
4th, the preparation of liquid fertilizer
18）Filtrate three, filtrate four, filtrate seven merge, behind adjusted pH=6.5, as liquid fertilizer.
Because above process uses ammoniacal liquor, nitric acid etc., therefore can be used for preparing liquid fertilizer, merging filtrate three, filtrate
Four（Certainly remaining liquid after ethanol reclaims can also be merged）, adjust pH to 6.5 or so, barrelling, as plant nutrient liquid
State fertilizer.Containing required for the plant growths such as a certain amount of N, P, K, mineral matter and small molecule organic material in gained liquid fertilizer
Nutrient.
The part of present invention process device therefor contacting material is stainless steel.
Claims (8)
- A kind of 1. method for preparing dissolving pulp and other high value added products using crop material, it is characterised in that including step：1）Stalk through impurity elimination, dedusting, rub silk, segment, washing after insert digester；2）The water of 1-20 times of stalk quality is added into digester, it is 1-10% to add alkali to alkali lye mass concentration；It is passed through steam extremely 60-100 DEG C is warming up in digester, inert gas is passed through into digester, by air emptying in digester；Then it is intermittent to Steam and inert gas are passed through in digester, to maintain boiling kettle temperature is 60-100 DEG C, pressure 0.5-1MPa, insulation Pressurize 10-120 minutes；3）Substance release in digester is come out, and is transferred in grinding mill and grinds；4）Separation of solid and liquid, obtain filter residue one and filtrate one；5）Filter residue one is inserted into digester, the water of 1-20 times of one mass of filter residue is added into digester and is passed through inert gas, is added Enter compound protease, interval 1-3 minutes, continue to be passed through inert gas, digest 10-80 minutes；Then add normal temperature type alphalise starch Enzyme, digest 10-80 minutes；Then pass to steam and be warming up to 60-70 DEG C, be incubated the activity of 2-20 minute inactivators；It is described compound Protease is made up of the Proteinase K for possessing the alkali protease of endopeptidase activity and possessing peptide ending enzyme activity；The normal temperature type α- Amylase by microwave induced gained variation bacillus licheniformis secretion gained alpha-amylase, the normal temperature type alpha-amylase it is suitable Temperature is 22-35 DEG C；6）After enzyme deactivation, it is 5-25% to add alkali to alkali lye mass concentration into digester, is passed through in inert gas emptying digester empty Gas, it is passed through steam to boiling kettle temperature and rises to 80-120 DEG C, intermittence is passed through inert gas and steam, to maintain in digester Temperature is 80-120 DEG C, pressure 1-2MPa, heat-insulation pressure keeping 20-180 minutes；7）Substance release in digester is come out, separation of solid and liquid, obtain filter residue two and filtrate two；8）Filter residue two is inserted into bleaching tank, adds the water of 1-10 times of two mass of filter residue, the quality for adding hydrogen peroxide to hydrogen peroxide is dense Spend for 0.1%-0.5%, be passed through air in inert gas emptying bleaching tank, be warming up to 50-80 DEG C, interval 1-3 minutes, continue to be passed through Inert gas 1-2 minutes, it is incubated 10-120 minutes；9）Continue to add hydrogen peroxide into bleaching tank, the mass concentration to hydrogen peroxide is 2%-5%, bleaching；10）Substance release in bleaching tank is come out, separation of solid and liquid, and the filter residue obtained by the alkali liquid washing of gradient concentration, it must filter Slag three and filtrate three；11）Filter residue three is placed in into progress alcohol in alcohol cleaning of evaporator to wash, finally with pure water, obtains filter residue four；12）Filter residue four produces dissolving pulp finished product through drying, crushing；Wherein drying temperature is less than 120 DEG C；13）The ethanol of 1-10 times of one volume of filtrate is added into the filtrate one, stable 1-3 hours, separate to obtain filter residue after stirring Five and filtrate five；14）Filter residue five is dissolved using sig water, then adds ethanol, stable complete to Precipitation after stirring, precipitation and separation with Clear liquid；15）Step 14）Gained precipitates repeat step 14）Operation several times, be finally recovered to obtain filter residue six and filtrate six；16）Filter residue the six channels drying and crushing obtains hemicellulose finished product；17）The pH of diluted acid regulation filtrate two is used to separate out solid for 4-6, separation of solid and liquid, obtain filter residue seven and filtrate seven；Filter residue seven Lignin finished product is obtained through drying and crushing；18）Filtrate three, filtrate four, filtrate seven mix, after adjusting pH=6.5, as liquid fertilizer.
- 2. the method for preparing dissolving pulp and other high value added products using crop material as claimed in claim 1, its feature exist In step 5）In, the obtaining step of the microwave induced gained variation bacillus licheniformis is specially：By bacillus licheniformis Nutrient solution is placed in microwave generator, and setting microwave power is 850-950W, pulse frequency 2300MHz, microwave treatment 20s, cold But 20s, it is reciprocal 25-35 times according to this；Nutrient solution after microwave treatment is coated on solid medium, 1- is cultivated under the conditions of 30 DEG C 2 days, by the dissociant that the bacillus licheniformis that alpha-amylase activity is high under four plants of normal temperature is screened in the bacterium colony that survives.
- 3. the method for preparing dissolving pulp and other high value added products using crop material as claimed in claim 2, its feature exist In：The dissociant for selecting alpha-amylase activity highest bacillus licheniformis under normal temperature expands culture, described normal so as to obtain Warm type alpha-amylase.
- 4. the method for preparing dissolving pulp and other high value added products using crop material as claimed in claim 1 or 2, its feature It is：Possess the alkali protease of endopeptidase activity in the compound protease and possess the ratio of the Proteinase K of peptide ending enzyme activity Example is 1:1-3；The addition of the compound protease meets every kilogram of butt stalk 400-800U, the normal temperature type alpha-amylase Addition meet every kilogram of butt stalk 300-700U.
- 5. the method for preparing dissolving pulp and other high value added products using crop material as claimed in claim 1, its feature exist In：Step 10）In, the alkali lye of the gradient concentration includes the alkali lye that mass concentration is respectively 10%, 6%, 3% and 1%.
- 6. the method for preparing dissolving pulp and other high value added products using crop material as claimed in claim 1, its feature exist In：Step 18）After adjusting pH=6.5, liquid fertilizer is used as after adjusted nutritional ingredient.
- 7. the method for preparing dissolving pulp and other high value added products using crop material as claimed in claim 1, its feature exist In：The alkali is sodium hydroxide, potassium hydroxide, ammoniacal liquor or calcium hydroxide.
- 8. the method for preparing dissolving pulp and other high value added products using crop material as claimed in claim 1, its feature exist In：The inert gas is nitrogen, helium or argon gas.
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| CN111556967B (en) * | 2017-12-20 | 2023-04-04 | 尤妮佳股份有限公司 | Method for producing recycled pulp fibers |
| CN111472186B (en) * | 2019-01-24 | 2021-11-26 | 中国科学院过程工程研究所 | Method for preparing high-quality crop straw dissolving pulp through hydrothermal pretreatment |
| CN112680991A (en) * | 2020-12-22 | 2021-04-20 | 浙江农林大学 | Method for preparing xylan and high-purity lignin by using gramineous plants as raw materials |
| CN112726249A (en) * | 2020-12-29 | 2021-04-30 | 陕西科技大学 | Dissolving pulp prepared from corn straw skins and method |
| CN115852723B (en) * | 2022-12-08 | 2024-04-05 | 浙江华康药业股份有限公司 | Method for extracting high-purity xylose liquid and cellulose by using corn straw |
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