CN101691699A - Deinking method of waste paper alkaline enzyme - Google Patents
Deinking method of waste paper alkaline enzyme Download PDFInfo
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- CN101691699A CN101691699A CN200910035842A CN200910035842A CN101691699A CN 101691699 A CN101691699 A CN 101691699A CN 200910035842 A CN200910035842 A CN 200910035842A CN 200910035842 A CN200910035842 A CN 200910035842A CN 101691699 A CN101691699 A CN 101691699A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
Abstract
The invention discloses a deinking method of waste paper alkaline enzyme, comprising the following steps: carrying out soaking, disintegration, enzyme processing and washing on the waste paper to obtain the processed pulp; adding surface active agent when soaking at a usage amount of 0.10%-2.00%wt, wherein the enzyme processing is carried out under the conditions that the pH is 6-11, the temperature is 45-75 DEG C, and xylanase 30-150 mu/g of oven dry stock, pectinase 40-100 mu/g of oven dry stock and amylase 50-120 mu/g of oven dry stock are adopted to process the disintegrated waste paper for 10-30min. Cellulase can also be added in the enzyme processing procedure with an added quantity of 100 mu/g of oven dry stock. The processing effect is better if enzyme activator, such as sodium chloride is added in the enzyme processing procedure; and the alkaline enzyme can be bathed and used in a matching manner with a plurality of surface active agent, even with compounds with certain oxidation functions; and the process of waste paper deinking technology can be shortened and the bleaching process in deinking by the conventional enzyme method can be left out.
Description
Technical field
The present invention relates to a kind of deinking process for waste paper, particularly a kind of method of utilizing biology enzyme to carry out deinking.
Background technology
Closely during the last ten years, the Waste Paper Handling technology is updated and is perfect, and the waste paper rate of recovery and utilization rate increase year by year.According to the statistics to main product paper countries and regions in 1998, reclaim 1.17 hundred million tons of secondary stocks altogether, the rate of recovery is 38.8%, utilization rate is 42.6%.The waste paper rate of recovery is the highest to be Korea S, reaches 73.8%, and utilization rate is the highest to be Mexico, and according to another the prediction of the United Nations and the World Food Programme, the waste paper utilization rate will reach 50.9% in 2010.Whenever, utilize one ton of waste paper, be equivalent to save 3m
3Timber, 1.2 tons of coals, 600 degree electricity, 100m
3Water.As seen; waste paper recycle to save plant resources with energy-conservation, reduce discharging and have the ten minutes important meaning. in the energy that economizes on resources; also can solve the pollution that the waste paper accumulation causes; realize the unity of opposites of economic development and environmental protection; be the effective way of paper industry sustainable development. in recent years; China's waste paper recovery utilization rate increases year by year; but compared with developed countries; gap is also bigger; old newspaper, outdated magazine paper, the wastepaper rate of recovery are relatively low, reclaim with the deinking technology also relatively backward.
Enzyme process deinking (Enzymatic deinking) is the focus of the current research of deinking papermaking both at home and abroad, after Korea S scholar reported first in 1991 is used cellulase and the poly-enzyme carbohydrase of wood printing ink is removed from the old newspaper slurry, the various countries scholar carries out the research of this respect one after another, the patent of relevant enzyme process deinking also has announcement both at home and abroad all the time, see CN97101654 for details, CN99120426 and Granted publication number are patent of CN1240900C etc.
Enzyme attack printing ink place fiber surface is used in the enzyme process deinking exactly, and is aided with flotation, washing, thereby removes the method for printing ink on the waste paper.This treatment technology can effectively be controlled shape and the Size Distribution thereof that breaks away from ink particle, improves flotation efficiency.In addition, enzyme also has the redeposited effect to fiber of the ink particle of obstruction, thereby can remove the ink toner in the wastepaper effectively. and required chemicals lacks than conventional chemical deinking method, and environmental pollution is little.Compare with chemical deinking slurry, enzyme deinking slurry has good water filtering performance, better physical intensity, higher whiteness and less residual ink.The enzyme process deinking has obtained positive result in the laboratory, what have successfully carries out intermediate experiment and shop test.The biology enzyme that becomes known for deinking mainly contains cellulase, the wooden complex enzyme that gathers enzyme carbohydrase, pectase, amylase and lipase etc. and be made up of them.J.M.Jobbims and N.E.Franks have studied enzymatic Deinking of Mixed Office Waste in September, 1997 on forefathers' basis.Used surfactant is a non-ionic surface active agent, and enzyme then is the mixed enzyme of cellulase and hemicellulase.The experiment of half commercial production scale shows: under neutrallty condition, adopting enzyme and surfactant to mix the method that adds hydrabrusher has obvious deinking efficiency to Mixed Office WasteMOW, and this method has been exempted the conventional chemical de-inking method to NaOH, H
2O
2, chelating and aliphatic acid needs.Printing ink clearance after enzyme/surfactant flotation will exceed more than 10% than conventional chemical deinking; For the deinking of conventional chemical method, whiteness improves 2%; Pulp strength is basic identical; Ash content reduces, and opacity also reduces, and it is believed that this mainly is owing to removed due to toner and the fiber fines.
Recently relevant deinking enzyme research based on zytase or amylase all has report at home and abroad more.Finland scholar Juha Saari once carried out the pilot scale that public paper deinking is operated jointly in overmulling in French moulin Vieux pulp from decoloured waste paper factory before and after 2003, used mixing deinking enzyme has two groups, wherein form by zytase and amylase fully for one group, another group is made up of sweet dextranase, amylase and cellulase, and the last combination of result deinking pulp brightness is better than the latter slightly.Two groups of tests all are added with 0.5% surfactant.
But according to existing, the deinking enzyme that current domestic experimental study is used, it nearly all is acidicenzym, abroad in the like product, except that there are novozyme 342 alkaline deinking enzyme product supplies in Denmark Novozymes Company, other products are also rare. because existing papermaking all carries out under alkali condition, use acidicenzym to want acid adjustment control pH value, when large-scale production, have big difficulty, in addition, mostly enzyme work is lower, the enzyme composition is also more single for existing acidicenzym, requires study and develops more suitable deinking enzyme.
Summary of the invention
The present invention mostly is acidicenzym for the deinking enzyme that solves the prior art existence, and activity is lower, forms more single, difficult shortcoming when being used for extensive deinking and producing, the invention provides a kind of alkaline enzymatic deinking method of waste paper, can deinking under the inclined to one side alkali condition of neutrality, the enzymatic activity height.
A kind of deinking method of waste paper alkaline enzyme, step is: the paper pulp after obtaining handling after waste paper is handled, washed through immersion, size degradation, enzyme, when soaking, add surfactant, use amount is 0.10%-2.00%wt, it is under pH is 6～11,45～75 ℃ condition that described enzyme is handled, adopt zytase 70-200 μ/g oven dry stock, pectase 70-120 μ/g oven dry stock, amylase 8 0-120U/g oven dry stock, to the Waste Paper Handling 10-30min behind the size degradation, former enzyme activity is: pectase 8500 μ/g, zytase 18000 μ/g, amylase 2000U/g.Can also add cellulase when enzyme is handled, the protoenzyme enzyme work of cellulase is 4000 μ/g, and the addition of cellulase is 100 μ/g oven dry stock.Add enzyme activator such as sodium chloride, sodium sulphate when enzyme is handled, the effect of processing can be better, and the addition of enzyme activator is 0.5%-2.0%wt.Described surfactant is nonionic, anion surfactant.Described non-ionic surface active agent is fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, and described anion surfactant is alkylbenzenesulfonate, bisphosphate.
Can after flotation, wash again after adopting method enzyme of the present invention to handle and also can directly wash.
Enzyme treatment step of the present invention is the complex enzyme formulation of being made up of multienzyme that adopts, and fermentation product mainly contain: zytase, pectase and amylase, in addition, can also suitable benefit with a small amount of enzyme activator, as sodium chloride, sodium sulphate etc.Good with nonionic, anion surfactant compatibility, favourable kinase activity improves the effect of deinking efficiency.
The mechanism of action of the present invention's used enzyme compound formulation in the enzyme treatment step is: cellulase, pectase, zytase and amylase mainly act on paper fiber and all kinds of starch based sizing agent, so that waste paper fibre component and printing ink in conjunction with loose, both are easy to separate;
The used zymogenic bacteria of the present invention belongs to the bacillus Sp that has a liking for alkali, is the dustless powder of brown with deinking enzyme product zytase, the pectase of its production, plays the main effect of deinking in the deinking process;
Zytase, pectase can be removed the hemicellulose and the pectin class composition of the association of paper fiber, better act on the paper fiber in order to enzyme, make the combination of ink particle and fiber loosening, and then are able to separate with paper.
Beneficial effect: this enzyme process deinking process has saved the bleaching process that general enzyme process deinking all often has behind flotation Xian Di, this reduces cost to energy-conservation water-saving all is very favourable.The alkaline deinking enzyme that the present invention developed has following obvious advantage
1 can be widely used in deinkings such as disregard message paper (comprising U.S. useless), secondhand book periodical, especially the paper in the office that general DEINKING CHEMICALS is difficult to deinking, as printing paper, copy paper good deinking efficiency is arranged, Mixed Office WasteMOW is carried out the deinking processing also obtained obvious deinking efficiency.
2 can or even have the compound of certain oxidative function to bathe, be used together with many surfactants, can shorten the deinking technical process, save the bleaching process of general enzyme process deinking.
The complex enzyme formulation appropriate pH broad that 3 the present invention are used can carry out deinking under nearly neutral and inclined to one side alkali condition, can exempt the conventional chemical de-inking method to NaOH, H
2O
2Deng needs, favourable raising printing ink clearance, reduce cost.
The used complex enzyme formulation of 4 the present invention can be used for disregard message paper (comprising U.S. useless) and paper in the office deinking, effect is obvious, all can finish with interior at 20min, can comprise existing patent such as CN97101654 by general enzyme process, the deinking time that CN99120426 etc. reported is saved more than 50%.
5. after having passed through enzyme and handling, can also can directly wash in the time of method deinking of the present invention, both simplify step, save the use amount of water again than the patent of CN1240900C through washing again after the flotation without flotation.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 is the waste paper fibre Electronic Speculum figure after the present invention handles.
Fig. 3 is the waste paper fibre Electronic Speculum figure that handles without enzyme.
By Fig. 2,3 more as can be seen, the fiber of handling through the enzyme deinking has broken away from substantially attached to the China ink grain on the fiber, and for the fiber of handling without enzyme, and is high-visible attached to black on the fiber.
The specific embodiment
Below in conjunction with Fig. 1, Fig. 2, Fig. 3, the present invention is elaborated:
The present invention relates to the various enzymes enzyme preparation that all adopts river, Nanjing flat scientific and technological development company to produce, be solid dosage forms.The work of protoenzyme enzyme is: the work of pectase enzyme is 8500 μ/g; Xylanase activity is 15000 μ/g; The amylase enzyme is lived and is 2000U/g; Cellulose enzyme activity is 4000 μ/g.
Embodiment 1
Handle and mix office waste paper
After in beaker, adding the dense required water of slurry of 15%wt, be placed in 60 ℃ the thermostat water bath, add 0.20%-2.00%wt surfactant such as fatty alcohol-polyoxyethylene ether, alkylbenzenesulfonate again.Get 15g over dry mixing office and use waste paper, wherein the ratio of laser stamping paper and electro-photographic paper is 7: 3, and its strip that is torn into 10 * 15cm is put into plastic beaker, soaks 3～5 minutes, starts powerful constant speed mixer, stirs to make repulping of waste paper.And use CH
2COOH or NaOH regulate the pH 7-11 of paper pulp.Add required enzyme amount then, zytase 100-200 μ/g oven dry stock, pectase 70-120 μ/g oven dry stock, amylase 50-100U/g oven dry stock.Reaction time 10-30min.Slurry after enzyme is handled is diluted to 1%wt, adds the anhydrous CaCl of 0.05%-0.20%wt again
2, in flotation cell, carry out flotation, flotation time be slurry after 8-15min, the flotation towards rare to 3L, then by having the sub-sieve washing of 60 order copper mesh.Behind gained slurry survey moisture, take by weighing the slurry that contains the 2g bone-dry paper and in standard fibre dissociates device, discongest, concentration 10%.The ZQJ1-B pattern of producing in machinery plant of northwest light industry institute is copied to get and is copied sheet on the device.
The deinking of Mixed Office WasteMOW alkalescence enzyme the results are shown in Table 1:
Table 1 result
Residual China ink
Surface-activity enzyme time whiteness yield is counted
(μ/g) (min) (%SBD) (%) is (individual in agent (%)
/9cm2)
1 0.220 120 18 91.72 75.1 10
2 0.224 140 16 94.4 83.7 8
3 0.216 160 14 92.56 76.1 16
Annotate: enzyme dosage chain timbers dextranase consumption in the table, down together.
Embodiment 2 handles old newsprint
Handling process is the same with embodiment 1, has just saved the flotation operation, directly washing.After in beaker, adding 15% the dense required water of slurry, be placed in 60 ℃ the thermostat water bath, add 0.20%-1.50% surfactant such as fatty alcohol-polyoxyethylene ether, sodium alkyl benzene sulfonate again, get 15g over dry old newsprint, this waste paper is taken from the Wuhan papermaking company of ringing morning, be U.S. useless 8# of import and 10#, the ratio of 8#/10# is 7/3, and its strip that is torn into 10 * 15cm is put into plastic beaker, soaks 3～5 minutes, start powerful constant speed mixer, stir and make repulping of waste paper.And the pH to 7-11 of adjusting paper pulp.Add required enzyme amount then, zytase 120-200 μ/g, pectase 80-100 μ/g, amylase 60-120U/g.Reaction time 15-30min.After enzyme is handled, with gained slurry batch aqueous cleaning, after the water dilution of every 1g paper pulp with 1000ml, by having the sub-sieve washing of 60 order copper mesh.Behind gained slurry survey moisture, take by weighing the slurry that contains the 2g bone-dry paper and in standard fibre dissociates device, discongest, concentration 10%.The ZQJ1-B pattern of producing in machinery plant of northwest light industry institute is copied to get and is copied sheet on the device.
The deinking of U.S. disregard message paper alkalescence enzyme the results are shown in Table 2:
Table 2 result
The residual ink dot number of testing surface activating agent enzyme pH time whiteness yield
(μ/g) (min) (%SBD) (%) is (individual/9cm for numbering (%)
2)
1 0.91 140 8 18 49.94 74.9 7
2 0.91 160 9 16 52.71 79 3
3 0.91 180 10 14 50.47 3.5 7
Embodiment 3
After in beaker, adding 15% the dense required water of slurry, be placed in 60 ℃ the thermostat water bath, add 0.24%-1.69% surfactant such as fatty alcohol-polyoxyethylene ether, alkylbenzenesulfonate again, get the 15g over dry and mix office waste paper, wherein the ratio of laser stamping paper and electro-photographic paper is 7: 3, and its strip that is torn into 10 * 15cm is put into plastic beaker, soaks 3～5 minutes, start powerful constant speed mixer, stir and make repulping of waste paper.And use CH
2COOH or NaOH regulate the pH 7-11 of paper pulp.Add required enzyme amount then, zytase 80-180 μ/g oven dry stock, pectase 70-100 μ/g oven dry stock, amylase 50-100U/g oven dry stock,, the addition 30-100 μ/g oven dry stock of cellulase, enzyme activator sodium chloride or sodium sulphate 0.5%-2.0%.Reaction time 10-30min.Slurry after enzyme is handled is diluted to 1%wt, adds the anhydrous CaCl of 0.05%-0.20%wt again
2, in flotation cell, carry out flotation, flotation time be slurry after 8-15min, the flotation towards rare to 3L, then by having the sub-sieve washing of 60 order copper mesh.Behind gained slurry survey moisture, take by weighing the slurry that contains the 2g bone-dry paper and in standard fibre dissociates device, discongest concentration 10%wt.The ZQJ1-B pattern of producing in machinery plant of northwest light industry institute is copied to get and is copied sheet on the device.
The deinking of Mixed Office WasteMOW alkalescence enzyme the results are shown in Table 3:
Table 3 result
Residual China ink
Surface-activity enzyme enzyme activator time whiteness yield is counted
(μ/g) (%) (min) (%SBD) is (%) (individual in agent (%)
/9cm
2)
1 0.50 140 0.8 18 91.52 77.1 10
2 1.00 150 1.2 16 92.4 83.5 8
3 1.50 160 1.6 14 95.26 86.1 6
When adding cellulase and enzyme activator as can be known when enzyme is handled by above several embodiment, it is good that the effect of processing will compare, and the consumption that improves surfactant also can obtain reasonable effect.
Claims (7)
1. deinking method of waste paper alkaline enzyme, it is characterized in that, step is: the paper pulp after obtaining handling after waste paper is handled, washed through immersion, size degradation, enzyme, add surfactant when soaking, use amount is 0.10%-2.00%wt, and it is under pH is 6～11,45～75 ℃ condition that described enzyme is handled, adopt zytase 70-200 μ/g oven dry stock, pectase 50-120 μ/g oven dry stock, amylase 70-120U/g oven dry stock is to the Waste Paper Handling 10-30min behind the size degradation.
2. deinking method of waste paper alkaline enzyme as claimed in claim 1 is characterized in that, adds cellulase when enzyme is handled, and the addition of cellulase is 100 μ/g oven dry stock.
3. deinking method of waste paper alkaline enzyme as claimed in claim 1 is characterized in that, adds enzyme activator sodium chloride, sodium sulphate when enzyme is handled, and the addition of enzyme activator is 0.5%-2.0%wt.
4. deinking method of waste paper alkaline enzyme as claimed in claim 1 is characterized in that, enzyme handles after washing again after the flotation.
5. deinking method of waste paper alkaline enzyme as claimed in claim 1 is characterized in that, described surfactant is nonionic, anion surfactant.
6. deinking method of waste paper alkaline enzyme as claimed in claim 5 is characterized in that, described non-ionic surface active agent is fatty alcohol-polyoxyethylene ether, bisphosphate.
7. deinking method of waste paper alkaline enzyme as claimed in claim 5 is characterized in that, described anion surfactant is alkylbenzenesulfonate, alkylphenol polyoxyethylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102517949A (en) * | 2011-12-08 | 2012-06-27 | 东莞市绿微康生物科技有限公司 | Environmentally friendly waste paper deinking method |
| CN103088688A (en) * | 2011-11-02 | 2013-05-08 | 东莞市绿微康生物科技有限公司 | Clean wastepaper deinking production method |
| CN105133409A (en) * | 2015-08-13 | 2015-12-09 | 合肥龙发包装有限公司 | Waste paper deinking method |
| CN107119480A (en) * | 2017-06-16 | 2017-09-01 | 江苏金沃机械有限公司 | A kind of waste paper recycles low ink pulping process |
| CN107974855A (en) * | 2017-12-06 | 2018-05-01 | 常州凯奥机电科技有限公司 | A kind of paper deinking method |
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| CN109024038A (en) * | 2018-08-06 | 2018-12-18 | 上海尤特尔生化有限公司 | The modification pulping process and modified slurry and papermaking process of secondary stock |
| CN110528304A (en) * | 2019-08-27 | 2019-12-03 | 绵阳禾本生物工程有限公司 | A kind of high-efficiency environment friendly Biologic Deinking Agent |
| CN116815537A (en) * | 2023-06-01 | 2023-09-29 | 华南理工大学 | Method for improving fiber strength of waste paper by utilizing modified xylanase and pectase system |
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| CN103088688A (en) * | 2011-11-02 | 2013-05-08 | 东莞市绿微康生物科技有限公司 | Clean wastepaper deinking production method |
| CN103088688B (en) * | 2011-11-02 | 2015-12-02 | 东莞市绿微康生物科技有限公司 | A kind of deinking process for waste paper of cleaner production |
| CN102517949B (en) * | 2011-12-08 | 2013-12-18 | 东莞市绿微康生物科技有限公司 | Environmentally friendly waste paper deinking method |
| CN102517949A (en) * | 2011-12-08 | 2012-06-27 | 东莞市绿微康生物科技有限公司 | Environmentally friendly waste paper deinking method |
| CN105133409A (en) * | 2015-08-13 | 2015-12-09 | 合肥龙发包装有限公司 | Waste paper deinking method |
| CN107119480B (en) * | 2017-06-16 | 2018-08-24 | 江苏浩宇电子科技有限公司 | A kind of waste paper recycles low ink pulping process |
| CN107119480A (en) * | 2017-06-16 | 2017-09-01 | 江苏金沃机械有限公司 | A kind of waste paper recycles low ink pulping process |
| CN107974855A (en) * | 2017-12-06 | 2018-05-01 | 常州凯奥机电科技有限公司 | A kind of paper deinking method |
| CN108787703A (en) * | 2018-05-30 | 2018-11-13 | 余庆县东瑞烟花爆竹有限责任公司 | A kind of processing method of firework display waste |
| CN108787703B (en) * | 2018-05-30 | 2020-05-12 | 余庆县东瑞烟花爆竹有限责任公司 | Method for treating firework setting-off waste |
| CN109024038A (en) * | 2018-08-06 | 2018-12-18 | 上海尤特尔生化有限公司 | The modification pulping process and modified slurry and papermaking process of secondary stock |
| CN110528304A (en) * | 2019-08-27 | 2019-12-03 | 绵阳禾本生物工程有限公司 | A kind of high-efficiency environment friendly Biologic Deinking Agent |
| CN116815537A (en) * | 2023-06-01 | 2023-09-29 | 华南理工大学 | Method for improving fiber strength of waste paper by utilizing modified xylanase and pectase system |
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