CN1718918A - Method of removing resin in paper pulp by multienzyme synergistic action - Google Patents

Method of removing resin in paper pulp by multienzyme synergistic action Download PDF

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Publication number
CN1718918A
CN1718918A CN 200510035390 CN200510035390A CN1718918A CN 1718918 A CN1718918 A CN 1718918A CN 200510035390 CN200510035390 CN 200510035390 CN 200510035390 A CN200510035390 A CN 200510035390A CN 1718918 A CN1718918 A CN 1718918A
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paper pulp
resin
lipase
lignin degradation
degradation enzyme
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CN1718918B (en
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何北海
林鹿
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

The present invention utilizes the combination action or composite action of lignin degradation enzyme and lipase to remove resin from paper pulp. Its resin removed rate is above 90%, and said method can obviously reduce COD pollution load in waste water.

Description

A kind of multienzyme synergism effect removes the method for resin in the paper pulp
Technical field
The present invention relates to the method that a kind of multienzyme synergism effect removes resin in the paper pulp, specifically relate to a kind of collaborative i.e. associating that utilizes lignin degradation enzyme and lipase or compound action to remove the method for resin in mechanical pulp, sulfite pulp and the chemi-mechanical pulp.
Background technology
Resin is a kind of composition of paper making raw material, generally accounts for about 2~6% of timber dry weight.The resinae material is to be present in paper making raw material and to follow major pollutants in the whole process of production, difficult degradation is not easy to handle, and these pollutants enter in the waste water with the paper machine system, though making after the wastewater treatment can qualified discharge but can't further clean reuse, has wasted abundant water resource.The existence of resinae material causes pulp-making waste-water to be difficult to handle back cleaning reuse; Be present in the resinae material of copying in the paper system and can cause " pitch trouble ", promptly cause paper machine broken end, paper whiteness and intensity decreases and cause phenomenon such as the serious obstruction of machinery equipment.At present, paper mill is removed resin and is realized on a kind of electrolytic film, need to consume a large amount of electric energy, and this method is a kind of method that shifts the resin composition, the resin composition is not removed; Also having a kind of method is to add some dispersants such as kaolin, and the resinae material is disperseed, and it is agglomerating to be not easy to condense on paper or equipment surface.The existing removal methods of domestic paper mill not only will expend a large amount of electric energy, and is a kind of method that shifts resin, does not have degradative resin, and a large amount of resin compositions still can enter and copy in paper and the waste water system, makes waste water be difficult to reuse up to standard.
Proposed in recent years both at home and abroad with fungi comprise Ceratocystis fimbriata Strains (Ophiostoma, piliferum) and whiterot fungi remove wood chip or remove the patented technology of resin in the paper pulp as penetrating arteries and veins side bacterium (Phlebia radiate) with lipase, have certain degreasing effect.But there are long action time (the fungi effect needs more than 3 days), degreasing effect few (lipase acts on degreasing rate<50% separately).Therefore, it is very necessary developing the deresinate new technology with independent intellectual property right.
Summary of the invention
The objective of the invention is to shortcoming, provide a kind of multienzyme synergism effect to remove the method for resin in the paper pulp at the prior art existence.Lignin degradation enzyme in this method has peroxidation to the resinae material, and the resin enzyme has hydrolysis to the resinae material.Compare with present defatting technology, have better degreasing effect, thereby eliminate paper industry " pitch trouble " problem that the resinae material causes, realize the pulping process cleaner production.
For achieving the above object, the present invention has taked following technical scheme:
The multienzyme synergism effect removes the method for resin in the paper pulp, it is characterized in that removing resin in the paper pulp for the synergy by lignin degradation enzyme and lipase or compound action.Described paper pulp is mechanical pulp, sulfite pulp or chemi-mechanical pulp.
The method that described multienzyme synergism effect removes resin in the paper pulp specifically comprises the steps: for the synergy by lignin degradation enzyme and lipase removes resin in the paper pulp
(1) the lignin degradation enzyme acts on paper pulp separately;
Mix with a kind of in the lignin degradation enzyme or by 1: 1 weight ratio wantonly two kinds or join in the paper pulp by three kinds of weight ratio mixing in 1: 1: 1, after paper pulp fully mixes, react 30~240min in the citric acid of 0.1~100mmol/L of pH2~6.5 or acetate buffer solution, reaction temperature is 18~50 ℃;
Total addition of lignin degradation enzyme is 0.001~5% of a paper pulp dry weight;
Described lignin degradation enzyme is respectively the lignin peroxidase of active 100~15000IU/ml, manganese peroxidase and the activity of active 100~15000IU/ml is the laccase of 100~15000IU/ml;
(2) after the lignin degradation enzyme reaction, add the lipase reaction that accounts for paper pulp dry weight 0.001~5% again, lipase active 10~20000IU/ml; Be reflected in the 0.025mol/L phosphate buffer of pH3~7.5 and carry out, action time 30~240min, room temperature.
The method that above-mentioned multienzyme synergism effect removes resin in the paper pulp also can remove the resin in the paper pulp for the compound action by lignin degradation enzyme and lipase, specifically comprises the steps:
Any and lipase in the lignin degradation enzyme are joined in the paper pulp lipase active 10~20000IU/ml simultaneously by 1: 1 weight ratio; Be reflected in the citric acid of 0.1~100mmol/L of pH2~6.5 or the acetate buffer solution and carry out, action time 30~240min, temperature is 28~45 ℃;
Described lignin degradation enzyme is respectively the lignin peroxidase of active 100~15000IU/ml, manganese peroxidase and the activity of active 100~15000IU/ml is the laccase of 100~15000IU/ml;
Total addition of lignin degradation enzyme is 0.001~5% of a paper pulp dry weight.
Lignin degradation enzyme described in the technique scheme is from whiterot fungi, and whiterot fungi produces consist of (g/L) of enzyme fluid nutrient medium: 0.1~1g K 2HPO 4, 1~10g KH 2PO 4, 0.24~2.4g MgSO 4, 0.1~1.0g CaCl 2, 0.01~0.1g NaCl, 0.1~1.0g FeSO 47H 2O 2, 0.01~0.1g ZnSO 47H 2O 2, 0.02~0.2gCuSO 45H 2O 2, 0.08~0.4g MnSO 4H 2O 2, 0.01~0.1gCoCl 2, 0.01~0.1g puridoxine hydrochloride and add 1~5% glucose and 0.1~1.0% ammonium tartrate as carbon source and nitrogenous source; During cultivation, pH2~6, temperature are 18~39 ℃;
Screening obtains the dote of whiterot fungi from forest through isolation and selection culture mediums (aperture>60 purpose wood powder culture mediums), and further pass through ultraviolet radiation mutagenesis, by the hereditary and selection in 7~10 generations, the bacterial strain that filters out is the microorganism of public use.Use the domestication of previous crops adaptability.
Described lipase is fruit trichosporon cutaneum, penicillium expansum, geotrichum candidum or rhizopus, and trichosporon cutaneum, penicillium expansum, geotrichum candidum and rhizopus screen in the spontaneous bacterium colony from wood chips such as masson pine, and use Co 60The width of cloth is according to 1~30min or 40Wt ultraviolet ray irradiation 1~5min; The bacterial strain that does not produce blue metabolite that obtains behind 10~18 generation hereditary and selections is the microorganism of public use.Use the domestication of previous crops adaptability.
The fermentation condition of above-mentioned lipase can be following two kinds:
(1) full fat soybean 1~4%, MgSO 40.01 K~1%, 2HPO 4~1%, 0.1 (NH4) 2SO 40.2~2%, peanut oil 0.1~2%, the pH nature.
(2) dried silkworm chrysalis meal 1~10%, sucrose 0.5~2%, olive oil 0.1~1.5%, (NH 4) 2SO 40.1 MgSO~2%, 47H 2O 0.05-2%, K 2HPO 40.01~1%, the pH nature.
The best condition of enzyme production of described lipase is: initial pH6.5~9.5,30 ℃ of cultivation 12~60h, produce alkaline fat enzyme activity 10~20000IU/ml.
Compared with the prior art, the beneficial effect that the present invention has is: the resin in the paper pulp is carried out effective elimination, and the total removal efficiency of resin surpasses 90%, and pulp-making waste-water can clean reuse after the one-level biochemical treatment.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment:
Embodiment 1
Raw material: Masson Pine TMP slurry, TG mean value 1.86%.Lignin degradation enzyme (for the lignin peroxidase of active 153IU/ml) and lipase (active is 178IU/ml) are joined in the paper pulp by 1: 1 liquor ratio, join in the paper pulp, total addition is 0.01% (v/w) of paper pulp dry weight; After fully mixing with paper pulp, react 40min in the citric acid of the 0.2mmol/L of pH6.5 or acetate buffer solution, temperature is 39 ℃; After the ligninase reaction, add the lipase that accounts for paper pulp dry weight 0.01%, lipase active 178IU/ml again; Be reflected in the 0.25mol/L phosphate buffer of pH7.2 and carry out, action time 50min; Room temperature.
The result is as shown in table 1:
The paper pulp degreasing result of table 1. after embodiment 1 described condition is handled
The enforcement time TG content (%) before enzyme is handled TG content (%) before enzyme is handled Resin removal efficiency (%)
2004.09.10 2004.11.12 2004.12.14 2005.01.25 1.86 1.88 1.83 1.85 0.14 0.12 0.15 0.11 92.5 93.6 91.8 94.1
Annotate: TG content is the content of resinous substances in the paper pulp.
Embodiment 2
Raw material: Masson Pine TMP slurry, TG mean value 1.86%.Lignin degradation enzyme (for the lignin peroxidase of active 267IU/ml) and lipase (active is 303IU/ml) join in the paper pulp by 1: 1 liquor ratio, and total addition is 0.03% (v/w) of paper pulp dry weight; Be reflected in the 0.3mmol/L citrate buffer solution of pH6.5 and carry out, action time 50min, temperature is 35 ℃.
The result is as shown in table 2:
The paper pulp degreasing result of table 1. after embodiment 1 described condition is handled
The enforcement time TG content (%) before enzyme is handled TG content (%) before enzyme is handled Resin removal efficiency (%)
2004.09.11 2004.11.13 2004.12.15 2005.01.26 1.85 1.87 1.89 1.86 0.13 0.09 0.11 0.08 93.0 95.2 94.2 95.7
Annotate: TG content is the content of resinous substances in the paper pulp.
Embodiment 3
Raw material: masson pine sulfonation machine slurry, TG mean value 1.93%.Lignin degradation enzyme (for the lignin peroxidase of active 219IU/ml) and lipase (active is 248IU/ml) join in the paper pulp by 1: 1 liquor ratio, and total addition is 0.03% (v/w) of paper pulp dry weight; Be reflected in the 0.15mmol/L citrate buffer solution of pH 6.5 and carry out, action time 55min, temperature is 36 ℃.
The result is as shown in table 2:
The paper pulp degreasing result of table 1. after embodiment 1 described condition is handled
The enforcement time TG content (%) before enzyme is handled TG content (%) before enzyme is handled Resin removal efficiency (%)
2004.09.11 2004.11.13 2004.12.15 2005.01.26 1.93 1.92 1.96 1.94 0.12 0.17 0.13 0.15 93.8 91.2 93.4 92.3
Annotate: TG content is the content of resinous substances in the paper pulp.

Claims (9)

1, a kind of multienzyme synergism effect removes the method for resin in the paper pulp, it is characterized in that removing resin in the paper pulp for the synergy by lignin degradation enzyme and lipase or compound action.
2, multienzyme synergism effect according to claim 1 removes the method for resin in the paper pulp, it is characterized in that described paper pulp is mechanical pulp, sulfite pulp or chemi-mechanical pulp.
3, multienzyme synergism effect according to claim 1 removes the method for resin in the paper pulp, it is characterized in that specifically comprising the steps: for the synergy by lignin degradation enzyme and lipase removes resin in the paper pulp
(1) the lignin degradation enzyme acts on paper pulp separately;
Mix with a kind of in the lignin degradation enzyme or by 1: 1 weight ratio wantonly two kinds or join in the paper pulp by three kinds of weight ratio mixing in 1: 1: 1, after paper pulp fully mixes, react 30~240min in the citric acid of 0.1~100mmol/L of pH 2~6.5 or acetate buffer solution, reaction temperature is 18~50 ℃;
Total addition of lignin degradation enzyme is 0.001~5% of a paper pulp dry weight;
Described lignin degradation enzyme is respectively the lignin peroxidase of active 100~15000IU/ml, manganese peroxidase and the activity of active 100~15000IU/ml is the laccase of 100~15000IU/ml;
(2) after the lignin degradation enzyme reaction, add the lipase reaction that accounts for paper pulp dry weight 0.001~5% again, lipase active>100IU/ml; Be reflected in 0.025~2.5mol/L phosphate buffer of pH3~7.5 and carry out, action time 30~240min, room temperature condition.
4, multienzyme synergism effect according to claim 1 removes the method for resin in the paper pulp, it is characterized in that specifically comprising the steps: for the compound action by lignin degradation enzyme and lipase removes resin in the paper pulp
Any and lipase in the lignin degradation enzyme are joined in the paper pulp lipase active 10~20000IU/ml simultaneously by 1: 1 weight ratio; Be reflected in the citric acid of 0.1~100mmol/L of pH2~6.5 or the acetate buffer solution and carry out, action time 30~240min, temperature is 28~45 ℃;
Described lignin degradation enzyme is respectively the lignin peroxidase of active 100~15000IU/ml, manganese peroxidase and the activity of active 100~15000IU/ml is the laccase of 100~15000IU/ml;
Total addition of lignin degradation enzyme is 0.001~5% of a paper pulp dry weight.
5, remove the method for resin in the paper pulp according to claim 3 or 4 described multienzyme synergism effects, it is characterized in that described lignin degradation enzyme from whiterot fungi, what whiterot fungi produced the enzyme fluid nutrient medium consists of (g/L): 0.1~1gK 2HPO 4, 1~10g KH 2PO 4, 0.24~2.4g MgSO 4, 0.1~1.0g CaCl 2, 0.01~0.1g NaCl, 0.1~1.0g FeSO 47H 2O 2, 0.01~0.1g ZnSO 47H 2O 2, 0.02~0.2g CuSO 45H 2O 2, 0.08~0.4g MnSO 4H 2O 2, 0.01~0.1g CoCl 2, 0.01~0.1g puridoxine hydrochloride and add 1~5% glucose and 0.1~1.0% ammonium tartrate as carbon source and nitrogenous source;
During cultivation, pH2~6, temperature are 18~39 ℃.
6, remove the method for resin in the paper pulp according to claim 3 or 4 described multienzyme synergism effects, it is characterized in that described lipase is fruit trichosporon cutaneum, penicillium expansum, geotrichum candidum or rhizopus.
7, multienzyme synergism effect according to claim 6 removes the method for resin in the paper pulp, it is characterized in that the fermentation condition of described lipase is:
Full fat soybean 1~4%, MgSO 40.01 K~1%, 2HPO 4~1%, 0.1 (NH4) 2SO 40.2~2%, peanut oil 0.1~2%, pH nature.
8, multienzyme synergism effect according to claim 6 removes the method for resin in the paper pulp, it is characterized in that the fermentation condition of described lipase is:
Dried silkworm chrysalis meal 1~10%, sucrose 0.5~2%, olive oil 0.1~1.5%, (NH 4) 2SO 40.1 MgSO~2%, 47H 2O 0.05-2%,, K 2HPO 40.01~1%.
9, multienzyme synergism effect according to claim 6 removes the method for resin in the paper pulp, it is characterized in that the condition of enzyme production of described lipase is: initial pH cultivates 12~60h for 6.5~9.5,30 ℃, produces alkaline fat enzyme activity 10~20000IU/ml.
CN 200510035390 2005-06-24 2005-06-24 Method of removing resin in paper pulp by multienzyme synergistic action Expired - Fee Related CN1718918B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN103061184A (en) * 2012-12-26 2013-04-24 泰兴市一鸣生物制品有限公司 Method of controlling secondary gummy substances by using lipase
CN103074795A (en) * 2012-12-26 2013-05-01 泰兴市一鸣生物制品有限公司 Method for controlling secondary stickies through lipase
CN103289982A (en) * 2012-03-01 2013-09-11 烟台大学 Preparation of novel immobile zymophore
CN106223090A (en) * 2016-07-29 2016-12-14 联盛纸业(龙海)有限公司 A kind of wood chip defibrator process slurry substitutes OCC and joins the production method copying high-grade single spreading coated duplex board with grey back
CN106223091A (en) * 2016-07-29 2016-12-14 联盛纸业(龙海)有限公司 A kind of brush wood wood chip defibrator process slurry substitutes OCC slurry and joins the production method copying high-grade cardboard

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN103289982A (en) * 2012-03-01 2013-09-11 烟台大学 Preparation of novel immobile zymophore
CN103289982B (en) * 2012-03-01 2015-09-30 烟台大学 A kind of preparation of novel fixed enzyme vector
CN103061184A (en) * 2012-12-26 2013-04-24 泰兴市一鸣生物制品有限公司 Method of controlling secondary gummy substances by using lipase
CN103074795A (en) * 2012-12-26 2013-05-01 泰兴市一鸣生物制品有限公司 Method for controlling secondary stickies through lipase
CN103074795B (en) * 2012-12-26 2015-04-29 泰兴市一鸣生物制品有限公司 Method for controlling secondary stickies through lipase
CN106223090A (en) * 2016-07-29 2016-12-14 联盛纸业(龙海)有限公司 A kind of wood chip defibrator process slurry substitutes OCC and joins the production method copying high-grade single spreading coated duplex board with grey back
CN106223091A (en) * 2016-07-29 2016-12-14 联盛纸业(龙海)有限公司 A kind of brush wood wood chip defibrator process slurry substitutes OCC slurry and joins the production method copying high-grade cardboard
CN106223091B (en) * 2016-07-29 2017-12-15 联盛纸业(龙海)有限公司 A kind of brush wood wood chip defibrator process slurry substitutes OCC slurries with the production method for copying high-grade cardboard
CN106223090B (en) * 2016-07-29 2017-12-15 联盛纸业(龙海)有限公司 A kind of wood chip defibrator process slurry substitutes OCC and matches somebody with somebody the production method for copying high-grade one side coating coated duplex board with grey back

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