CN100494566C - Biocatalytic clean pulping agent and application process thereof - Google Patents
Biocatalytic clean pulping agent and application process thereof Download PDFInfo
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- CN100494566C CN100494566C CNB200610011936XA CN200610011936A CN100494566C CN 100494566 C CN100494566 C CN 100494566C CN B200610011936X A CNB200610011936X A CN B200610011936XA CN 200610011936 A CN200610011936 A CN 200610011936A CN 100494566 C CN100494566 C CN 100494566C
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Abstract
The invention relates to a biochemical catalysis cleaning slurry agent and relative application. Said invention is formed by: amylase, laccase, hydroxybenztriazole, calcii chloridum SL-1 slurry braise agent, sodium carbonate, and water. And the application comprises: 1, cutting raw material to be kneaded and dedusted; 2, preparing material with wet method; 3, dipping to remove lignin colloid; 4, extruding slurry to replaced and separated, dipping to filter the left liquid to be recycled; 5, rough milling and combing wire; 6, screening slurry to remove foreign matters; 7, washing slurry; 8, finish milling slurry; 9, poaching slurry; 10, washing poached slurry; 11, stepped treating and recycling used water. The invention is characterized in dipping said raw material in normal temperature and pressure. The left liquid is not discharged, but be recycled. And the pulp is poached pulp. The invention can support industrial production.
Description
Technical field:
The present invention relates to a kind of urging and separate agent and technique for applying thereof.Be that a kind of biochemistry that is used for industrial papermaking is urged and separated pulping agent and technique for applying thereof specifically.Do not discharge slurrying in the production and pollute black liquor, realize cleaner production.
Background technology:
Based on non-wood fibrous raw material, timber is deficient relatively at China's paper-making pulping, and non-wood fibrous raw material is abundant, cheap, economic advantages are significantly arranged, its main production has soda processes, sulfate process, ammonia process etc. wherein based on soda processes, account for 60% of slurrying production.
The critical defect of existing soda pulping process technology, generation contains the organic black liquor of alkalization in a large number exactly, and serious environment pollution is administered very difficulty.The governance approach of comparative maturity is a Silvola recovery at present, this technology effect in wood pulp is produced is not bad, processing still is difficult to thorough contaminated solution problem to the non-wood fibrous raw material black liquor of pulp making, and one-time investment is huge, the operating cost height, general enterprise is difficult to accept, and 70% paper mill is closed down in the whole nation for this reason, has more than 7000 families.
Summary of the invention:
Effect of the present invention is the serious environment pollution problem that solves existing pulping technology for paper-making.A kind of biocatalytic clean pulping agent and technique for applying thereof are provided, energy-conservation, economize on water, economize in raw materials, not only cleaner production but also increase productivity effect.
Content of the present invention is that a kind of biochemistry of invention preparation is urged and separated pulping agent, adopts its corresponding production technology, and the processing pulping raw material is realized cleaner production.
The present invention realizes by following technical solution.
The composition of raw materials of biocatalytic clean pulping agent of the present invention is (percentage by weight):
Amylase 0.5-5 ‰
Laccase 0.5-5 ‰
Hydroxy-triazole 1-10 ‰
Calcium chloride 0.5-10 ‰
SL-digesting assistant in use for papermaking 0.5-20 ‰
Dodecyl sodium sulfate 0.5-20 ‰
Sodium carbonate 0.5-5%
Surplus is a water.
Amylase in the prescription, laccase are that letter (China) investment company of Novi produces, and supply of material transportation service is provided.
Hydroxy-triazole is middle amboceptor, makes enzyme preparation be able to the ehter bond of lignin unit in the oxidation pulping raw material, phenol key, makes the cracking of lignin macromolecular chain, removes lignin.And not with the reaction of the glycosidic bond of fiber polymer, the protection fiber is not degraded.Itself is reduced enzyme again, plays the effect of separating of urging, and is not consumed again in theory, realizes urging separating the pulping agent circulating and recovering and not discharging.Dodecyl sodium sulfate is a surfactant, increase the infiltration speed and the degree of depth, calcium chloride is the synergist that increases the enzyme preparation activity, the SL-1 digesting assistant in use for papermaking, synergy oxidation lignin ehter bond reduces enzyme agent consumption, and self is reduced again in the reaction, sodium carbonate improves urges the pH value of separating agent, is the necessary condition of lignin ehter bond cracking.
The preparation production method of biocatalytic clean pulping agent of the present invention is:
Above-mentioned raw material except that enzyme preparation is added in the reactor in proportion, stirred 30 minutes, leave standstill and stirred again in 2 hours 30 minutes, after leaving standstill 4-6 hour, the sediment that filters out impurities is heated to 65 ℃ afterwards and adds enzyme preparations, stirs 1.5 hours, and this biocatalytic clean pulping agent preparation is finished.This is nontoxic for this liquid, odorless, non-corrosiveness.
The technique for applying flow process of biocatalytic clean pulping agent of the present invention is:
The enforcement production technology is as follows: be example with the ryegrass pulping
1, removal of impurities is cut off, rubbed to wheat straw
Wheat straw is sent into the cut-out kneading machine, cuts off long 2.5-4cm, the moving wheat straw sheet of deciding the wide 4cm length of abrasive disc rubbing wheat straw one-tenth 3mm in machine, and the band stem wheat straw straw joint wheat head, wheat, husky mixing seldom told by selection by winnowing.
2, wet feed preparation
In the good wheat straw silk tablet raw material of cutting, add the isolated immersion raffinate of shove displacement operation, its addition is the 3-5% of wheat straw weight, be delivered to the immersion operation through the stirring of wet feed preparation machine, after wet feed preparation was handled, wheat straw reduced the absorption of wheat straw surface gas by the even moist surface of soak, in immersion machine, increase and add solid-liquid ratio, raising immersion production efficiency.
3, the wheat straw of immersion machine immersion wet feed preparation removes lignin colloid
The wheat straw of wet feed preparation is input in the immersion machine to be soaked, and soaking temperature is 25-60 ℃ under the normal pressure, drives bubble away under agitator in machine (or the auger conveyer) effect, fully soaks wheat straw.Soak is urged for this biochemistry and is separated pulping agent, soak than 10%, (calculatings of wheat straw over dry) soaked the production time at 5-8 hour, finished this operation, the careless shape slurry hardness number detection qualified (permanganate number) of immersion after getting inspection.There is 35% soak nature drop to go out during liquor ratio 10%.
4, shove separates, and the displacement shove soaks the raffinate recycling
Soak qualified careless shape slurry and import the first road press master and separate, isolated straw pulp concentration is about 35%, adds one times in water and stirs and send into the second road press master, extrudes liquid and separates and reach the purpose that reclaims raffinate 65-70%.Raffinate through mechanical filter equipment such as microporous filter, leach diameter greater than the particle more than the 20 μ m, wherein mostly be the colloid that lignin presents the jelly lignin.Biochemistry after the filtration is urged and is separated the pulping agent raffinate and soak wheat straw and remove lignin circulating and recovering performance still.
5, corase grind, coloured glaze are separated the branch silk
In the slurry that press master is extracted, still contain 30% soak, should starch concentration dilution and send into high-concentration paste mill corase grind to 5-8% and finish and discongest the branch silk.
6, screening the pulp impurity and purification
Straw pulp after the corase grind is removed residual wheat in the straw pulp, the wheat head and soaked sward etc. not through screening plants such as pressurized screens, again through scummer wherein residue such as sandy and stony soil separate.
7, pulp washing
The above-mentioned slurry of having finished purification adopts conventional washing device (wash drum, level band wash engine, vacuum pulp washing machine etc.) to finish pulp washing.
8, defibrination
Clean to starch on mill, to finish grind to reach and use the slurry standard, and concentration
9, float slurry, pulp washing
Slurry after concentrating, the same process equipment of use and soda pulping process method is bleached, and pulp washing was removed the residual agent of floating after bleaching was finished.
10, purify, remove the gred, concentrate the manufactured goods bleached pulp
Above operation use equipment and technical process mostly with the alkaline process production line on general, the workman operates also no change, just soaks operation and carries out on immersion machine, need not high pressure-temperature steam digesting apparatus, this product slurry does not also have especially and operates when manufacturing paper with pulp paper.
11, each technical process water cycle of treatment reuse step by step
A. this water of pulp washing water treatment (the first road pulp washing water, float and wash and starch pulp-water) is added into the composite flocculation agent rapid flocculation in pipeline, particle diameter is not more than 5 μ m in the pulp washing water after secondary woven wire, sintering web filter filter, the COD value is not more than 400mg/L, reached circulating and recovering and produced degree of purification, the water treatment expense is 0.24-0.28 unit/m
3Further purification also can enter the milipore filter device processes as need, and water quality can reach the pure water quality standard of earning eventually.Concentrate whole water 1% water treatment of making arrangements for his funeral.
Concentrating and separating water treatment in b, the operation
Processing procedure and above-mentioned basic identical, cost of water treatment is at 0.34-0.38 unit/m
3, the clear water after the filtration treatment is transmitted back to clear water reserviors, or directly to thinned water.
In the production overall process, take financial cost and emission compliance into account, water 12-18m
3/ ton dry pulp, purpose are the salt amounts of discharging in the cyclic process.
If need to force not discharge, system's design also has the desalinization film to concentrate, and the spraying oven dry is taken out solid shape salt, the reuse of purifying waste water.Just the too high nearly 60-80 of cost unit/ton dry pulp owing to present technique production cost ton dry pulp decline 700-1000 unit, is to have implementation.
Adjust formula rate of the present invention and pharmacy variety and technical process and can obtain hardness 10.5 (permanganate number) and float preceding slurry, hardness is low more certainly, and cost is high more, and hardness number is controlled in the production.
Use bleached pulp whiteness 〉=73%ISO that present technique makes, the beating degree making beating is as good as with alkaline pulp-making technology, and fibre length, intensity are higher than the soda pulping process handicraft product.
The application present technique makes bleached pulp and manufactures paper with pulp into 48g/m at production line
2Writing paper reaches national QB1211-91QB12654-90 standard, and it is as follows that (B level) detects numerical value:
| Quantitatively | 48g/m 2 |
| Whiteness | 83％ |
| Fracture length | Vertical/the average 3.45KM of horizontal 4.32/2.62 |
| Folding strength | More than 8 times |
| Degree of sizing | 0.75mm |
| Moisture content | 6.2％ |
| Ash | 11.5％ |
The invention has the beneficial effects as follows:
1, soak at room temperature slurrying, raffinate do not have the black liquor of pulp making discharging through mechanical filter reuse capable of circulation, and be free from environmental pollution.
2, but the colloid in the pulp washing water, lignin mechanical filter are deviate from, circulating and recovering after the pulp washing water filtration, and water saving is discharged environment protection standard more than 85%.
3, slurry yield is higher than soda pulping process technology 6-10%, economizes on resources remarkable in economical benefits.
4, do not have high pressure-temperature in the production, compare with the soda pulping process technology, security is better, and energy-conservation 60%.
5, above technology maturation process stabilizing is controlled, and the equipment typing is easy to continuous mass production, also is easy to simple and easy production on a small scale, is beneficial to making full use of of raw material dispersion resource.
6, compare slurrying cost decline 700-1000 unit/ton dry pulp with soda pulping process technology, the income repayment is high.
7, with the soda pulping process production line mutually specific investment descend more than 30%.
8, present technique is suitable for plurality of raw materials such as wheat straw, straw, cotton stalk, giantreed, reed, wood chip, mangosteen and soaks slurrying.
The specific embodiment:
Embodiment 1
The preparation biocatalytic clean pulping agent soaks ryegrass pulping
Place: Yinchuan, Ningxia, 9 tons of ingredients quantity
The preparation prescription is as follows: (percentage by weight)
Amylase 3 ‰
Laccase 2 ‰
Hydroxy-triazole 5 ‰
Calcium chloride 5 ‰
SL-1 digesting assistant in use for papermaking 5 ‰
Dodecyl sodium sulfate 5 ‰
Sodium carbonate 3%
All the other are water.
Soaking temperature 50-60 ℃.
The immersion process time spent is soaked the thick starch degree (permanganate number) in back
5.5 hours 11.2 for the first time
5 hours 12.2 for the second time
5+10 hour for the third time 30 ℃ 13.7
The 4th time 5.5 hours 40 ℃ 15.3
Float slurry bleachability 6.5%, soak is than 8%, and 18g/m manufactures paper with pulp
2Toilet paper soaks the continuous reuse of black liquor and does not discharge the same alkaline paper-making pulping technique of other technologies.General workman can both operate and finish.
Ryegrass pulping adopts this biochemistry to urge to separate pulping technique to soak in the example, discongests the branch wire process and spurts with the rotary spherical digester high-voltage high-speed and finish pressure reduction 0.5MPA.
Embodiment 2
Prepare this biocatalytic clean pulping agent and soak wheat straw for 9 tons.
Place: Wei County, Hebei Condar paper industry alkaline process production line
Urge and separate agent and prepare proportioning:
Amylase 2 ‰
Laccase 1 ‰
Hydroxy-triazole 4 ‰
Calcium chloride 5 ‰
SL-1 digesting assistant in use for papermaking 1%
Sodium carbonate 3%
Surplus is a water.
Soaking temperature 50-60 ℃.
Immersion process time: 4.5-6.5 hour.
Immersion is implemented in 1.2m
3Carry out in the hydrabrusher.
Liquor ratio 12%-14%
Continuous dipping circulating and recovering 32 times, the each filtration treatment reuse of black liquor, none discharging, slurry bleaching bleachability 6.7%, yield measuring and calculating 46.75% (this factory's alkaline process production line is 38.3% with batch wheat straw yield)
Starch degree 13.2-14 (permanganate number) before floating
48g/m has manufactured paper with pulp
2Writing paper mainly detects index.The writing paper standard, whiteness 82%ISO reaches QB12911-90, the QB12654-91B level.It is good that biocatalytic clean pulping agent of the present invention and technique for applying thereof are copied on the paper machine paper pulp drainability in the production line pilot scale, occurs sticking cylinder phenomenon in the operation, and product does not have the brightness reversion phenomenon yet.
Embodiment 3
Prepare this biochemistry and urge that to separate pulping agent close with above-mentioned formulation ratio.Process conditions are close, soak to pulverize and rub cotton stalk.Soaked 12 hours, starch degree 13.2, bleached pulp whiteness 〉=73%ISO, fibre bundle are obviously long, white, the example success.
Embodiment 4
Preparing this biochemistry urges and separates agent prescription proportioning and above-mentioned close, pulping raw material 107 white poplars
Place: Yinchuan
Technical process is real close with above-mentioned example, before just soaking the poplar sheet is smashed to present less than match shaft-likely, and the soak ratio is more than 22%, and soak time 6 hours is copied bleached pulp pattern whiteness 76%ISO.
Embodiment 5
This biochemistry is urged and is separated agent prescription with example 1, soaks giantreed, soaks and discongests defibrination behind the branch silk in 5.5 hours, bleached pulp hardness 14.1 (permanganate number) not, bleachability 7%, pulp brightness 71%ISO.
Biochemistry of the present invention is urged and is separated pulping agent and technique for applying pilot scale on production line thereof, and the formulation ratio of soak and medicine kind are according to the different corresponding adjustment of process implementing.Generally need soak time short, when temperature was identical, concentration was heightened.When brown stock hardness requires to hang down, take the soak time lengthening, or the dense increasing of medicine.During continuous dipping was produced, investment increased, the soak time lengthening, and concentration can descend, and production cost descends.In the practical application because of condition difference design implementation difference, implement to adjust principle and be with efficient, guarantee the quality, low cost, high yield, environmental protection be as the criterion.
Claims (5)
1, a kind of biocatalytic clean pulping agent is characterized in that it is that the raw material of following weight percentage prescription is made:
Amylase 0.5-5 ‰
Laccase 0.5-5 ‰
Hydroxy-triazole 1-10 ‰
Calcium chloride 1-10 ‰
SL-1 digesting assistant in use for papermaking 0.5-20 ‰
Dodecyl sodium sulfate 0.5-10 ‰
Sodium carbonate 0.5-5%
Surplus is a water.
2, adopt a kind of technique for applying of biocatalytic clean pulping agent slurrying as claimed in claim 1, it is characterized in that with the non-wood plant fibre being raw material, comprise the step of following pulping process:
(1) raw material cut off rub, dedusting, removal of impurities;
(2) wet feed preparation;
(3) in immersion machine, urge and separate pulping agent and soak pulping raw material, remove the lignin colloid in the raw material with biochemistry;
(4) shove replaced and separated raffinate soaks raffinate filtered and recycled circulating and recovering;
(5) corase grind is discongested the branch silk;
(6) screening the pulp impurity and purification;
(7) pulp washing;
(8) finish milling slurry, concentrating and separating;
(9) bleached pulp;
(10) clean bleached pulp, the concentrated finished product slurry that makes of impurity and purification;
(11) technical process water handle step by step, circulating and recovering.
3, the technique for applying of biocatalytic clean pulping agent according to claim 2 in slurrying is characterized in that the immersion machine that soaks pulping raw material has the stirring pulping device.
4, the technique for applying of biocatalytic clean pulping agent according to claim 2 in slurrying is characterized in that the pulping process water treatment is that each process water is handled step by step, reaches to meet the instructions for use of production process water, reuse economically.
5, the technique for applying of biocatalytic clean pulping agent according to claim 2 in slurrying is characterized in that described non-wood-fiber plant material is wheat straw, straw, cotton bar, reed, giantreed, mulberry shoot.
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| CN101200862B (en) * | 2007-05-30 | 2011-09-21 | 山东华林环保科技有限公司 | Clean pulping process |
| CN101381967B (en) * | 2007-09-05 | 2010-08-04 | 杨黎明 | Clean method for making paper pulp |
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| CN102677511B (en) * | 2012-05-28 | 2014-07-09 | 黄润燕 | Method for preparing virgin pulp for papermaking by utilizing organic enzyme to carry out enzyme treatment on herbaceous plants |
| CN103031297B (en) * | 2012-12-21 | 2014-03-12 | 青岛蔚蓝生物集团有限公司 | Composite enzyme for grinding of bleached pulp and application process of composite enzyme |
| CN103614942B (en) * | 2013-11-08 | 2016-04-13 | 尚诚德 | One utilizes agricultural crop straw pollution-free paper-making technology |
| CN104947495A (en) * | 2015-05-28 | 2015-09-30 | 姚婷婷 | Preparation method of paper for industry |
| CN106996049A (en) * | 2017-06-01 | 2017-08-01 | 无锡集安自动化科技有限公司 | A kind of plant equipment based on bio-pulping method in paper-making industry |
| CN107460753A (en) * | 2017-09-04 | 2017-12-12 | 山东东平容业达植物纤维科技有限公司 | A kind of compound drug and compound method for string extraction |
| CN107542012A (en) * | 2017-09-04 | 2018-01-05 | 山东东平容业达植物纤维科技有限公司 | A kind of disposable environmental protection tableware |
| CN107513875A (en) * | 2017-09-04 | 2017-12-26 | 天津容业达科技发展有限公司 | A kind of technique of weak alkalinity extraction rice-wheat straw fibre |
| CN107723809A (en) * | 2017-11-02 | 2018-02-23 | 天津容业达科技发展有限公司 | A kind of stalk fibre extraction process |
| CN109930408B (en) * | 2017-12-15 | 2021-04-06 | 中国制浆造纸研究院有限公司 | Method for treating unvulcanized damaged materials of papermaking method fiber sealing material |
| CN109537352B (en) * | 2018-11-05 | 2021-06-01 | 郓城海沁纤维有限公司 | Catalyst for catalyzing plant fiber pulping by ZYX presoaking and application process |
| CN112342831A (en) * | 2019-08-06 | 2021-02-09 | 王利权 | Process for producing paper pulp by using water and rice straw only and without any additive |
| AR122640A1 (en) * | 2020-06-17 | 2022-09-28 | Suzano Sa | METHOD TO TREAT A CONDENSATE IN A PULP MANUFACTURING PROCESS |
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Non-Patent Citations (2)
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| 造纸工业中生物制浆和生物漂白技术研究. 李汉全，何江浔，陈胜军.九江师专学报，第6期. 2003 |
| 造纸工业中生物制浆和生物漂白技术研究. 李汉全，何江浔，陈胜军.九江师专学报，第6期. 2003 * |
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