CN105199048A - APMP pulping waste water graft copolymerization crosslinking modification and application in corrugated paper surface sizing - Google Patents
APMP pulping waste water graft copolymerization crosslinking modification and application in corrugated paper surface sizing Download PDFInfo
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- CN105199048A CN105199048A CN201410290658.0A CN201410290658A CN105199048A CN 105199048 A CN105199048 A CN 105199048A CN 201410290658 A CN201410290658 A CN 201410290658A CN 105199048 A CN105199048 A CN 105199048A
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Abstract
The invention relates to an alkaline peroxide mechanical pulp (APMP) pulping waste water graft copolymerization crosslinking modification. A corrugated paper surface sizing agent is prepared. The surface sizing agent is compounded with an inorganic crosslinking agent or compounded with starch and an inorganic crosslinking agent, so that the physical strength index of corrugated paper is improved, and the water resistance of the corrugated paper is improved; compared with a starch surface sizing agent, the cost is low, and the effect is more obvious. By means of the APMP pulping waste water graft copolymerization crosslinking modification, pulping waste water emissions are reduced, grain resources are saved, biomass resources in pulping waste water are recycled, and the purpose of changing waste materials into things of value is achieved.
Description
Technical field
The invention belongs to pulping waste liquor process and utilize field, the grafting, copolymerization and modification being specifically related to a kind of APMP pulping waste liquor and the method applied in fluting board top sizing thereof
Background technology
APMP (Alkaline Peroxide Mechanical Pulp) domesticly developed pulping process faster in recent years, thereupon also by producing a large amount of waste water, directly by these discharge of wastewater, caused serious pollution by environment.At present, domestic factory many employings tertiary treatment APMP reducing rules waste liquid, first removes suspended substance wherein and colloidalmaterial with physical method, and then cooling carries out anaerobic and aerobic process after reducing water temperature, finally carries out advanced treatment with chemical or physical chemistry method again.Indivedual paper plants adopt Technique of Heat Pump Evaporation to evaporate APMP pulping waste liquor, and concentrated solution is incorporated to utilizing black pulp liquor chemical recovery system, to reclaim chemical wherein and heat energy.Above two kinds for the treatment of processs cause waste to a certain degree to biomass resource.
What propose according to country 12 development outline adheres to using built environment friendly society as the important impetus of accelerating transformation of the mode of economic development.The fundamental state policy economized on resources with protection of the environment is deeply implemented during 12.This development being China's paper-making industry specifies direction.Along with rising year by year of APMP reducing rules production capacity, how reducing rules waste liquid can be turned waste into wealth, this is not only conducive to the development of Environmental Protection in China cause, is also conducive to papermaking enterprise and reduces production cost, for enterprise brings higher added value.
The organic substance contained in APMP waste liquid mainly comprises Mierocrystalline cellulose, hemicellulose, the degraded product of lignin, and lipid acid and fatty acid ester material.The present invention is intended to carry out modification by the method for graft copolymerization to the composition in waste liquid, then modified product is applied to the top sizing process of fluting board.
Summary of the invention
The present invention is reacted by free yl solution polymerization, adds sequestrant, linking agent in APMP pulping waste liquor, non-ionic monomer and cationic monomer, is reacted by redox initiation system initiation grafting crosslinking copolymerization.The graft copolymerization crosslinking product obtained has the characteristic of high viscosity (4000-12000mPas).Diluted for concentration be 8% time, its viscosity is 30-40mPas, and this viscosity is comparatively applicable to the top sizing of fluting board.
The concentration of the APMP pulping waste liquor that the present invention is used is 10-16%.
The present invention the sequestrant that is suitable for comprise EDTA, DTPA, HEDTA, be wherein optimum with EDTA.The add-on of sequestrant is the 0.015-0.1% of reactant quality.
Non-ionic monomer selected by the present invention mainly comprises: acrylamide, (methyl) acrylamide, N-methyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-methyl-N ethyl (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.Wherein preferred acrylamide.Reaction density is 2.5-8mol/L.
Cationic monomer selected by the present invention mainly comprises: MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, methylacryloxyethyldimethyl benzyl ammonium chloride and acrylamidopropyl dimethyl benzyl ammonium chloride.10: 1 ~ 10: 7 of the proportioning of cationic monomer and non-ionic monomer.
Linking agent selected by the present invention must have the ethylenic unsaturated group that 2 can produce free radical, and in water, have solvability to a certain degree.So the linking agent meeting this requirement comprises: N-methylene radical two (methyl) acrylamide, N, N ' 3-methylbutylene two (methyl) acrylamide, N, N ' (1,2 dihydroxyl ethylidene) two (methyl) acrylamide, N, N '-hexylidene two (methyl) acrylamide, N, N '-methylene-bis (methyl) acrylamide and N, N '-methylene-bisacrylamide.Wherein with N, N, '-methylene-bis (methyl) acrylamide and N, N '-methylene-bisacrylamide is optimum.The add-on of linking agent accounts for the 0.01-0.09% of reactant quality.
The redox system that the present invention adopts comprises: ferrous sulfate and hydrogen peroxide, ammonium persulphate and S-WAT, Potassium Persulphate and Sulfothiorine, ceric ammonium nitrate and thiocarbamide, potassium permanganate and sodium bisulfite.The initiation effect of the redox initiation system that ferrous sulfate and hydrogen peroxide form is best.The consumption of initiator is the 0.1-0.8% of reactant quality.
Kick off temperature of the present invention is mainly determined by trigger monomer, initiator.Kick off temperature of the present invention is 30-70 DEG C.
The pH scope of reaction system of the present invention is 3-12, take 6-8 as the best.
The reaction times of graft copolymerization of the present invention is 2-6 hour.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not limited only to the following examples.
Embodiment 1:
First 240mlAPMP pulping waste liquor is added in four-hole boiling flask, add sequestrant EDTA (consumption 0.1%) again, add after mixing acrylamide (AM) (4mol/L), MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) (AM and DMC mol ratio 10: 7) and linking agent N, N '-methylene-bis (methyl) acrylamide (consumption 0.08%), mix and blend 10min, to be mixed evenly after add initiator (FeSO
4: H
2o
2mol ratio is 4: 1, initiator amount 0.1%), then add sulfuric acid adjust ph to 8, logical N
2gas 20min, when temperature is increased to temperature of reaction 50 DEG C, with peristaltic pump, certain density oxidants hydrogen peroxide is added drop-wise in reaction system according to the regular hour, to be oxidized dose drips full-time beginning timing, namely reaction 4H obtains graft copolymerization product (EDTA, linking agent, initiator amount all relative to reactant hemicellulose in waste liquid, the total mass of AM and DMC).
Embodiment 2:
First 240mlAPMP pulping waste liquor is added in four-hole boiling flask, add sequestrant HEDTA (consumption 0.05%) again, add after mixing acrylamide (AM) (5mol/L), acrylyl oxy-ethyl-trimethyl salmiac (DAC) (AM and DAC mol ratio 10: 1) and linking agent N, N '-methylene-bis (methyl) acrylamide (consumption 0.06%), mix and blend 10min, to be mixed evenly after add initiator (ammonium persulphate and sodium bisulfite mol ratio be 1: 1, initiator amount 0.3%), add sulfuric acid adjust ph again to 6, logical N
2gas 20min, when temperature is increased to temperature of reaction 30 DEG C, with peristaltic pump, certain density oxygenant ammonium persulphate is added drop-wise in reaction system according to the regular hour, to be oxidized dose drips full-time beginning timing, namely reaction 5H obtains graft copolymerization product (HEDTA, linking agent, initiator amount all relative to reactant hemicellulose in waste liquid, the total mass of AM and DAC).
Embodiment 3:
First 240mlAPMP pulping waste liquor is added in four-hole boiling flask, add sequestrant HEDTA (consumption 0.05%) again, add after mixing acrylamide (AM) (5mol/L), acrylyl oxy-ethyl-trimethyl salmiac (DAC) (AM and DAC mol ratio 10: 3) and linking agent N-methylene radical two (methyl) acrylamide (consumption 0.03%), mix and blend 10min, to be mixed evenly after add initiator (potassium permanganate and sodium bisulfite mol ratio be 1: 1, initiator amount 0.4%), add sulfuric acid adjust ph again to 7, logical N
2gas 20min, when temperature is increased to temperature of reaction 60 DEG C, with peristaltic pump, certain density oxidant potassium permanganate is added drop-wise in reaction system according to the regular hour, to be oxidized dose drips full-time beginning timing, namely reaction 4H obtains graft copolymerization product (HEDTA, linking agent, initiator amount all relative to reactant hemicellulose in waste liquid, the total mass of AM and DAC).
Claims (7)
1. the APMP pulping waste liquor concentration used by the present invention is 10-16%.
2. sequestrant used in the present invention comprises EDTA, DTPA, HEDTA, and the add-on of sequestrant is the 0.015-0.1% of reactant quality.
3. the non-ionic monomer selected by the present invention mainly comprises: acrylamide, (methyl) acrylamide, N-methyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-methyl-N ethyl (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.Reaction density is 2.5-8mol/L.
4. the cationic monomer selected by the present invention mainly comprises: MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, methylacryloxyethyldimethyl benzyl ammonium chloride and acrylamidopropyl dimethyl benzyl ammonium chloride.10: 1 ~ 10: 7 of the proportioning of cationic monomer and non-ionic monomer.
5. the linking agent selected by the present invention comprises: N-methylene radical two (methyl) acrylamide, N, N '-3-methylbutylene two (methyl) acrylamide, N, N '-(1,2-dihydroxyl ethylidene) two (methyl) acrylamide, N, N '-hexylidene two (methyl) acrylamide, N, N '-methylene-bis (methyl) acrylamide and N, N '-methylene-bisacrylamide.The add-on of linking agent accounts for the 0.01-0.09% of reactant quality.
6. the redox system selected by the present invention comprises: ferrous sulfate and hydrogen peroxide, ammonium persulphate and S-WAT, Potassium Persulphate and Sulfothiorine, ceric ammonium nitrate and thiocarbamide, potassium permanganate and sodium bisulfite.The consumption of initiator is the 0.1-0.8% of reactant quality.
7. kick off temperature of the present invention is 30-70 DEG C, and the pH scope of reaction system is 3-12, and the reaction times is 2-6 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410290658.0A CN105199048A (en) | 2014-06-21 | 2014-06-21 | APMP pulping waste water graft copolymerization crosslinking modification and application in corrugated paper surface sizing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410290658.0A CN105199048A (en) | 2014-06-21 | 2014-06-21 | APMP pulping waste water graft copolymerization crosslinking modification and application in corrugated paper surface sizing |
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| CN105199048A true CN105199048A (en) | 2015-12-30 |
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|---|---|---|---|
| CN201410290658.0A Pending CN105199048A (en) | 2014-06-21 | 2014-06-21 | APMP pulping waste water graft copolymerization crosslinking modification and application in corrugated paper surface sizing |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110373938A (en) * | 2019-07-19 | 2019-10-25 | 天津科技大学 | A kind of water resistant composite paper-plastic material and preparation method thereof |
| CN114686119A (en) * | 2020-12-31 | 2022-07-01 | 上海昶法新材料有限公司 | Adhesive, raw material composition thereof, preparation method and application |
-
2014
- 2014-06-21 CN CN201410290658.0A patent/CN105199048A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 董丽颖等: "APMP制浆废液接枝共聚交联改性及其应用的研究", 《中国造纸》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110373938A (en) * | 2019-07-19 | 2019-10-25 | 天津科技大学 | A kind of water resistant composite paper-plastic material and preparation method thereof |
| CN110373938B (en) * | 2019-07-19 | 2021-12-10 | 天津科技大学 | Water-resistant paper-plastic composite material and preparation method thereof |
| CN114686119A (en) * | 2020-12-31 | 2022-07-01 | 上海昶法新材料有限公司 | Adhesive, raw material composition thereof, preparation method and application |
| CN114686119B (en) * | 2020-12-31 | 2024-03-29 | 上海昶法新材料有限公司 | Adhesive and raw material composition, preparation method and application thereof |
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Application publication date: 20151230 |