CN107604726A - A kind of method that paper making pulp is handled using complex enzyme liquid - Google Patents
A kind of method that paper making pulp is handled using complex enzyme liquid Download PDFInfo
- Publication number
- CN107604726A CN107604726A CN201710859395.4A CN201710859395A CN107604726A CN 107604726 A CN107604726 A CN 107604726A CN 201710859395 A CN201710859395 A CN 201710859395A CN 107604726 A CN107604726 A CN 107604726A
- Authority
- CN
- China
- Prior art keywords
- enzyme
- complex enzyme
- enzyme activity
- bleaching
- complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 413
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 413
- 239000007788 liquid Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 57
- 229940088598 enzyme Drugs 0.000 claims abstract description 401
- 230000000694 effects Effects 0.000 claims abstract description 161
- 238000004061 bleaching Methods 0.000 claims abstract description 107
- 239000002671 adjuvant Substances 0.000 claims abstract description 52
- 108010059892 Cellulase Proteins 0.000 claims abstract description 31
- 229940106157 cellulase Drugs 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 71
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 56
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- 229920001661 Chitosan Polymers 0.000 claims description 48
- 239000002002 slurry Substances 0.000 claims description 44
- 108010029541 Laccase Proteins 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 33
- 101710088194 Dehydrogenase Proteins 0.000 claims description 29
- 229940015043 glyoxal Drugs 0.000 claims description 28
- 108010001336 Horseradish Peroxidase Proteins 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 238000004537 pulping Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 108010059896 Manganese peroxidase Proteins 0.000 claims description 14
- 108010054320 Lignin peroxidase Proteins 0.000 claims description 13
- 238000007654 immersion Methods 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 102000016938 Catalase Human genes 0.000 claims description 10
- 108010053835 Catalase Proteins 0.000 claims description 10
- 108010055059 beta-Mannosidase Proteins 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000004382 Amylase Substances 0.000 claims description 9
- 108010065511 Amylases Proteins 0.000 claims description 9
- 102000013142 Amylases Human genes 0.000 claims description 9
- 102100032487 Beta-mannosidase Human genes 0.000 claims description 9
- 108090000526 Papain Proteins 0.000 claims description 9
- 239000004365 Protease Substances 0.000 claims description 9
- 235000019418 amylase Nutrition 0.000 claims description 9
- 229940055729 papain Drugs 0.000 claims description 9
- 235000019834 papain Nutrition 0.000 claims description 9
- 102000057297 Pepsin A Human genes 0.000 claims description 8
- 108090000284 Pepsin A Proteins 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229940111202 pepsin Drugs 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 5
- AEMOLEFTQBMNLQ-BKBMJHBISA-N alpha-D-galacturonic acid Chemical compound O[C@H]1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-BKBMJHBISA-N 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 229920000053 polysorbate 80 Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000005057 refrigeration Methods 0.000 claims description 5
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000007836 KH2PO4 Substances 0.000 claims description 4
- RWSXRVCMGQZWBV-PHDIDXHHSA-N L-Glutathione Natural products OC(=O)[C@H](N)CCC(=O)N[C@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-PHDIDXHHSA-N 0.000 claims description 4
- 239000002211 L-ascorbic acid Substances 0.000 claims description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 4
- 235000010443 alginic acid Nutrition 0.000 claims description 4
- 229920000615 alginic acid Polymers 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000007844 bleaching agent Substances 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 4
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 239000011686 zinc sulphate Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 3
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 claims 1
- 229920005610 lignin Polymers 0.000 abstract description 39
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 239000002023 wood Substances 0.000 description 9
- -1 Manganese peroxide Compound Chemical class 0.000 description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000010902 straw Substances 0.000 description 5
- 240000003291 Armoracia rusticana Species 0.000 description 4
- 235000011330 Armoracia rusticana Nutrition 0.000 description 4
- 229920002488 Hemicellulose Polymers 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000009264 composting Methods 0.000 description 3
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 206010033546 Pallor Diseases 0.000 description 2
- 244000082204 Phyllostachys viridis Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001221 xylan Polymers 0.000 description 2
- 150000004823 xylans Chemical class 0.000 description 2
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical class C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 1
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZVGCGHVMJAECEG-UHFFFAOYSA-N Chinol Natural products COC1=C(O)C(C)=C(C)C(O)=C1OC ZVGCGHVMJAECEG-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 101710129170 Extensin Proteins 0.000 description 1
- 241001349804 Juncus alpinoarticulatus Species 0.000 description 1
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 101710155614 Ligninase A Proteins 0.000 description 1
- 101710155621 Ligninase B Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 240000007263 Pinus koraiensis Species 0.000 description 1
- 235000011615 Pinus koraiensis Nutrition 0.000 description 1
- 235000011609 Pinus massoniana Nutrition 0.000 description 1
- 241000018650 Pinus massoniana Species 0.000 description 1
- 235000005456 Pinus sylvestris var mongolica Nutrition 0.000 description 1
- 241000114025 Pinus sylvestris var. mongolica Species 0.000 description 1
- 235000011611 Pinus yunnanensis Nutrition 0.000 description 1
- 241000018652 Pinus yunnanensis Species 0.000 description 1
- 108010059820 Polygalacturonase Proteins 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- XOKREDGJQHOCBW-UHFFFAOYSA-N [Mn].OO Chemical compound [Mn].OO XOKREDGJQHOCBW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 108010093305 exopolygalacturonase Proteins 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229940059442 hemicellulase Drugs 0.000 description 1
- 108010002430 hemicellulase Proteins 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229930013686 lignan Natural products 0.000 description 1
- 235000009408 lignans Nutrition 0.000 description 1
- 150000005692 lignans Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Paper (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
A kind of method that paper making pulp is handled using complex enzyme liquid, it is related to a kind of method for handling paper making pulp.The invention aims to solve to use a variety of enzyme Synergistic degradation lignin effects of cellulase treatment paper pulp in cellulase treatment paper pulp undesirable, and the problem of using enzyme bleaching effect difference, the present invention carries out lignin removal to paper making raw material using complex enzyme and complex enzyme adjuvant, and carries out bleaching using bleaching enzymes and bleaching enzymes adjuvant simultaneously.The Lignin degradation rate of the present invention is up to 49% or so.The whiteness of bleached pulp after processing is up to 70~85%.
Description
Technical field
The present invention relates to a kind of method for handling paper making pulp.
Background technology
The former material used in existing paper industry is biological material, such as timber, stalk, bamboo wood, and biological material
In include substantial amounts of lignin, hemicellulose and cellulose, lignin is thermoplastic material, and papermaking is fine using plant
The cellulose and part hemicellulose in raw material are tieed up, and lignin serves binding agent effect, therefore, fiber in fibrous raw material
Raw material can not be dispersed into single fiber, and the combination of page is realized by interfibrous Hydrogenbond, and lignin
In the presence of causing the easy yellowing of paper.Therefore, in paper-making process, especially prepare paper pulp and remove most of lignin.
At present, paper-making pulping mainly has two major class technology paths.1st, chemical pulp processes, addition auxiliary agent, adjusting process pair
Contamination is recycled.2nd, biological pulping method, reduce and pollute from source using bio-pulping technology.The former is come
Say：Mainly by international usual technology --- " alkali collection " system solves pollution problem, but " alkali collection " system still deposits throwing
Money is big, and processing cost is high, and white clay secondary pollution problems.For the latter：Bio-pulping technology is reduced from source
Pollution, the utilization rate of raw material is improved, and the black liquor after biological treatment can be again converted to organic fertilizer and carry out secondary use, be near
Paid close attention to a kind of Novel cement slurry preparing technology of exploitation over year energetically by experts and scholars and enterprise.
Existing biological pulping method mainly has two classes：One kind is directly to handle raw material using microorganism；One kind is to use
Enzyme treated feed stock.
Using enzyme treated feed stock, such as Publication No. CN1616758A, entitled bio-pulping process；Publication No.
The patent such as CN1421570A, the method for entitled enzymatic straw material pulping, the major defect of the technique are：Enzyme liquid into
This height, the not owning cost advantage in industrialized production；Meanwhile lignoenzyme, zytase, hemicellulase are to corresponding composition
Destruction be difficult to control, may excessively remove lignin, xylan, hemicellulose, influence paper pulp yield.Publication No. CN
The patent of 101914510A, a kind of entitled alkaline pectinase production method and the application in paper-making pulping discloses one
Kind alkaline pectase and the application in paper-making pulping, i.e., paper making raw material is soaked after pickling processing with alkaline pectin enzyme liquid,
The boiling in digester again after ferment treatment.But its complex process, raw material carry out ferment treatment again after needing pickling, caustic dip, exist with
Lower deficiency：First, enzyme is single, leaching enzyme time length；Second, needing newly added equipment, increase cost；Third, pickling, caustic dip step need to be increased newly
Suddenly, new pollution, it is unfavorable for industrialized production use.
Moreover, the complex enzyme used at present is only to be used after several enzymes are combined, seldom it is related to the phase of addition enzyme
The content of adjuvant is closed, existing enzyme is that several intimate enzymes are grouped together, and effect is single.Lignin removal effect is not
Ideal, general lignin removing rate can only be 30% or so.
Now widely used is lignoenzyme, it be have Catalytic lignin oxidative degradation ability class of enzymes it is total
Claim, this kind of enzymatic oxidation reduction reaction, the entitled oxidoreducing enzyme of system, popular name is dehydrogenase, and it includes four components：Laccase
That is entitled diphenol oxidoreducing enzyme of system, effect is with o-quinone alcohol and to chinol, the oxidation reaction of amino-phenol and this diamines；Wood
Lignin peroxidase is the entitled lignin hydrogen peroxide redox enzyme of system, the oxidation reaction of Catalytic lignin；Manganese peroxide
Compound enzyme is the entitled bivalent manganese hydrogen peroxide redox enzyme of system, and catalysis bivalent manganese is oxidized to the reaction of manganic, is wooden
Plain oxidative degradation；Diarylpropane peroxidase is also known as the entitled diarylpropane of lignoenzyme I i.e. system：Oxygen, hydrogen peroxide
Oxidoreducing enzyme, it is catalyzed fracture and the benzyl alcohol oxidation generation aldehydes or ketones of many related typical compound carbon-carbon keys.
Lignoenzyme is not only to lignin, and the organic pollution that the organic matter to numerous species is especially artificial synthesized
There is very strong degradation capability, and there is high spectrum, efficient, low consumption, high applicability.This special degradation mechanism exists
Huge application prospect is presented in terms of feed industry, chemical industry, coal chemistry and environmental protection, has caused academia
With the extensive concern of industrial quarters.
The effect of the enzyme how is preferably played, and is acted synergistically with other enzymes, is urgent problem.
In addition, also to be bleached after lignin is removed, because most of raw material that papermaking uses all are days
Right macromolecule organic, its main component are cellulose, hemicellulose, lignin etc., and they are not only double containing carbonyl, unsaturation
Build and conjugated system chromophoric group, but also contain the auxochrome groups such as hydroxyl.These are present in lignin structure and a small amount of
The combination of component brass, lignan, chromophoric group in stilbene class formation, makes timber show colourful color.But
The process for removing lignin is only capable of realizing single performance, it is necessary to carry out bleaching process again after being removed such as boiling.This is due to existing
In the removal process of lignin, preferable bleaching effect can not be reached by bleaching process is in conjunction.And existing removed
The intensity of cellulose is easily damaged in journey.
How biology enzyme effect in bleaching process is improved, at present not good technology.
The content of the invention
The present invention is directed to a variety of enzyme Synergistic degradation lignin effect for using cellulase treatment paper pulp in cellulase treatment paper pulp
Fruit is undesirable, and the problem of use enzyme bleaching effect difference.And provide a kind of method that paper making pulp is handled using complex enzyme liquid.
A kind of method that paper making pulp is handled using complex enzyme liquid of the present invention, bio-pulping method is used in pulp stage；
Detailed process is as follows：
Paper making raw material is prepared into thick slurry, is put into complex enzyme liquid immersion treatment into thick slurry, treatment conditions are：Temperature is 20
DEG C~60 DEG C, pH be 2~7.0, be passed through air, digest 36h~60h, bleaching enzyme mixation is put into after complex enzyme liquid processing,
PH is 7.0~9.5, and temperature is 40 DEG C~60 DEG C, digests 30min~80min；Wherein, complex enzyme liquid addition is thick slurry dry weight
0.001%~5%；Enzyme mixation addition is bleached as the 0.1%~2% of thick slurry dry weight；
Described complex enzyme liquid includes complex enzyme and complex enzyme adjuvant；Wherein, the matter of complex enzyme and complex enzyme adjuvant
Amount is than being 1:30~50；
Wherein, the enzyme activity of laccase is 50U/mL~2000U/mL, the enzyme activity of lignin peroxidase in complex enzyme
Enzyme activity for 50U/mL~1000U/mL, manganese peroxidase is 50U/mL~2000U/mL, the enzyme activity of pectase is
100U/mL~1000U/mL, cellulase and enzyme enzyme activity are 100U/mL~1000U/mL, the vigor of amylase is 100U/
ML~1000U/mL, the enzyme activity of pepsin are 100U/mL~1000U/mL, the enzyme activity of papain is 100U/mL
~1000U/mL, the enzyme activity of glyoxal dehydrogenase are 50U/mL~2000U/mL and the enzyme activity of horseradish peroxidase is
50U/mL~2000U/mL；
Complex enzyme adjuvant includes 1~10mM MnSO using acetic acid as solvent4, 0.1~2mM FeSO4, 0.1~
6mM CuSO4, 1~8mM Na2SO3, 0.1~2mM sodium dithionite and 0.08g/L~0.15g/L Tween 80；
Described bleaching enzyme mixation includes the adjuvant of bleaching enzymes and bleaching enzymes；Wherein, bleaching enzymes and bleaching enzymes is auxiliary
The mass ratio of auxiliary agent is 1:10~30；
The enzyme activity of zytase is 2500U/mL~3000U/mL, the enzyme activity of mannase in described bleaching enzymes
Enzyme activity for 1500U/mL~2000U/mL, catalase is 500U/mL~1000U/mL, the enzyme activity of laccase is 50U/
The enzyme activity of mL~2000U/mL and alkaline pectase is 500U/mL~1500U/mL；
The adjuvant of bleaching enzymes is that concentration is 0.08g/L~0.15g/L N- hydroxyls phthalimides or different hydroxyl oxime
Acid.
A kind of method that paper making pulp is handled using complex enzyme liquid of the present invention, bio-pulping method is used in pulp stage；
Detailed process is as follows：
Paper making raw material is prepared into thick slurry, is put into complex enzyme liquid immersion treatment into thick slurry, treatment conditions are：Temperature is 20
DEG C~48 DEG C, pH be 2~6.0, be passed through air, digest 36h~60h, bleaching enzyme mixation is put into after complex enzyme liquid processing,
PH is 7.0~9.5, and temperature is 40 DEG C~60 DEG C, digests 30min~80min；Wherein, complex enzyme liquid addition is thick slurry dry weight
0.001%~5%；Enzyme mixation addition is bleached as the 0.1%~2% of thick slurry dry weight；
Described complex enzyme liquid includes complex enzyme and complex enzyme adjuvant；Wherein, the matter of complex enzyme and complex enzyme adjuvant
Amount is than being 1:30~50；
Wherein, the enzyme activity of laccase is 50U/mL~2000U/mL, the enzyme activity of lignin peroxidase in complex enzyme
Enzyme activity for 50U/mL~1000U/mL, manganese peroxidase is 50U/mL~2000U/mL, the enzyme activity of pectase is
100U/mL~1000U/mL, the enzyme activity of cellulase are 100U/mL~1000U/mL and the enzyme activity of amylase is 100U/
ML~1000U/mL, the enzyme activity of pepsin are 100U/mL~1000U/mL, the enzyme activity of papain is 100U/mL
~1000U/mL, the enzyme activity of glyoxal dehydrogenase are 50U/mL~2000U/mL and the enzyme activity of horseradish peroxidase is
50U/mL~2000U/mL；
Complex enzyme adjuvant includes 1~10mol/L MnSO using acetic acid as solvent4, 1~3g/L ascorbic acid,
1~2g/L glucose, 1~2g/L alginates, 1~2g/L pectic substance, 1~2mol/L KH2PO4, 0.1~1.0g/L
ZnSO4, 0.01~0.1g/L H2BO3, 1~2g/L NaCl and 1~5g/L glutathione；
Described bleaching enzyme mixation includes the adjuvant of bleaching enzymes and bleaching enzymes；Wherein, bleaching enzymes and bleaching enzymes is auxiliary
The mass ratio of auxiliary agent is 1:10~30；
The enzyme activity of zytase is 2500U/mL~3000U/mL, the enzyme activity of mannase in described bleaching enzymes
Enzyme activity for 1500U/mL~2000U/mL, catalase is 500U/mL~1000U/mL, the enzyme activity of laccase is 50U/
ML~2000U/mL, the enzyme activity of alkaline pectase are 500U/mL~1500U/mL, the enzyme activity of glyoxal dehydrogenase is 50U/
The enzyme activity of mL~2000U/mL and horseradish peroxidase is 50U/mL~2000U/mL；
The adjuvant of bleaching enzymes is that concentration is 0.08g/L~0.15g/L N- hydroxyls phthalimides or different hydroxyl oxime
Acid.
Paper making raw material of the present invention is wood of coniferous tree (such as larch, Korean pine, masson pine, pinus yunnanensis, pinus sylvestris var. mongolica
Deng) or broadleaf tree timber (such as poplar, birch, Eucalyptus) wood chip or straw or like vegetable (such as reed, bamboo, awns stalk, wheat straw,
Straw, Chinese alpine rush, sorghum stalk, bagasse etc.).
The above-mentioned complex enzyme or bleaching enzymes of the present invention in use, can be according to actual conditions, in order to complex enzyme
Or bleaching enzyme effect is played most preferably, and various enzymes in complex enzyme or bleaching enzymes are added separately to, i.e., will first be reacted after the addition of several enzymes
For a period of time, remaining several enzymes are added.
The present invention includes following beneficial effect：
The present invention is by adding the lignin degradings such as amylase laccase, manganese peroxidase, and by adding stomach egg
White enzyme and papain are used to decompose the extensin being present in timber, so that the enzyme of lignin degrading can preferably connect
Lignin is contacted, lignin is removed as far as possible, the pectase of addition can decompose pectic substance, dissolve the cell of softening tissue
Interbed, dissociate fibre bundle, paper pulp is ultimately become wandering fibre.Degradation effect in order to better improve, present invention addition Mn,
The metal inducement such as Fe, Cu thing has induction incentive action well to manganese peroxidase and lignin peroxidase, to wooden
Non- phenolic fragrance hydrocarbon polymer (accounting for main component in lignin) in element has extraordinary degradation effect.Surface active agent tween
80 addition causes laccase to be preferably adsorbed onto on lignin, further improves hydrolysis result.The lignin drop of the present invention
Solution rate is up to 49% or so.
Moreover, the present invention it is innovative using glyoxal dehydrogenase and horseradish peroxidase production hydrogen peroxide, laccase,
In the presence of manganese peroxidase and lignin peroxidase, hydrogen peroxide carries out catalytic reaction, improves the degraded effect of enzyme
Fruit, and without being additionally passed through hydrogen peroxide, moreover, caused hydrogen peroxide, can also play a part of bleached pulp；
Zytase that the present invention adds, mannase are partially covered in residual lignin after mainly suppressing boiling
Reprecipitation xylan effect, and by its degraded improve lignin to bleaching chemical used in hereafter bleaching process
The accessible property of (such as chlorine dioxide).
The N- hydroxyls phthalimide or hydroxamic acid of addition and alkaline pectase, zytase, mannase
After being combined with catalase, the bleaching to paper pulp play with unexpected effect, in 1~4 hour, Kappa is from 30
It is down to 10.
Moreover, another innovation of the invention is：Before bleaching enzymes are added, ultraviolet irradiation is carried out, in order to produce
Raw negative oxygen ion, because negative oxygen ion is unstable, it is easy to lose an electronics and become ozone, and catalase etc. reacts
During ozone be important reaction substrate, therefore, the generation of ozone causes the activity of biology enzyme to greatly increase, and negative oxygen from
Son or ozone can enter inside wood structure, and the lignin net macromolecular of timber is destroyed, and link the loosening of other molecules, because
This, method of the invention not only increases the removal of lignin, while adds bleaching effect, can without following bleaching processing
To reach blanching effect.
Ozone is indispensable reaction substrate in course of reaction, and therefore, the generation of ozone make it that the activity of biology enzyme is big
Big increase, and negative oxygen ion or ozone can enter inside wood structure, the lignin net macromolecular of timber be destroyed, linkage
Other molecules loosen, and therefore, method of the invention not only increases the removal of lignin, while adds bleaching effect, without
Following bleaching processing can reaches blanching effect.
By complex enzyme adjuvant of the present invention manganese peroxidase in complex enzyme can increase active 1.63 times, wooden
Plain 5.7 times of peroxidase increase activity, 4.1 times of laccase increase activity, 1.3 times of cellulase increase activity.In addition, it can improve
In aerobic composting process in various raw materials lignin 0.7~1.2 times of degradation rate.
Embodiment
Embodiment one：A kind of method that paper making pulp is handled using complex enzyme liquid of present embodiment, in slurrying
Stage uses bio-pulping method；Detailed process is as follows：
Paper making raw material is prepared into thick slurry, is put into complex enzyme liquid immersion treatment into thick slurry, treatment conditions are：Temperature is 20
DEG C~60 DEG C, pH be 2~7.0, be passed through air, digest 36h~60h, bleaching enzyme mixation is put into after complex enzyme liquid processing,
PH is 7.0~9.5, and temperature is 40 DEG C~60 DEG C, digests 30min~80min；Wherein, complex enzyme liquid addition is thick slurry dry weight
0.001%~5%；Enzyme mixation addition is bleached as the 0.1%~2% of thick slurry dry weight；
Described complex enzyme liquid includes complex enzyme and complex enzyme adjuvant；Wherein, the matter of complex enzyme and complex enzyme adjuvant
Amount is than being 1:30~50；
Wherein, the enzyme activity of laccase is 50U/mL~2000U/mL, the enzyme activity of lignin peroxidase in complex enzyme
Enzyme activity for 50U/mL~1000U/mL, manganese peroxidase is 50U/mL~2000U/mL, the enzyme activity of pectase is
100U/mL~1000U/mL, cellulase and enzyme enzyme activity are 100U/mL~1000U/mL, the vigor of amylase is 100U/
ML~1000U/mL, the enzyme activity of pepsin are 100U/mL~1000U/mL, the enzyme activity of papain is 100U/mL
~1000U/mL, the enzyme activity of glyoxal dehydrogenase are 50U/mL~2000U/mL and the enzyme activity of horseradish peroxidase is
50U/mL~2000U/mL；
Complex enzyme adjuvant includes 1~10mM MnSO using acetic acid as solvent4, 0.1~2mM FeSO4, 0.1~
6mM CuSO4, 1~8mM Na2SO3, 0.1~2mM sodium dithionite and 0.08g/L~0.15g/L Tween 80；
Described bleaching enzyme mixation includes the adjuvant of bleaching enzymes and bleaching enzymes；Wherein, bleaching enzymes and bleaching enzymes is auxiliary
The mass ratio of auxiliary agent is 1:10~30；
The enzyme activity of zytase is 2500U/mL~3000U/mL, the enzyme activity of mannase in described bleaching enzymes
Enzyme activity for 1500U/mL~2000U/mL, catalase is 500U/mL~1000U/mL, the enzyme activity of laccase is 50U/
The enzyme activity of mL~2000U/mL and alkaline pectase is 500U/mL~1500U/mL；
The adjuvant of bleaching enzymes is that concentration is 0.08g/L~0.15g/L N- hydroxyls phthalimides or different hydroxyl oxime
Acid.
Above-mentioned enzyme activity described in present embodiment, adjuvant, and the ratio of above-mentioned enzyme and adjuvant, reaction condition institute
All numerical value in the value range of statement are applied to the scheme of present embodiment.
Embodiment two：Present embodiment is unlike embodiment one：Enzyme mixation is bleached adding
Before, the slurries after being digested to complex enzyme liquid carry out ultraviolet irradiation, and bleaching enzyme mixation, ultraviolet irradiation are added after irradiation
Condition is：In the case where wavelength is 250nm~380nm ultraviolet light, 10min~30min is irradiated.It is other with the phase of embodiment one
Together.
Embodiment three：Present embodiment is unlike embodiment one：Enzyme mixation is bleached adding
Before, the slurries after being digested to complex enzyme liquid carry out ultraviolet irradiation, after stopping 5~10min of irradiation, add bleaching enzymes and mix
Close liquid.It is other identical with embodiment one.
Embodiment four：Present embodiment is unlike embodiment one：Described laccase is
C.thermophilium laccases (are commercially available).It is other identical with embodiment one.
Embodiment five：Present embodiment is unlike embodiment one：Described glyoxal dehydrogenase
It is to be placed into after being fixed by carrier in paper pulp with horseradish peroxidase；Wherein, glyoxal dehydrogenase and horseradish peroxidating
Thing zymophore fixing means is as follows：
(1) Chitosan powder is dissolved in acetic acid aqueous solution, being heated to 40~60 DEG C is completely dissolved chitosan, then will
Macroreticular resin is added in the chitosan solution, reacts 1~10h, Chitosan-coated is on macroreticular resin；Chitosan will be coated
Macroreticular resin be added in the mixed liquor of the NaOH aqueous solution and absolute ethyl alcohol, soaked in the mixed liquor of NaOH and absolute ethyl alcohol
30~120min, suction filtration obtain Chitosan-coated macroreticular resin particle, and it is neutral finally fully to be washed with deionized water to pH value；
The mass volume ratio of the chitosan and acetic acid is 1g：1~5mL；The mass ratio of chitosan and macroreticular resin is 1：1~10；
NaOH concentration is 1-4mol/L in the NaOH aqueous solution；The volume ratio of the NaOH aqueous solution and absolute ethyl alcohol is 4~8：1；
(2) by Chitosan-coated macroreticular resin particle obtained by step (1) add to mass concentration be 0.0025%~
In 0.05% glutaraldehyde water solution, it is placed in shaking table after 10~60min of cross-linking reaction, is washed with deionized water at room temperature
Property, double enzyme liquids are added, are placed in shaking table after vibrating 1~6h, is washed with deionized water and remains double enzyme liquids, refrigeration is standby；The shell
It is 1g that glycan, which coats macroreticular resin particle and the mass volume ratio of double enzyme liquids,：2~10mL；Double enzyme liquids are by volume 1：2~5 is mixed
The glyoxal dehydrogenase and horseradish peroxidase of conjunction.
It is other identical with embodiment one.
Embodiment six：Present embodiment is unlike embodiment one：Described cellulase is resistance to
Neutral cellulase CelH61.Described heat-resistance neutral cellulase CelH61 is disclosed in the B of patent CN 103275956
Cellulase.It is other identical with embodiment one.
Embodiment seven：Present embodiment is unlike embodiment one：Paper making raw material is prepared into paper
Slurry, complex enzyme liquid immersion treatment is put into paper pulp, treatment conditions are：Temperature is 30 DEG C~60 DEG C, pH is 2.5~6.8, is passed through
Air, digest 36h~60h；Bleaching enzyme mixation is put into after complex enzyme liquid processing, is 7.0~9.0 in pH, temperature is 40 DEG C
~55 DEG C, digest 30min~80min；Wherein, complex enzyme liquid addition is the 0.001~5% of pulp dry weight；Bleaching enzymes mix
Liquid addition is the 0.1~2% of pulp dry weight.It is other identical with embodiment one.
Embodiment eight：Present embodiment uses bio-pulping method in pulp stage；Detailed process is as follows：
Paper making raw material is prepared into thick slurry, is put into complex enzyme liquid immersion treatment into thick slurry, treatment conditions are：Temperature is 20
DEG C~48 DEG C, pH be 2~6.0, be passed through air, digest 36h~60h；Bleaching enzyme mixation is put into after complex enzyme liquid processing,
PH is 7.0~9.5, and temperature is 40 DEG C~60 DEG C, digests 30min~80min；Wherein, complex enzyme liquid addition is thick slurry dry weight
0.001%~5%；Enzyme mixation addition is bleached as the 0.1%~2% of thick slurry dry weight；
Described complex enzyme liquid includes complex enzyme and complex enzyme adjuvant；Wherein, the matter of complex enzyme and complex enzyme adjuvant
Amount is than being 1:30~50；
Wherein, the enzyme activity of laccase is 50U/mL~2000U/mL, the enzyme activity of lignin peroxidase in complex enzyme
Enzyme activity for 50U/mL~1000U/mL, manganese peroxidase is 50U/mL~2000U/mL, the enzyme activity of pectase is
100U/mL~1000U/mL, the enzyme activity of cellulase are 100U/mL~1000U/mL and the enzyme activity of amylase is 100U/
ML~1000U/mL, the enzyme activity of pepsin are 100U/mL~1000U/mL, the enzyme activity of papain is 100U/mL
~1000U/mL, the enzyme activity of glyoxal dehydrogenase are 50U/mL~2000U/mL and the enzyme activity of horseradish peroxidase is
50U/mL~2000U/mL；
Complex enzyme adjuvant includes 1~10mol/L MnSO using acetic acid as solvent4, 1~3g/L ascorbic acid,
1~2g/L glucose, 1~2g/L alginates, 1~2g/L pectic substance, 1~2mol/L KH2PO4, 0.1~1.0g/L
ZnSO4, 0.01~0.1g/L H2BO3, 1~2g/L NaCl and 1~5g/L glutathione；
Described bleaching enzyme mixation includes the adjuvant of bleaching enzymes and bleaching enzymes；Wherein, bleaching enzymes and bleaching enzymes is auxiliary
The mass ratio of auxiliary agent is 1:10~30；
The enzyme activity of zytase is 2500U/mL~3000U/mL, the enzyme activity of mannase in described bleaching enzymes
Enzyme activity for 1500U/mL~2000U/mL, catalase is 500U/mL~1000U/mL, the enzyme activity of laccase is 50U/
ML~2000U/mL, the enzyme activity of alkaline pectase are 500U/mL~1500U/mL, the enzyme activity of glyoxal dehydrogenase is 50U/
The enzyme activity of mL~2000U/mL and horseradish peroxidase is 50U/mL~2000U/mL；
The adjuvant of bleaching enzymes is that concentration is 0.08g/L~0.15g/L N- hydroxyls phthalimides or different hydroxyl oxime
Acid.
Above-mentioned enzyme activity described in present embodiment, adjuvant, and the ratio of above-mentioned enzyme and adjuvant, reaction condition institute
All numerical value in the value range of statement are applied to the scheme of present embodiment.
Embodiment nine：Present embodiment is unlike embodiment eight：Paper making raw material is prepared into paper
Slurry, complex enzyme liquid immersion treatment is put into paper pulp, treatment conditions are：30 DEG C~60 DEG C, under the conditions of pH is 2.5~6.8, and lead to
Enter air, digest 36h~60h；Bleaching enzyme mixation is put into after complex enzyme liquid processing, is 7.0~9.0 in pH, 40 DEG C of temperature
~55 DEG C, digest 30min~80min；Wherein, complex enzyme liquid addition is the 0.001~5% of pulp dry weight；Bleaching enzymes mix
Liquid addition is the 0.1~2% of pulp dry weight.It is other identical with embodiment eight.
Embodiment ten：Present embodiment is unlike embodiment eight：Enzyme mixation is bleached adding
Before, the slurries after enzyme connects are carried out to complex enzyme liquid and carries out ultraviolet irradiation, bleaching enzyme mixation, ultraviolet irradiation are added after irradiation
Condition is：In the case where wavelength is 250nm~380nm ultraviolet light, 10min~30min is irradiated.It is other with the phase of embodiment eight
Together.
Embodiment 11：Present embodiment is unlike embodiment eight：Adding bleaching enzymes mixing
Before liquid, the slurries after enzyme connects are carried out to complex enzyme liquid and carry out ultraviolet irradiation, after stopping 5~10min of irradiation, add bleaching enzymes
Mixed liquor.It is other identical with embodiment eight.
Embodiment 12：Present embodiment is unlike embodiment eight：Described laccase is
C.thermophilium laccases (are commercially available).It is other identical with embodiment eight.
Embodiment 13：Present embodiment glyoxal dehydrogenase described unlike embodiment eight
It is to be placed into after being fixed by carrier in paper pulp with horseradish peroxidase；Wherein, glyoxal dehydrogenase and horseradish peroxidating
Thing zymophore fixing means is as follows：
(1) Chitosan powder is dissolved in acetic acid aqueous solution, being heated to 40~60 DEG C is completely dissolved chitosan, then will
Macroreticular resin is added in the chitosan solution, reacts 1~10h, Chitosan-coated is on macroreticular resin；Chitosan will be coated
Macroreticular resin be added in the mixed liquor of the NaOH aqueous solution and absolute ethyl alcohol, soaked in the mixed liquor of NaOH and absolute ethyl alcohol
30~120min, suction filtration obtain Chitosan-coated macroreticular resin particle, and it is neutral finally fully to be washed with deionized water to pH value；
The mass volume ratio of the chitosan and acetic acid is 1g：1~5mL；The mass ratio of chitosan and macroreticular resin is 1：1~10；
NaOH concentration is 1-4mol/L in the NaOH aqueous solution；The volume ratio of the NaOH aqueous solution and absolute ethyl alcohol is 4~8：1；
(2) by Chitosan-coated macroreticular resin particle obtained by step (1) add to mass concentration be 0.0025%~
In 0.05% glutaraldehyde water solution, it is placed in shaking table after 10~60min of cross-linking reaction, is washed with deionized water at room temperature
Property, double enzyme liquids are added, are placed in shaking table after vibrating 1~6h, is washed with deionized water and remains double enzyme liquids, refrigeration is standby；The shell
It is 1g that glycan, which coats macroreticular resin particle and the mass volume ratio of double enzyme liquids,：2~10mL；Double enzyme liquids are by volume 1：2~5 is mixed
The glyoxal dehydrogenase and horseradish peroxidase of conjunction.
It is other identical with embodiment eight.
Embodiment 14：Present embodiment is unlike embodiment eight：Described cellulase is
Heat-resistance neutral cellulase CelH61.Described heat-resistance neutral cellulase CelH61 is disclosed in the B of patent CN 103275956
Cellulase.It is other identical with embodiment eight.
Present invention is not limited only to the content of the respective embodiments described above, the group of one of them or several embodiments
Contract sample can also realize the purpose of invention.
Beneficial effects of the present invention are verified by following examples：
Embodiment 1
A kind of method that paper making pulp is handled using complex enzyme liquid of the present embodiment, bio-pulping is used in pulp stage
Method；Detailed process is as follows：
Paper making raw material is prepared into thick slurry, is put into complex enzyme liquid immersion treatment into thick slurry, treatment conditions are：Temperature is 30
DEG C~60 DEG C, pH be 2~7.0, and be passed through air, digest 45h；Bleaching enzyme mixation is put into after complex enzyme liquid processing, in pH
For 7.0~9.5,40 DEG C~60 DEG C of temperature, 30min is digested；Wherein, complex enzyme liquid addition is the 1% of thick slurry dry weight；Bleaching enzymes
Mixed liquor addition is the 0.5% of thick slurry dry weight；
Described complex enzyme liquid includes complex enzyme and complex enzyme adjuvant；Wherein, the matter of complex enzyme and complex enzyme adjuvant
Amount is than being 1:35；
Wherein, in complex enzyme the enzyme activity of laccase be 1200U/mL, the enzyme activity of lignin peroxidase be 1000U/
ML, the enzyme activity of manganese peroxidase are 1000U/mL, the enzyme activity of pectase is 800U/mL, the enzyme activity of cellulase is
The enzyme activity of 1000U/mL and amylase is 400U/mL, the enzyme activity of pepsin is 400U/mL, the enzyme activity of papain
Power is 500U/mL, the enzyme activity of glyoxal dehydrogenase is 600U/mL and the enzyme activity of horseradish peroxidase is 700U/mL；
Complex enzyme adjuvant includes 6.3mM MnSO using acetic acid as solvent4, 0.7mM FeSO4, 2.0mM's
CuSO4, 2.5mM Na2SO3, 0.8mM sodium dithionite and 0.10g/L Tween 80；
Described bleaching enzyme mixation includes the adjuvant of bleaching enzymes and bleaching enzymes；Wherein, bleaching enzymes and bleaching enzymes is auxiliary
The mass ratio of auxiliary agent is 1:23；
The enzyme activity of zytase is that 2500U/mL, mannase enzyme activity is 1600U/ in described bleaching enzymes
ML, the enzyme activity of catalase are 1000U/mL, the enzyme activity of laccase is 1000U/mL and the enzyme activity of alkaline pectase is
1000U/mL；
The adjuvant of bleaching enzymes is that concentration is 0.10g/L N- hydroxyl phthalimides.
For the present embodiment before bleaching enzyme mixation is added, the slurries after being digested to complex enzyme liquid carry out ultraviolet photograph
Penetrate, add bleaching enzyme mixation after stopping irradiation 5min, ultraviolet irradiation condition is：It is the ultraviolet of 250nm~300nm in wavelength
Under light, 15min is irradiated.
Laccase described in the present embodiment is C.thermophilium laccases.
Cellulase described in the present embodiment is heat-resistance neutral cellulase CelH61, and it is the B of patent CN 103275956
Disclosed cellulase.
Paper making raw material described in the present embodiment is the wood chip of poplar.
Glyoxal dehydrogenase and horseradish peroxidase described in the present embodiment are to place into paper pulp after being fixed by carrier
Interior；Wherein, glyoxal dehydrogenase and horseradish peroxidase carrier fixing means are as follows：
(1) Chitosan powder is dissolved in acetic acid aqueous solution, being heated to 40 DEG C is completely dissolved chitosan, then by macropore
Resin is added in the chitosan solution, reacts 1h, Chitosan-coated is on macroreticular resin；The macropore tree of chitosan will be coated
Fat is added in the mixed liquor of the NaOH aqueous solution and absolute ethyl alcohol, is soaked 30min in the mixed liquor of NaOH and absolute ethyl alcohol, is taken out
Filter obtains Chitosan-coated macroreticular resin particle, and it is neutral finally fully to be washed with deionized water to pH value；The chitosan with
The mass volume ratio of acetic acid is 1g: 5mL；The mass ratio of chitosan and macroreticular resin is 1：10；NaOH concentration in the NaOH aqueous solution
For 1mol/L；The volume ratio of the NaOH aqueous solution and absolute ethyl alcohol is 4：1；
(2) Chitosan-coated macroreticular resin particle obtained by step (1) is added to penta 2 that mass concentration is 0.0025%
In the aldehyde aqueous solution, it is placed in shaking table after cross-linking reaction 10min, is washed with deionized water to neutrality at room temperature, adds double enzyme liquids, be placed in
After vibrating 1h in shaking table, it is washed with deionized water and remains double enzyme liquids, refrigeration is standby；The Chitosan-coated macroreticular resin particle with
The mass volume ratio of double enzyme liquids is 1g：5mL；Double enzyme liquids are by volume 1：The glyoxal dehydrogenase of 2 mixing and horseradish peroxidating
Thing enzyme.
The paper pulp handled through the present embodiment, Lignin degradation rate reach as high as 49.2%.Bleach pulp brightness 73~81%.
The manganese peroxidase in complex enzyme can be made to increase by 1.63 times of activity, wood by the present embodiment complex enzyme adjuvant
5.7 times of lignin peroxidase increase activity, 4.1 times of laccase increase activity, 1.3 times of cellulase increase activity.In addition, it can carry
In high aerobic composting process in various raw materials lignin 0.7~1.2 times of degradation rate.
Embodiment 2
A kind of method that paper making pulp is handled using complex enzyme liquid of the present embodiment, bio-pulping is used in pulp stage
Method；Detailed process is as follows：
Paper making raw material is prepared into thick slurry, is put into complex enzyme liquid immersion treatment into thick slurry, treatment conditions are：Temperature is 30
DEG C~60 DEG C, pH be 2~7.0, be passed through air, digest 45h；Bleaching enzyme mixation is put into after complex enzyme liquid processing, is in pH
7.0~9.5, temperature is 40 DEG C~60 DEG C, digests 30min；Wherein, complex enzyme liquid addition is the 1% of thick slurry dry weight；Bleaching enzymes
Mixed liquor addition is the 0.5% of thick slurry dry weight；
Described complex enzyme liquid includes complex enzyme and complex enzyme adjuvant；Wherein, the matter of complex enzyme and complex enzyme adjuvant
Amount is than being 1:35；
Wherein, in complex enzyme the enzyme activity of laccase be 1200U/mL, the enzyme activity of lignin peroxidase be 1000U/
ML, the enzyme activity of manganese peroxidase are 1000U/mL, the enzyme activity of pectase is 800U/mL, the enzyme activity of cellulase is
The enzyme activity of 1000U/mL and amylase is 400U/mL, the enzyme activity of pepsin is 400U/mL, the enzyme activity of papain
Power is 500U/mL, the enzyme activity of glyoxal dehydrogenase is 600U/mL and the enzyme activity of horseradish peroxidase is 700U/mL；
Complex enzyme adjuvant includes 5.0mM MnSO using acetic acid as solvent4, 2g/L ascorbic acid, 1g/L Portugal
Grape sugar, 1g/L alginates, 1g/L pectic substance, 1mol/L KH2PO4, 0.3g/L ZnSO4, 0.05g/L H2BO3、1g/L
NaCl and 1g/L glutathione；
Described bleaching enzyme mixation includes the adjuvant of bleaching enzymes and bleaching enzymes；Wherein, bleaching enzymes and bleaching enzymes is auxiliary
The mass ratio of auxiliary agent is 1:20；
The enzyme activity that described bleaching enzymes include zytase is 2500u/mL, the enzyme activity of mannase is 1600U/
ML, the enzyme activity of catalase are 1000U/mL, the enzyme activity of laccase is 1000U/mL, the enzyme activity of alkaline pectase is
1000U/mL, the enzyme activity of glyoxal dehydrogenase are 1000U/mL and the enzyme activity of horseradish peroxidase is 1000U/mL；
The adjuvant of bleaching enzymes is that concentration is 0.10g/L hydroxamic acid.
The present embodiment carries out the slurries after enzyme connects before bleaching enzyme mixation is added, to complex enzyme liquid and carries out ultraviolet photograph
Penetrate, add bleaching enzyme mixation after stopping irradiation 5min, ultraviolet irradiation condition is：It is the ultraviolet of 250nm~300nm in wavelength
Under light, 15min is irradiated.
Laccase described in the present embodiment is C.thermophilium laccases.
Cellulase described in the present embodiment is heat-resistance neutral cellulase CelH61, and it is the B of patent CN 103275956
Disclosed cellulase.
Paper making raw material described in the present embodiment is rice straw.
Glyoxal dehydrogenase and horseradish peroxidase described in the present embodiment are to place into paper pulp after being fixed by carrier
Interior；Wherein, glyoxal dehydrogenase and horseradish peroxidase carrier fixing means are as follows：
(1) Chitosan powder is dissolved in acetic acid aqueous solution, being heated to 40 DEG C is completely dissolved chitosan, then by macropore
Resin is added in the chitosan solution, reacts 1h, Chitosan-coated is on macroreticular resin；The macropore tree of chitosan will be coated
Fat is added in the mixed liquor of the NaOH aqueous solution and absolute ethyl alcohol, is soaked 30min in the mixed liquor of NaOH and absolute ethyl alcohol, is taken out
Filter obtains Chitosan-coated macroreticular resin particle, and it is neutral finally fully to be washed with deionized water to pH value；The chitosan with
The mass volume ratio of acetic acid is 1g：5mL；The mass ratio of chitosan and macroreticular resin is 1：10；NaOH concentration in the NaOH aqueous solution
For 1mol/L；The volume ratio of the NaOH aqueous solution and absolute ethyl alcohol is 4：1；
(2) Chitosan-coated macroreticular resin particle obtained by step (1) is added to penta 2 that mass concentration is 0.0025%
In the aldehyde aqueous solution, it is placed in shaking table after cross-linking reaction 10min, is washed with deionized water to neutrality at room temperature, adds double enzyme liquids, be placed in
After vibrating 1h in shaking table, it is washed with deionized water and remains double enzyme liquids, refrigeration is standby；The Chitosan-coated macroreticular resin particle with
The mass volume ratio of double enzyme liquids is 1g: 5mL；Glyoxal dehydrogenase and horseradish peroxidating of double enzyme liquids for by volume 1: 2 mixing
Thing enzyme.
The paper pulp handled through the present embodiment, Lignin degradation rate reach as high as 46%.Bleach pulp brightness 70~85%.
The manganese peroxidase in complex enzyme can be made to increase by 1.63 times of activity, wood by the present embodiment complex enzyme adjuvant
5.7 times of lignin peroxidase increase activity, 4.1 times of laccase increase activity, 1.3 times of cellulase increase activity.In addition, it can carry
In high aerobic composting process in various raw materials lignin 0.7~1.2 times of degradation rate.
Claims (10)
- A kind of 1. method that paper making pulp is handled using complex enzyme liquid, it is characterised in that use bio-pulping method in pulp stage； Detailed process is as follows：Paper making raw material is prepared into thick slurry, is put into complex enzyme liquid immersion treatment into thick slurry, treatment conditions are：Temperature be 20 DEG C~ 60 DEG C, pH be 2~7.0, be passed through air, digest 36h~60h, be put into bleaching enzyme mixation after complex enzyme liquid processing, be in pH 7.0~9.5, temperature is 40 DEG C~60 DEG C, digests 30min~80min；Wherein, complex enzyme liquid addition is thick slurry dry weight 0.001%~5%；Enzyme mixation addition is bleached as the 0.1%~2% of thick slurry dry weight；Described complex enzyme liquid includes complex enzyme and complex enzyme adjuvant；Wherein, the mass ratio of complex enzyme and complex enzyme adjuvant For 1:30~50；Wherein, in complex enzyme the enzyme activity of laccase be 50U/mL~2000U/mL, the enzyme activity of lignin peroxidase be 50U/mL~1000U/mL, the enzyme activity of manganese peroxidase are 50U/mL~2000U/mL, the enzyme activity of pectase is 100U/ ML~1000U/mL, cellulase and enzyme enzyme activity are 100U/mL~1000U/mL, the vigor of amylase be 100U/mL~ 1000U/mL, the enzyme activity of pepsin are 100U/mL~1000U/mL, the enzyme activity of papain be 100U/mL~ 1000U/mL, the enzyme activity of glyoxal dehydrogenase are 50U/mL~2000U/mL and the enzyme activity of horseradish peroxidase is 50U/ ML~2000U/mL；Complex enzyme adjuvant includes 1~10mM MnSO using acetic acid as solvent4, 0.1~2mM FeSO4, 0.1~6mM's CuSO4, 1~8mM Na2SO3, 0.1~2mM sodium dithionite and 0.08g/L~0.15g/L Tween 80；Described bleaching enzyme mixation includes the adjuvant of bleaching enzymes and bleaching enzymes；Wherein, the adjuvant of bleaching enzymes and bleaching enzymes Mass ratio be 1:10~30；In described bleaching enzymes the enzyme activity of zytase be 2500U/mL~3000U/mL, the enzyme activity of mannase be 1500U/mL~2000U/mL, the enzyme activity of catalase are 500U/mL~1000U/mL, the enzyme activity of laccase is 50U/mL The enzyme activity of~2000U/mL and alkaline pectase is 500U/mL~1500U/mL；The adjuvant of bleaching enzymes is that concentration is 0.08g/L~0.15g/L N- hydroxyls phthalimides or hydroxamic acid.
- 2. a kind of method that paper making pulp is handled using complex enzyme liquid according to claim 1, it is characterised in that adding Before bleaching enzyme mixation, the slurries after being digested to complex enzyme liquid carry out ultraviolet irradiation, add bleaching enzymes after irradiation and mix Liquid is closed, ultraviolet irradiation condition is：In the case where wavelength is 250nm~380nm ultraviolet light, 10min~30min is irradiated.
- 3. a kind of method that paper making pulp is handled using complex enzyme liquid according to claim 1, it is characterised in that adding Before bleaching enzyme mixation, the slurries after being digested to complex enzyme liquid carry out ultraviolet irradiation, after stopping 5~10min of irradiation, then Add bleaching enzyme mixation.
- 4. a kind of method that paper making pulp is handled using complex enzyme liquid according to claim 1, it is characterised in that described Laccase is C.thermophilium laccases.
- 5. a kind of method that paper making pulp is handled using complex enzyme liquid according to claim 1, it is characterised in that described Glyoxal dehydrogenase and horseradish peroxidase are to be placed into after being fixed by carrier in paper pulp；Wherein, glyoxal dehydrogenase It is as follows with horseradish peroxidase carrier fixing means：(1) Chitosan powder is dissolved in acetic acid aqueous solution, being heated to 40~60 DEG C is completely dissolved chitosan, then by macropore Resin is added in the chitosan solution, reacts 1~10h, Chitosan-coated is on macroreticular resin；The big of chitosan will be coated Hole resin is added in the mixed liquor of the NaOH aqueous solution and absolute ethyl alcohol, in the mixed liquor of NaOH and absolute ethyl alcohol soak 30~ 120min, suction filtration obtain Chitosan-coated macroreticular resin particle, and it is neutral finally fully to be washed with deionized water to pH value；It is described The mass volume ratio of chitosan and acetic acid is 1g：1~5mL；The mass ratio of chitosan and macroreticular resin is 1：1~10；NaOH water NaOH concentration is 1-4mol/L in solution；The volume ratio of the NaOH aqueous solution and absolute ethyl alcohol is 4~8：1；(2) it is 0.0025%~0.05% to add Chitosan-coated macroreticular resin particle obtained by step (1) to mass concentration In glutaraldehyde water solution, it is placed in shaking table after 10~60min of cross-linking reaction, is washed with deionized water to neutrality at room temperature, is added double Enzyme liquid, it is placed in shaking table after vibrating 1~6h, is washed with deionized water and remains double enzyme liquids, refrigeration is standby；The Chitosan-coated is big Hole resin particle and the mass volume ratio of double enzyme liquids are 1g：2~10mL；Double enzyme liquids are by volume 1：The glyoxal of 2~5 mixing Dehydrogenase and horseradish peroxidase.
- 6. a kind of method that paper making pulp is handled using complex enzyme liquid according to claim 1, it is characterised in that described Cellulase is heat-resistance neutral cellulase CelH61.
- 7. a kind of method that paper making pulp is handled using complex enzyme liquid according to claim 1, it is characterised in that by papermaking Raw material is prepared into paper pulp, and complex enzyme liquid immersion treatment is put into paper pulp, and treatment conditions are：Temperature is 30 DEG C~60 DEG C, pH is 2.5~6.8, be passed through air, digest 36h~60h, bleaching enzyme mixation is put into after complex enzyme liquid processing, pH be 7.0~ 9.0, temperature is 40 DEG C~55 DEG C, digests 30min~80min；Wherein, complex enzyme liquid addition is the 0.001% of pulp dry weight ~5%；Bleach 0.1%~2% that enzyme mixation addition is pulp dry weight.
- A kind of 8. method that paper making pulp is handled using complex enzyme liquid, it is characterised in that use bio-pulping method in pulp stage； Detailed process is as follows：Paper making raw material is prepared into thick slurry, is put into complex enzyme liquid immersion treatment into thick slurry, treatment conditions are：Temperature be 20 DEG C~ 48 DEG C, pH be 2~6.0, be passed through air, digest 36h~60h, be put into bleaching enzyme mixation after complex enzyme liquid processing, be in pH 7.0~9.5, temperature is 40 DEG C~60 DEG C, digests 30min~80min；Wherein, complex enzyme liquid addition is thick slurry dry weight 0.001%~5%；Enzyme mixation addition is bleached as the 0.1%~2% of thick slurry dry weight；Described complex enzyme liquid includes complex enzyme and complex enzyme adjuvant；Wherein, the mass ratio of complex enzyme and complex enzyme adjuvant For 1:30~50；Wherein, in complex enzyme the enzyme activity of laccase be 50U/mL~2000U/mL, the enzyme activity of lignin peroxidase be 50U/mL~1000U/mL, the enzyme activity of manganese peroxidase are 50U/mL~2000U/mL, the enzyme activity of pectase is 100U/ ML~1000U/mL, the enzyme activity of cellulase be 100U/mL~1000U/mL and the enzyme activity of amylase be 100U/mL~ 1000U/mL, the enzyme activity of pepsin are 100U/mL~1000U/mL, the enzyme activity of papain be 100U/mL~ 1000U/mL, the enzyme activity of glyoxal dehydrogenase are 50U/mL~2000U/mL and the enzyme activity of horseradish peroxidase is 50U/ ML~2000U/mL；Complex enzyme adjuvant includes 1~10mol/L MnSO using acetic acid as solvent4, 1~3g/L ascorbic acid, 1~ 2g/L glucose, 1~2g/L alginates, 1~2g/L pectic substance, 1~2mol/L KH2PO4, 0.1~1.0g/L ZnSO4, 0.01~0.1g/L H2BO3, 1~2g/L NaCl and 1~5g/L glutathione；Described bleaching enzyme mixation includes the adjuvant of bleaching enzymes and bleaching enzymes；Wherein, the adjuvant of bleaching enzymes and bleaching enzymes Mass ratio be 1:10~30；In described bleaching enzymes the enzyme activity of zytase be 2500U/mL~3000U/mL, the enzyme activity of mannase be 1500U/mL~2000U/mL, the enzyme activity of catalase are 500U/mL~1000U/mL, the enzyme activity of laccase is 50U/mL ~2000U/mL, the enzyme activity of alkaline pectase are 500U/mL~1500U/mL, the enzyme activity of glyoxal dehydrogenase is 50U/mL The enzyme activity of~2000U/mL and horseradish peroxidase is 50U/mL~2000U/mL；The adjuvant of bleaching enzymes is that concentration is 0.08g/L~0.15g/L N- hydroxyls phthalimides or hydroxamic acid.
- 9. a kind of method that paper making pulp is handled using complex enzyme liquid according to claim 8, it is characterised in that by papermaking Raw material is prepared into paper pulp, and complex enzyme liquid immersion treatment is put into paper pulp, and treatment conditions are：Temperature is 30 DEG C~60 DEG C, pH is 2.5~6.8, be passed through air, digest 36h~60h, bleaching enzyme mixation is put into after complex enzyme liquid processing, pH be 7.0~ 9.0, temperature is 40 DEG C~55 DEG C, digests 30min~80min；Wherein, complex enzyme liquid addition is the 0.001% of pulp dry weight ~5%；Bleach 0.1%~2% that enzyme mixation addition is pulp dry weight.
- 10. a kind of method that paper making pulp is handled using complex enzyme liquid according to claim 8, it is characterised in that adding Before bleaching enzyme mixation, the slurries after being digested to complex enzyme liquid carry out ultraviolet irradiation, add bleaching enzymes after irradiation and mix Liquid is closed, ultraviolet irradiation condition is：In the case where wavelength is 250nm~380nm ultraviolet light, 10min~30min is irradiated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710859395.4A CN107604726B (en) | 2017-09-21 | 2017-09-21 | Method for treating papermaking pulp by using compound enzyme liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710859395.4A CN107604726B (en) | 2017-09-21 | 2017-09-21 | Method for treating papermaking pulp by using compound enzyme liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107604726A true CN107604726A (en) | 2018-01-19 |
| CN107604726B CN107604726B (en) | 2020-07-10 |
Family
ID=61060466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710859395.4A Expired - Fee Related CN107604726B (en) | 2017-09-21 | 2017-09-21 | Method for treating papermaking pulp by using compound enzyme liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107604726B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108411672A (en) * | 2018-04-09 | 2018-08-17 | 山东双圆生物科技有限公司 | A kind of new process using special efficacy composite biological enzyme preparation bamboo chemical pulp |
| CN108505375A (en) * | 2018-03-07 | 2018-09-07 | 山东双圆生物科技有限公司 | Special efficacy composite biological enzyme preparation |
| CN108707321A (en) * | 2018-04-20 | 2018-10-26 | 苏州凌科特新材料有限公司 | A kind of preparation method of compound light blocking film |
| CN111286789A (en) * | 2020-04-08 | 2020-06-16 | 四川玉竹麻业有限公司 | Complex enzyme degumming agent and degumming method |
| CN115404078A (en) * | 2022-09-06 | 2022-11-29 | 太原师范学院 | A method for preparing antioxidant by co-degrading lignin with ionic liquid-compound enzyme |
| CN117887693A (en) * | 2023-12-28 | 2024-04-16 | 河北秸润农业科技有限公司 | Preparation and application methods of novel wheat straw pulping catalyst |
| CN118461348A (en) * | 2024-07-11 | 2024-08-09 | 临邑县临兴木业有限公司 | A pulping process using plant fiber raw materials |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1421570A (en) * | 2002-12-20 | 2003-06-04 | 山东大学 | Enzymatic straw material pulping process |
| US20030102095A1 (en) * | 2001-11-29 | 2003-06-05 | Hill Walter B. | Papermaking process using enzyme-treated sludge, and products |
| CN1616758A (en) * | 2003-11-13 | 2005-05-18 | 中国印钞造币总公司 | Process for biologically pulping |
| US20080066879A1 (en) * | 2006-09-15 | 2008-03-20 | Covarrubias Rosa M | Methods To Control Lipophilic Extractives In Acacia Wood Pulp and Fiber |
| CN101492892A (en) * | 2009-03-11 | 2009-07-29 | 凌受明 | Method for producing paper-pulp by using cotton stalk core or kendir stalk core |
| CN102174504A (en) * | 2011-01-14 | 2011-09-07 | 华南理工大学 | Granular carrier immobilized lipase for treating papermaking white water and preparation method thereof |
| CN102174505A (en) * | 2011-01-14 | 2011-09-07 | 华南理工大学 | Preparation method of granular carrier immobilized bienzyme for treating papermaking white water |
| CN102345244A (en) * | 2010-08-05 | 2012-02-08 | 王凤忠 | Pulping and papermaking process through multiple-composition biological enzyme method |
| CN103555701A (en) * | 2013-10-19 | 2014-02-05 | 沅江浣溪沙酶技术有限公司 | Production method and application of compound enzyme liquid for paper pulp bleaching |
| CN104499337A (en) * | 2014-11-30 | 2015-04-08 | 邵素英 | Bleached compound enzyme and preparation method thereof |
| CN103555702B (en) * | 2013-10-19 | 2015-12-09 | 沅江浣溪沙酶技术有限公司 | The production method of chemical-mechanical pulping complex enzyme liquid and application |
| CN105441412A (en) * | 2014-09-29 | 2016-03-30 | 湖南新鸿鹰生物工程有限公司 | Paper pulp bleaching compound enzyme and preparation method thereof |
| CN106223097A (en) * | 2016-08-28 | 2016-12-14 | 仇颖超 | A kind of method of high paper pulp yield deinking |
-
2017
- 2017-09-21 CN CN201710859395.4A patent/CN107604726B/en not_active Expired - Fee Related
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030102095A1 (en) * | 2001-11-29 | 2003-06-05 | Hill Walter B. | Papermaking process using enzyme-treated sludge, and products |
| CN1421570A (en) * | 2002-12-20 | 2003-06-04 | 山东大学 | Enzymatic straw material pulping process |
| CN1616758A (en) * | 2003-11-13 | 2005-05-18 | 中国印钞造币总公司 | Process for biologically pulping |
| US20080066879A1 (en) * | 2006-09-15 | 2008-03-20 | Covarrubias Rosa M | Methods To Control Lipophilic Extractives In Acacia Wood Pulp and Fiber |
| CN101492892A (en) * | 2009-03-11 | 2009-07-29 | 凌受明 | Method for producing paper-pulp by using cotton stalk core or kendir stalk core |
| CN102345244A (en) * | 2010-08-05 | 2012-02-08 | 王凤忠 | Pulping and papermaking process through multiple-composition biological enzyme method |
| CN102174505A (en) * | 2011-01-14 | 2011-09-07 | 华南理工大学 | Preparation method of granular carrier immobilized bienzyme for treating papermaking white water |
| CN102174504A (en) * | 2011-01-14 | 2011-09-07 | 华南理工大学 | Granular carrier immobilized lipase for treating papermaking white water and preparation method thereof |
| CN103555701A (en) * | 2013-10-19 | 2014-02-05 | 沅江浣溪沙酶技术有限公司 | Production method and application of compound enzyme liquid for paper pulp bleaching |
| CN103555702B (en) * | 2013-10-19 | 2015-12-09 | 沅江浣溪沙酶技术有限公司 | The production method of chemical-mechanical pulping complex enzyme liquid and application |
| CN105441412A (en) * | 2014-09-29 | 2016-03-30 | 湖南新鸿鹰生物工程有限公司 | Paper pulp bleaching compound enzyme and preparation method thereof |
| CN104499337A (en) * | 2014-11-30 | 2015-04-08 | 邵素英 | Bleached compound enzyme and preparation method thereof |
| CN106223097A (en) * | 2016-08-28 | 2016-12-14 | 仇颖超 | A kind of method of high paper pulp yield deinking |
Non-Patent Citations (1)
| Title |
|---|
| 季祥 等: "《生物质能源及废物利用新技术》", 31 December 2012 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108505375A (en) * | 2018-03-07 | 2018-09-07 | 山东双圆生物科技有限公司 | Special efficacy composite biological enzyme preparation |
| WO2019170027A1 (en) * | 2018-03-07 | 2019-09-12 | 山东双圆生物科技有限公司 | Biological enzyme preparation for specific complex |
| CN108411672A (en) * | 2018-04-09 | 2018-08-17 | 山东双圆生物科技有限公司 | A kind of new process using special efficacy composite biological enzyme preparation bamboo chemical pulp |
| CN108707321A (en) * | 2018-04-20 | 2018-10-26 | 苏州凌科特新材料有限公司 | A kind of preparation method of compound light blocking film |
| CN111286789A (en) * | 2020-04-08 | 2020-06-16 | 四川玉竹麻业有限公司 | Complex enzyme degumming agent and degumming method |
| CN111286789B (en) * | 2020-04-08 | 2022-11-15 | 四川玉竹麻业有限公司 | Complex enzyme degumming agent and degumming method |
| CN115404078A (en) * | 2022-09-06 | 2022-11-29 | 太原师范学院 | A method for preparing antioxidant by co-degrading lignin with ionic liquid-compound enzyme |
| CN115404078B (en) * | 2022-09-06 | 2024-02-02 | 太原师范学院 | A method for preparing antioxidants by co-degrading lignin with ionic liquid-complex enzyme |
| CN117887693A (en) * | 2023-12-28 | 2024-04-16 | 河北秸润农业科技有限公司 | Preparation and application methods of novel wheat straw pulping catalyst |
| CN117887693B (en) * | 2023-12-28 | 2024-10-01 | 河北秸润农业科技有限公司 | Preparation and application methods of novel wheat straw pulping catalyst |
| CN118461348A (en) * | 2024-07-11 | 2024-08-09 | 临邑县临兴木业有限公司 | A pulping process using plant fiber raw materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107604726B (en) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107604726A (en) | A kind of method that paper making pulp is handled using complex enzyme liquid | |
| US9683329B2 (en) | Methods of producing a paper product | |
| Valentín et al. | Scots pine (Pinus sylvestris) bark composition and degradation by fungi: Potential substrate for bioremediation | |
| CN100513680C (en) | Paper pulp making technology by biological catalytic cracking method | |
| WO1994029510A1 (en) | Process for modifying, breaking down or bleaching lignin, materials containing lignin or like substances | |
| US9834886B2 (en) | Enzymatic pretreatment of wood in a method for producing mechanical paper pulp | |
| CN108978305B (en) | Complex enzyme preparation and process for preparing paper pulp | |
| CN101223314A (en) | New products and process for integrated forest biorefinery | |
| CN113265898A (en) | Method for pulping wheat straw by using xylanase and pectinase | |
| Yadav et al. | Ligninolytic microbes and their role in effluent management of pulp and paper industry | |
| CN103082393B (en) | Preparation method of tobacco flakes through tobacco stems using biochemical machinery method | |
| Tanveer et al. | Innovations in papermaking using enzymatic intervention: an ecofriendly approach | |
| Kumar et al. | Enzyme cocktail: a greener approach for biobleaching in paper and pulp industry | |
| Puri | Ozone pretreatment to increase digestibility of lignocellulose | |
| CA2541229A1 (en) | Modified method for mechanical pulp production | |
| KR20130058921A (en) | Production method of solubility pulp made from dioscorea batatas | |
| US11091564B2 (en) | Methods for producing a manure-derived bioplastic and bioproducts | |
| Henriksson et al. | 12 Biotechnology in the Forest Industry | |
| CN104611964B (en) | A kind of pulping process of Acacia sulphite process high whiteness semi-chemical pulp | |
| KR100652975B1 (en) | Process for preparing semi-chemical mechanical pulp of corn | |
| KR101282831B1 (en) | Solubility Pulp Made From Dioscorea batatas | |
| CN106283800A (en) | A kind of method of biological pretreatment slurry before defibrination | |
| JPH09273092A (en) | Pretreatment Method for Pulping Oil Palm Petiole | |
| Gupta | A review on advancement of pulp and paper industry | |
| RU2813172C1 (en) | Fibrous semi-finished product from sunflower husks and a method of its production (options) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200710 |