CN103147334A - Waste paper deinking method using mixed enzyme - Google Patents
Waste paper deinking method using mixed enzyme Download PDFInfo
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- CN103147334A CN103147334A CN201210574470XA CN201210574470A CN103147334A CN 103147334 A CN103147334 A CN 103147334A CN 201210574470X A CN201210574470X A CN 201210574470XA CN 201210574470 A CN201210574470 A CN 201210574470A CN 103147334 A CN103147334 A CN 103147334A
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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
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- 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
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Abstract
The invention relates to a waste paper deinking method using mixed enzyme. The waste paper deinking method using the mixed enzyme mainly solves the problem in the prior art of poor deinking effect. The waste paper deinking method using the mixed enzyme includes a first step of obtaining serous fluid A by stirring and mixing deinking agent aqueous solution with waste papers under the condition that potential of hydrogen (pH) is equal to 7.0 to 7.5, wherein the deinking agent aqueous solution comprises sodium aliphatate which is a source of vegetable oil and/ or non-ionic surface active agent which is expressed by sylvite, formula RO(CH2CH2O)nH, wherein R is C10 to C18 of alkyl group, and n is equal to 3 to 12, and the deinking agent aqueous solution further comprises cellulase, lipase and amylase, a second step of adding water to the serous fluid A and obtaining serous fluid B by mediating the pH to be equal to 6.5 to 6.9, and a third step of obtaining deinking serous fluid by conducting flotation process on the serous fluid B. The waste paper deinking method using the mixed enzyme has the advantages of being capable of well solving the technical problems and being used in waste paper deinking production.
Description
Technical field
The present invention relates to adopt the deinking process for waste paper of mixed enzyme.
Background technology
Waste paper regenerated utilization meets the growth requirement of low-carbon (LC) conservation-minded society.Make high-quality paper product for the fiber that reclaims is satisfied from waste paper, usually the printing ink in waste paper need to be removed.
The method of tradition deinking is chemical method.In the chemical method deinking process for waste paper, usually can use NaOH, sodium metasilicate, chelating agent, hydrogen peroxide, dispersant, trapping agent and agglomerant.In order to make ink particle fully break away from the surface of waste paper fibre, Chemical Deinking technique need to be carried out in the medium of higher alkalisation usually, and for example pH is even up to 11.Use due to high alkalinity medium in Chemical Deinking technique, cause the flavescence of cellulose fiber peacekeeping ligno-ccllulose, in order to obtain the recycled writing paper fiber of high whiteness, also need to use oxidative bleaches (for example hydrogen peroxide) or reducibility bleaching agent (for example industrial insurance powder) in deinking process for this reason.The existence of high alkalinity medium in deinking process it is reported and also can cause the paper pulp fiber recurring structure to change that make the degradations such as paper strength that make, a large amount of employings due to chemicals simultaneously all cause adverse influence to production equipment and environment.
In view of the foregoing, the method for Researches of Enzymatic-Deinking on Waste Paper occurred, Enzymatic Deinking is due to the use amount that can reduce chemicals thereby environmental protection more.
Sui Zhenying etc. (mixed enzyme is used for the research [J] of laser printing deinking. Chemical Engineering, 2009,37 (9): 44～47) studied cellulase, amylase and lipase and their mixed enzyme, mixed enzyme and their mixed enzyme in the impact on deinking efficiency of different proportionings, temperature, pH value.
Chinese patent literature CN101718050A (applying date 2009.11.13, open day 2010.06.02) a kind of method of Researches of Enzymatic-Deinking on Waste Paper is disclosed, comprise cellulase, lipase, amylase, zytase, surfactant in its deinking agent that adopts, comprise following technological process: the preparation of (1) deinking agent: one or more make complex enzyme to add alkaline lipase, amylase, zytase in cellulase; In complex enzyme, each component ratio is: 2000～10000u cellulase, 10000～100000u alkaline lipase, 1000～5000u zytase and 8000～15000u amylase, then add the surfactant of 0.05～0.15 kilogram to obtain described deinking agent in described complex enzyme; (2) pulper pulping: add the water of 40～60 ℃ in pulper, carry out the shredded paper operation after dropping into deinking agent and sodium metasilicate in the waste paper; (3) enter FLOTATION SEPARATION printing ink operation and obtain the deinking slurries.Can find out from above-mentioned disclosed content, the method still needs to use the alkaline matter sodium metasilicate.Entirely so its record is not about the pH actual conditions in claimed technical scheme, but owing to having used sodium metasilicate, and the deinking wastewater pH that lists in the table of the 4/5th page, its specification 8.08 can find out, the pH in its deinking process should be more than 8.
(its priority data is 10164835.0 2010.06.03EP and 61/303 to another part patent documentation CN102753753A, 828 2010.02.12US) a kind of Researches of Enzymatic-Deinking on Waste Paper method is also disclosed subsequently, as follows to its claimed technical scheme summary: (a) will be wherein under at least about 3% denseness at least 25wt% be that the printing paper slurrying of old newsprint obtains slush pulp; (b) process described slush pulp with the deinking system, described system comprises: (i) lipase and at least a combination that is selected from the second enzyme of amylase, xylosidase or cellulase, and (ii) its amount is the non-ionic surface active agent that effectively printing ink discharged from described slush pulp; (c) separate the printing ink that discharges in the deinking step from described slush pulp, so that the slush pulp of deinking to be provided.It is also to comprise alkaline reagent and derived from the soap of vegetable oil in deinking that the document further discloses its preferred technical scheme in its claim 31.
But there is the poor problem of deinking efficiency in existing mixed enzyme Deinking Technology.
Summary of the invention
There is the poor problem of deinking efficiency in the existing mixed enzyme Deinking Technology that the present invention will solve, and a kind of deinking process for waste paper that adopts mixed enzyme is provided, and the method has advantages of that deinking efficiency is good.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: adopt the deinking process for waste paper of mixed enzyme, comprise the steps:
(1) under temperature was 25～55 ℃, the condition of pH=7.0～7.5, the deinking agent aqueous solution and waste paper mixed, and incorporation time is 5～40 minutes, obtains spent pulp liquors A; Wherein the weight ratio that feeds intake of waste paper and the deinking agent aqueous solution is 100: (300～900); The described deinking agent aqueous solution contains anion surfactant and non-ionic surface active agent, and in weight ratio, waste paper: anion surfactant: non-ionic surface active agent is 100: (0.05～0.15): (0.05～1.0); Described anion surfactant is at least a in the aliphatic acid potassium in vegetable oil source or sodium soap; Described non-ionic surface active agent general molecular formula is RO (CH
2CH
2O)
nH, wherein R is C
10～C
18Alkyl, n=3～12; Go back cellulase 0.2～0.5u/g, lipase 0.3～1.0u/g and amylase 0.2～1.0u/g in the described deinking agent aqueous solution;
(2) thin up and add acidic ph modifier in the spent pulp liquors A obtains take the waste paper weight concentration as 0.6～1.0wt%, the spent pulp liquors B of pH=6.5～6.9;
(3) spent pulp liquors B is carried out the flotation processing and obtain the deinking slurries.
The temperature of step in technique scheme (1) is preferably 40～50 ℃.The pH of step (1) is preferably 7.2～7.4.The described vegetable oil of step (1) is at least a in soybean oil, sunflower oil, corn oil, rapeseed oil, peanut oil, cottonseed oil, olive oil, tea oil, palm oil or coconut oil preferably; Further preferred at least a in soybean oil, sunflower oil, corn oil, rapeseed oil, peanut oil, cottonseed oil, olive oil, tea oil; Preferred at least a in soybean oil, sunflower oil, corn oil, rapeseed oil, peanut oil, cottonseed oil further; At least a in soybean oil, sunflower oil, corn oil most preferably; The described anion surfactant of step (1) the most preferably forms by the anion surfactant in soybean oil source with by the anion surfactant in cottonseed oil source.
The incorporation time of step in technique scheme (1) is preferably 10～20 minutes.R is preferably C
12～C
14Alkyl, preferred n=5～10.Described in step (2), pH adjusting agent can be organic acid or inorganic acid, can be also that the aqueous solution is acid salt, but is preferably in EDTA Dipotassium salt or disodium EDTA, ethylenediamine tetra-acetic acid di-ammonium salts at least a.The described pH of step (2) is preferably 6.5～6.8.
The temperature of step in technique scheme (3) flotation is preferably 20～85 ℃; More preferably 20～60 ℃ of flotation temperatures.Preferred 10～the 30min of flotation time, more preferably 10～20min.
Technique scheme is applicable to the deinking of various waste paper, and described waste paper can be for example at least a in crushed news, useless laser printing word, useless magazine paper.
For satisfying the requirements at the higher level to pulp brightness, technical scheme of the present invention can also increase the hydrogen peroxide bleaching operation afterwards in completing steps (1), for example hydrogen peroxide bleaching can: (a) carry out afterwards and between step (2) in step (1); (b) carry out afterwards in step (3).
The connotation that the aliphatic acid potassium of originating as the vegetable oil of anion surfactant in the present invention or sodium soap have is: these aliphatic acid potassium or sodium soap can (i) obtain from the vegetable oil saponification, can be also that (ii) soap stock from corresponding vegetable oil industry obtains for the source.The anion surfactant that these two kinds of approach obtain all is applicable to the present invention and has identical result of use, but obtains more to one's profit economically from the soap stock with corresponding vegetable oil.
Contain the amount of various enzymes in the solution of deinking agent described in the present invention take u/g as unit representation, its implication is stipulated by light industry standard QB 2583-2003 when relating to cellulase content, by GB/T 23535-2009 regulation, stipulated by GB 8275-2009 when relating to amylase when relating to lipase.As long as the enzyme dosage that represents with u/g is as described in above-mentioned technical scheme, the source of concrete enzyme used is not particularly limited, and above-mentioned enzyme can use with the form of the zymotic fluid of bacterium producing multi enzyme preparation, can be also the commercially available enzyme product through purifying.All adopt commercially available cellulase (cellulase EC3.2.1.4), commercially available lipase (Lipase EC3,1,1,3), commercially available amylase (α-amylase EC3.2.1.1) to be used for experiment in the embodiment of the present invention.
In an embodiment to being not that the factor of key point of the present invention is fixed, so that obtain having more the experimental result of comparativity, be not that the inventive method only adopts these rigid conditions just can reach purpose of the present invention, on technical scheme disclosed by the invention basis, those skilled in the art can rationally determine these factors in conjunction with this area customary means.Corresponding to step of the present invention (1), fixed following factor at embodiment: step (1) is carried out in the cylinder body volume is the FORMAX450H high-concentration pulper of 12L, with paper knife, the fragment that waste paper is cut into 25mm * 25mm is used for experiment, the pulper rotating speed is 1500r/min.Corresponding to having fixed following factor in step of the present invention (3) embodiment: step (3) is carried out in the FORMAX of 28L L-100 type flotation cell, and take air as flotation gas, volume of air is take status of criterion lower volume air intake as 20m
3/ h.
The water of using in the deinking agent aqueous solution of step in the embodiment of the inventive method (1), step (2) are diluted added water, all adopt running water.pH fluctuation between 6.5～8.5 usually due to running water, exceed the required pH condition of step (1) after can causing the deinking agent aqueous solution and waste paper mixing, at this moment for the accurate control of performing step (1) pH, those skilled in the art will know that by under accurate pH test paper or the indication of accurate pH meter, by adding acidic materials (acetic acid for example in the mixture that consists of to the deinking agent aqueous solution and waste paper, hydrochloric acid, sulfuric acid) or add alkali (ammoniacal liquor for example, sodium carbonate, potassium hydroxide, NaOH) pH is controlled the required value of step (1), and weak acid (for example acetic acid), weak base (ammoniacal liquor for example, sodium carbonate) easier for pH value fine setting operation.
Deinking Efficiency in embodiment is to adopt Technidyne Color Touch ERIC950 type residual ink analyzer, and the ERIC value of measuring the contrast slurries according to international standard ISO-22754-2008 regulated procedure (is expressed as ERIC
The contrast slurries) and the ERIC value of the deinking slurries that obtain of step (3) (be expressed as ERIC
The deinking slurries), the computing formula of Deinking Efficiency is: Deinking Efficiency=[(ERIC
The contrast slurries-ERIC
The deinking slurries)/ERIC
The contrast slurries] * 100%; Wherein for measuring Deinking Efficiency, the preparation method of contrast slurries is except the water consumption substitution deinking agent aqueous solution, and all the other operations and condition are all identical with step (1).
After adopting technical scheme of the present invention, can find out from embodiment, Deinking Efficiency can reach 86.7%, has obtained technique effect preferably, can be used in the deinking production of waste paper.
The present invention will be further described below in conjunction with the specific embodiment.
The specific embodiment
[embodiment 1]
Step (1): under temperature is 45 ℃, pH=7.3 condition, the deinking agent aqueous solution and waste paper are mixed in the FORMAX450H high-concentration pulper, incorporation time is 15min, obtains spent pulp liquors A; Wherein the weight ratio that feeds intake of waste paper and the deinking agent aqueous solution is 100: 600; The deinking agent aqueous solution contains anion surfactant and non-ionic surface active agent, and in weight ratio, waste paper: anion surfactant: non-ionic surface active agent is 100: 0.10: 0.5; Anion surfactant is the sodium soap in soybean oil source; Non-ionic surface active agent is lauryl alcohol polyoxyethylene (7) ether, i.e. RO (CH in general molecular formula
2CH
2O)
nThe R of H is C
12Alkyl, n=7; Cellulase 0.4u/g, lipase 0.6u/g and amylase 0.6u/g in the deinking agent aqueous solution.The deinking agent aqueous solution and waste paper gross weight are 8000 grams.Waste paper is the People's Daily in November, 2011.
Step (2): thin up and add acidic ph modifier in the spent pulp liquors A, obtain take the waste paper weight concentration as 0.8wt%, the spent pulp liquors B of pH=6.7, acidic ph modifier is EDTA2Na.
Step (3): 25 kilograms of waste liquid slurries B are placed in the flotation of BFORMAX L-100 type flotation cell obtain the deinking slurries.Flotation gas is air, and volume of air is take status of criterion lower volume air intake as 20m
3/ h.30 ℃ of flotation temperatures, flotation time 15min.
After tested, Deinking Efficiency is 83.4%.For ease of relatively main technological parameter and test result being listed in table 1 and table 2
[embodiment 2]～[embodiment 20]
Step (1): except anion surfactant changed, other operations were all with the step (1) of embodiment 1.
Step (2): all the step (2) with embodiment 1 is identical in operation.
Step (3): except flotation temperature changed, all the other operations were all identical with embodiment 1 step (3).Measure Deinking Efficiency.For ease of relatively the technological parameter and the measurement result that change being listed in table 1 and table 2.
[embodiment 21]～[embodiment 32]
Step (1): except the weight ratio that feeds intake of temperature, pH, incorporation time, waste paper and the deinking agent aqueous solution, in the waste paper of weight ratio: anion surfactant: non-ionic surface active agent, anion surface active can agent, the consumption of three kinds of enzymes changes in the R in the non-ionic surface active agent structure and n, the deinking agent aqueous solution, other operations were all with the step (1) of embodiment 1.
Step (2): except the pH of the concentration of pH adjusting agent, spent pulp liquors B, spent pulp liquors changed, all the step (2) with embodiment 1 was identical in all the other operations.
Step (3): except flotation temperature and flotation time changed, all the other operations were all identical with embodiment 1 step (3).Measure Deinking Efficiency.For ease of relatively the technological parameter and the measurement result that change being listed in table 3 and table 4.
[embodiment 33]
The useless laser stamping paper of waste paper employing except step (1) takes laser stamping paper through the laser printing of single face black and white, and all the other operations are all identical with embodiment 1.After measured, Deinking Efficiency is 83.6%.For ease of relatively, technological parameter and measurement result are listed in table 3 and table 4.
[embodiment 34]
Except step (2) adopted the useless magazine of waste paper employing, all the other operating conditions were all identical with embodiment 1.Wherein useless magazine is " China youth " (periodical publisher of China youth edits and publishes, the 18th phase in 2009) after the removal front cover.After measured, Deinking Efficiency is 82.1%.For ease of relatively, technological parameter and measurement result are listed in table 3 and table 4.
[comparative example 1]～[comparative example 3]
Except step (1) pH, step (2) pH, step (2) pH adjusting agent changed, all the other operating conditions were all identical with embodiment 1.Measure Deinking Efficiency.For ease of relatively, technological parameter and measurement result are listed in table 3 and table 4.
At last, as summary of the present invention, the present inventor finds through a large amount of experiments:
One, about vegetable oil source and flotation temperature relation
Flotation temperature between 20～40 ℃ the time deinking efficiency by good to poor be sequentially soybean oil ≈ sunflower oil ≈ corn oil＞rapeseed oil ≈ peanut oil ≈ cottonseed oil＞olive oil ≈ tea oil＞palm oil ≈ coconut oil; This also can be confirmed from the data of embodiment 1～embodiment 10.
When flotation temperature is brought up to 45～50 ℃, Deinking Efficiency improves obviously when aliphatic acid potassium or sodium are derived from rapeseed oil, peanut oil or cottonseed oil, the level of having originated near soybean oil, sunflower oil or corn oil, the deinking efficiency that is derived from soybean oil, sunflower oil, corn oil, olive oil, tea oil increases, and the Deinking Efficiency that is derived from palm oil or coconut oil does not have significant change.This also can be confirmed by the data of embodiment 1～embodiment 20.When flotation temperature is further brought up to 55～60 ℃, the aliphatic acid potassium in olive oil, tea oil, palm oil, coconut origin source or the deinking efficiency of sodium salt are just demonstrated fully, thereby the fat acid potassium in above-mentioned various fat oils source or the Deinking Efficiency of sodium salt are tending towards close, and these data from embodiment 21～embodiment 23 are confirmed.therefore, in order to reach deinking efficiency preferably, soybean oil, sunflower oil, aliphatic acid sylvite or the sodium salt in corn oil source have the widest flotation temperature scope (more preferably selecting 20～60 ℃), and larger temperature range is arranged near environment temperature, therefore not only being conducive to improve operating flexibility that flotation produces also helps and realizes that floatation process realizes energy-saving and cost-reducing, from this angle, next is rapeseed oil, peanut oil, aliphatic acid sylvite or the sodium salt in cottonseed oil source, its preferred flotation temperature scope is 45～60 ℃, secondly be olive oil again, tea oil, palm oil, coconut oil, its preferred flotation temperature scope is 55～60 ℃.
Two, about the acidic ph modifier of step (2)
When adopting disodium ethylene diamine tetraacetate, EDTAP dipotassium ethylene diamine tetraacetate, ethylenediamine tetra-acetic acid two ammonium, Deinking Efficiency is suitable, but all be better than other common acid, for example hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, this can be confirmed from the data of embodiment 1, embodiment 24～embodiment 26.
Three, the aliphatic acid sylvite (or sodium) in soybean oil source uses simultaneously with the aliphatic acid sylvite (or sodium salt) in cottonseed oil source
For unaccountable reason, both have synergy on deinking efficiency, and this can be confirmed from the experimental result of embodiment 1, embodiment 6 and embodiment 30.
Claims (10)
1. adopt the deinking process for waste paper of mixed enzyme, comprise the steps:
(1) under temperature was 25～55 ℃, the condition of pH=7.0～7.5, the deinking agent aqueous solution and waste paper mixed, and incorporation time is 5～40 minutes, obtains spent pulp liquors A; Wherein the weight ratio that feeds intake of waste paper and the deinking agent aqueous solution is 100: (300～900); The described deinking agent aqueous solution contains anion surfactant and non-ionic surface active agent, and in weight ratio, waste paper: anion surfactant: non-ionic surface active agent is 100: (0.05～0.15): (0.05～1.0); Described anion surfactant is at least a in the aliphatic acid potassium in vegetable oil source or sodium soap; Described non-ionic surface active agent general molecular formula is RO (CH
2CH
2O)
nH, wherein R is C
10～C
18Alkyl, n=3～12; Go back cellulase 0.2～0.5u/g, lipase 0.3～1.0u/g and amylase 0.2～1.0u/g in the described deinking agent aqueous solution;
(2) thin up and add acidic ph modifier in the spent pulp liquors A obtains take the waste paper weight concentration as 0.6～1.0wt%, the spent pulp liquors B of pH=6.5～6.9;
(3) spent pulp liquors B is carried out the flotation processing and obtain the deinking slurries.
2. deinking process for waste paper according to claim 1, the temperature that it is characterized in that step (1) is 40～50 ℃.
3. deinking process for waste paper according to claim 1, the pH that it is characterized in that step (1) is 7.2～7.4.
4. deinking process for waste paper according to claim 1 is characterized in that the described vegetable oil of step (1) is selected from least a in soybean oil, sunflower oil, corn oil, rapeseed oil, peanut oil, cottonseed oil, olive oil, tea oil, palm oil or coconut oil.
5. deinking process for waste paper according to claim 4 is characterized in that the described anion surfactant of step (1) is comprised of the anion surfactant in the anion surfactant in soybean oil source and cottonseed oil source.
6. want its 1 described deinking process for waste paper according to right, the incorporation time that it is characterized in that step (1) is 10～20 minutes.
7. deinking process for waste paper according to claim 1, is characterized in that R is C
12～C
14Alkyl, n=5～10.
8. deinking process for waste paper according to claim 1 is characterized in that pH adjusting agent described in step (2) is at least a in EDTA Dipotassium salt or disodium EDTA, ethylenediamine tetra-acetic acid di-ammonium salts.
9. deinking process for waste paper according to claim 1, is characterized in that the described pH of step (2) is 6.5～6.8.
10. deinking process for waste paper according to claim 1, is characterized in that the temperature of step (3) flotation is 20～85 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861764A (en) * | 2014-02-26 | 2015-08-26 | 胡锴 | Technology for removing laser printed or copied writings on paper surface |
| CN107059454A (en) * | 2017-05-08 | 2017-08-18 | 南京林业大学 | A kind of method that deinking is carried out using bifunctional fusion enzyme Lip EG1CD |
| CN109208367A (en) * | 2018-09-30 | 2019-01-15 | 兰溪泛仕达新材料科技有限公司 | A kind of novel waste paper floatation and ink removing agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104861764A (en) * | 2014-02-26 | 2015-08-26 | 胡锴 | Technology for removing laser printed or copied writings on paper surface |
| CN104861764B (en) * | 2014-02-26 | 2020-08-11 | 胡锴 | Technology for removing laser printing or copying handwriting on surface of paper |
| CN107059454A (en) * | 2017-05-08 | 2017-08-18 | 南京林业大学 | A kind of method that deinking is carried out using bifunctional fusion enzyme Lip EG1CD |
| CN107059454B (en) * | 2017-05-08 | 2018-05-15 | 南京林业大学 | A kind of method that deinking is carried out using bifunctional fusion enzyme Lip-EG1CD |
| CN109208367A (en) * | 2018-09-30 | 2019-01-15 | 兰溪泛仕达新材料科技有限公司 | A kind of novel waste paper floatation and ink removing agent |
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| CN103147334B (en) | 2014-09-24 |
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