CN103382671B - Clean pulping technology for high-polymerization-degree bamboo pulp - Google Patents
Clean pulping technology for high-polymerization-degree bamboo pulp Download PDFInfo
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- CN103382671B CN103382671B CN201310320265.5A CN201310320265A CN103382671B CN 103382671 B CN103382671 B CN 103382671B CN 201310320265 A CN201310320265 A CN 201310320265A CN 103382671 B CN103382671 B CN 103382671B
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- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 50
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 50
- 241001330002 Bambuseae Species 0.000 title claims abstract description 50
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 50
- 239000011425 bamboo Substances 0.000 title claims abstract description 50
- 238000004537 pulping Methods 0.000 title claims abstract description 17
- 238000005516 engineering process Methods 0.000 title abstract description 23
- 238000004061 bleaching Methods 0.000 claims abstract description 108
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000001301 oxygen Substances 0.000 claims abstract description 51
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003513 alkali Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- 238000010411 cooking Methods 0.000 claims abstract description 15
- 238000000605 extraction Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000010306 acid treatment Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 134
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- 239000002002 slurry Substances 0.000 claims description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 40
- 229920002472 Starch Polymers 0.000 claims description 29
- 235000019698 starch Nutrition 0.000 claims description 29
- 239000008107 starch Substances 0.000 claims description 25
- 239000004155 Chlorine dioxide Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 21
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 16
- 239000002738 chelating agent Substances 0.000 claims description 14
- 150000004965 peroxy acids Chemical class 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002023 wood Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 159000000003 magnesium salts Chemical class 0.000 claims description 9
- 239000003223 protective agent Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
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- 239000007844 bleaching agent Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical group [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
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- 229960001484 edetic acid Drugs 0.000 claims description 3
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- 239000001488 sodium phosphate Substances 0.000 claims description 3
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- 239000013638 trimer Substances 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229960003339 sodium phosphate Drugs 0.000 claims 1
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- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 5
- 235000019832 sodium triphosphate Nutrition 0.000 description 5
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- 238000012913 prioritisation Methods 0.000 description 4
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- 238000004140 cleaning Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
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- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
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- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- XOMKZKJEJBZBJJ-UHFFFAOYSA-N 1,2-dichloro-3-phenylbenzene Chemical group ClC1=CC=CC(C=2C=CC=CC=2)=C1Cl XOMKZKJEJBZBJJ-UHFFFAOYSA-N 0.000 description 1
- 241000209128 Bambusa Species 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 229920001407 Modal (textile) Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
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Abstract
The invention belongs to the field of paper pulp manufacturing and particularly relates to a method for utilizing a bamboo raw material to produce high-polymerization-degree dissolving pulp. The method is characterized by comprising the steps of material preparation, prehydrolysis, hot alkali extraction, alkaline method cooking, oxygen bleaching, bleaching and acid treatment and the like, and the clean pulping method for the high-polymerization-degree bamboo pulp solves the problems that existing production raw materials for the high-polymerization-degree dissolving pulp is sufficient, the technology falls behind, and pollution is severe, and the like. The polymerization degree of the manufactured bleached bamboo pulp is over 2000, the whiteness is over (90+/-2)%ISO, a-cellulose is over 96%, the ash content is below 0.1%, the Fe ion is below 20ppm, S18 is below 3%, S10 is below 4%, and (S10-S18) is below 2%.
Description
Technical field
The invention belongs to paper pulp field processed, particularly relate to a kind of free pulping method utilizing bamboo material to produce a kind of high polymerization degree bamboo pulp of high polymerization degree dissolving pulp.
Background technology
After entering 21 century, along with the quick growth of economy both at home and abroad and the raising of living standards of the people, the variety requirement of dissolving pulp is also constantly increased, not only large to viscose (as Lyocell fiber, Modal fibre, polynosic etc.) demand, and the degree of polymerization such as Dichlorodiphenyl Acetate fiber, cellulose nitrate and cellulose ether require that high product demand increases severely day by day.
At present, timber and cotton linter is mainly utilized to produce high polymerization degree dissolving pulp both at home and abroad, because cotton linter and timber are subject to the constraint of arable land and cost to cause limits throughput, in addition China is originally timber resource shortage country, existing timber dissolving pulp mostly is import, dissolving pulp is caused to hold at high price, larger cost pressure is brought to domestic relevant industries, therefore, how to develop the new resources of applicable China's national situation to make up the deficiency of raw material, meet the needs of market to dissolving pulp, promote the sustainable and healthy development of industry, become a very actual and urgent problem.The bamboo material of China's enriched, features such as having that distribution is wide, strong adaptability, growth are fast, become a useful person early, be biodegradable, and the pulping and paper-making characteristic of bamboo fiber is between needle-leaved wood fibre and broad-leaved wood fiber, average fiber length is 1.5-2.0mm, the longest 5mm that reaches, width is generally 15-18 μm, and fibrocyte accounts for the 50%-60% of total cell content.Based on the above-mentioned characteristic of bamboo material, good utilisation producing dissolving pulp from bamboo is seen very much by domestic many enterprises, more especially be the old factory of raw material or newly-built middle-size and small-size slurry factory with bamboo wood, willingness to invest is very high, the liquid phase prehydrolysis of the large liquor ratio of many employings and traditional bleaching technology such as chlorination-alkali treatment-hypochlorite (i.e. CEH) tri-stage bleaching produce dissolving pulp, the product degree of polymerization is lower many between 300-500, be mainly used in the production of viscose, the lower degree of polymerization limits the range of application of bamboo pulp, and the waste water environmental pollution that production process produces is serious, the pollution sources of its discharge mainly contain:
One is liquid phase prehydrolysis, and the liquid waste processing after hydrolysis is more difficult, if be equipped with waste hydrolyzed liquid recycling plant, and the high and problems such as complicated operation of construction cost, current enterprise discharges after being through more and rushing cinder, environmental pollution weight;
Two is that traditional bleaching effluent amount is large, pollutional load weight, and containing having carcinogenic, teratogenesis, mutagenic AOX to organism in a large number in waste water, has a strong impact on the living environment of the mankind and other organism.
Explore solve that bleaching effluent pollutes the most directly, effectively pollution-free or oligosaprobic bleaching agent and bleaching process be at present needed for.
Summary of the invention
For solving above technical problem, the invention provides a kind of free pulping method solving a kind of high polymerization degree bamboo pulp of the problems such as existing high polymerization degree dissolving pulp raw materials for production are not enough, backward in technique, seriously polluted.
Solve the free pulping method of a kind of high polymerization degree bamboo pulp of above technical problem, it is characterized in that: comprise the following steps:
(1) material prepares: bamboo wood is cut into 10-50mm long, wide 5-20mm, gets the raw materials ready with dry method, wet method or dry wet combined techniques, removing impurity;
(2) prehydrolysis: bamboo chip step (1) obtained carries out the prehydrolysis of little liquor ratio in digester, liquor ratio is 1 ﹕ 0.5-1.3, temperature 100-150 DEG C, time 80-180min;
(3) hot alkali extraction: be that the tablet that the heat alkali liquid of 100-140 DEG C adds in step (2) after hydrolysis carries out hot alkali extraction by temperature, relative to over dry material quality, alkali lye mass concentration 50-85g/L, alkali charge 6-15%, time 40-100min;
(4) alkaline cooking: add alkaline matter in the tablet after step (3) hot alkali extraction and carry out alkaline cooking, relative to over dry material quality, the alkaline matter consumption 10-30% in alkaline cooking, time 30-120min, temperature 130-170 DEG C, liquor ratio 1 ﹕ 3-6, sulphidity 15-30%;
(5) concentrated: to be concentrated at spraying pot pulp thickening, screening and thickener by the slurry that step (4) obtains, the mass concentration of concentrated disposed slurry is 8-16%;
(6) oxygen bleaching: is added sodium hydroxide solution and magnesium salt protective agent in the slurry that step (5) is obtained, through preheating or directly enter stock pump standpipe, then enter high-shear mixer and add oxygen and steam, then entering bleaching tower and carry out oxygen bleaching, tower top pressure 0.3-0.6MPa, temperature 80-120 DEG C, time 20-90min, relative to over dry material quality, sodium hydroxide concentration 1-4%, magnesium salt protective agent consumption 0.1-1.0%, flow of oxygen 1.8-3.0%;
(7) bleach:
A, chlorine dioxide are once bleached: add NaOH or sulfuric acid adjust ph by after the slurry washing of step (6) gained, through preheating or directly enter stock pump standpipe, then enter shear mixer and add chlorine dioxide and steam, then entering bleaching tower and carry out ClO 2 bleaching;
Wherein starch dense 8-16%, time 30-240min, temperature 40-95 DEG C, relative to oven dry stock quality, Chlorine 0.8-2.0%, the consumption of NaOH or sulfuric acid is 0-0.5%;
B, EOP bleach: slurry steps A obtained adds sodium hydroxide solution and chelating agent after washing, through preheating or directly enter stock pump standpipe, then enter shear mixer and add hydrogen peroxide, oxygen and steam, then entering bleaching tower and carry out EOP bleaching;
Wherein starch dense 8-16%, time 30-120min, temperature 50-95 DEG C, oxygen pressure 0.1-0.3MPa, relative to oven dry stock quality, sodium hydroxide concentration 0.5-1.5%, oxygen consuming amount 0.2-1%, hydrogen peroxide use 0.1-1.0%, chelating agent 0.1-0.5%;
C, chlorine dioxide secondary are bleached: the slurry of step B gained is added NaOH or sulfuric acid adjust ph after washing, through preheating or directly enter stock pump standpipe, then enter shear mixer and add chlorine dioxide and steam, then entering bleaching tower and carry out ClO 2 bleaching;
Wherein starch dense 8-16%, time 60-240min, temperature 40-70 DEG C, relative to oven dry stock quality, Chlorine 0.2-0.6%, the consumption of NaOH or sulfuric acid is 0-0.5%;
(8) acid treatment: the slurry of step C gained is entered double roller mixer and adds acid and steam after washing, through conveying worm conveying, then enters bleaching tower and carries out acid treatment;
Wherein starch dense 3-5%, time 10-100min, temperature 20-80 DEG C, relative to oven dry stock quality, sour consumption 0.2-5.0%, pH value 1.5-4.5.
Step (3) is caustic soda, vulcanized sodium with alkaline matter described in (4).
Described in step (6), magnesium salt protective agent is magnesium carbonate, magnesium sulfate or magnesia.
Described in step (8), acid is hydrochloric acid, sulfuric acid or sulfurous acid.
Further prioritization scheme in the present invention, also added hydrogen peroxide and chelating agent during the oxygen bleaching of step (6), relative to over dry material quality, and hydrogen peroxide use 0.2-2.0%, amount of chelant 0.1-0.5%.
Described chelating agent is EDTA, DTPA, STPP, DTPMPA;
Another prioritization scheme in the present invention, also added peroxy acid during the ClO 2 bleaching of step (7), relative to over dry material quality, and peroxy acid consumption 0.2-1%.
Described peroxy acid is Peracetic Acid, peroxosulphuric, mixing peroxy acid.
In step (7), in step A, pH value is 2-4, and in step C, pH value is 3.5-4.
The present invention adopts prehydrolysis-hot alkali extraction-sulfate process to carry out boiling to bamboo chip, prehydrolysis adopts the liquid phase prehydrolysis of little liquor ratio, hydrolyzate major part after being hydrolyzed still is attracted in tablet, by hot alkali extraction in subsequent process, waste liquid after hot alkali extraction send alkali collection together with the waste liquid after prehydrolysis, reach energy-conservation, reduce discharging, consumption reduction cleaner production object, and hot alkali extraction can remove hemicellulose further, low molecular weight lignin, organic solvent extract, ash grade, for subsequent sulphuric acid bisulfite cooking process carry out smoothly create advantage.Following bleaching adopts modern cleaning and bleaching flow process oxygen delignification-chlorine dioxide (delignification stages)-alkali treatment-chlorine dioxide (section of brightening)-acid-treated bleaching (i.e. O
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1) A) technology replacement traditional C EH tri-sections drift, the problem that the difficulty of governance of prehydrolysis waste liquid and traditional bleaching effluent is large is solved from source.
The present invention has the following advantages:
1, the present invention is a kind of free pulping method of high polymerization degree bamboo pulp:
In conjunction with the actual conditions of China, the bamboo wood that china natural resources is abundant is utilized to replace or partly replace timber and cotton linter to produce high polymerization degree dissolving pulp, not only solve the natural material such as cotton linter, timber to be ploughed and the constraint of cost causes the problem of limits throughput, and having made in the production field of dissolving pulp a kind of new raw material of sustainable regeneration newly many again, production cost reduces greatly simultaneously;
2, the present invention proposes the pulping process of the high polymerization degree bamboo pulp of an environmental protection, solve prehydrolysis waste liquid and the large problem of traditional bleaching effluent difficulty of governance from source, effectively alleviate factory effluent to the impact of environment and harm:
(1) prehydrolysis adopts little liquor ratio prehydrolysis, and the hydrolyzate major part after being hydrolyzed still is attracted in tablet, by heat alkali liquid extracting in subsequent technique process, can be sent alkali collection by the waste liquid after hot alkali extraction.Therefore, solve Traditional liquid phase prehydrolysis from source, the heating-up time is long, and the steam consumption is high, and time efficiency is low, and the liquid waste processing after hydrolysis is more difficult, if be equipped with waste hydrolyzed liquid recycling plant, and the high and problems such as complicated operation of construction cost;
(2) explore pollution-free or oligosaprobic bleaching agent and bleaching process be solve that bleaching effluent pollutes the most directly, effective approach.Invention adopts modernization clean bleaching technology-O
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oP(P
axd
1) A replacement traditional C EH tri-sections drift, the problem that traditional bleaching effluent amount is large, pollutional load heavy, difficulty of governance is large is solved from source, therefore low (or nothing) pollutes the needs that bleaching technology is environmental protection, the production requirement of multiple dissolving pulp product can be met simultaneously, there is higher economic value added;
Adopt present invention process to produce high polymerization degree bamboo pulp, can meet the requirement of most of dissolving pulp product completely, market prospects are fine, if can apply aborning, can bring good economic interests and environmental benefit and social benefit to enterprise.
The present invention adopts little liquor ratio liquid phase prehydrolysis-KP boiling and modern bleaching technology to produce high polymerised pulp, and the obtained bleached bamboo pulp dregs of rice degree of polymerization reaches more than 2000, whiteness (90 ± 2) more than %ISO, а-cellulose is more than 96%, ash content less than 0.1%, Fe below ion 20ppm, S
18less than 3%, S
10less than 4%, (S
10-S
18) less than 2%.
Detailed description of the invention
In the present invention, production procedure is the-prehydrolysis-hot alkali extraction-KP boiling-O that gets the raw materials ready
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oP(P
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1) A bleaching, solves existing high polymerization degree dissolving pulp raw materials for production and be only limitted to cotton linter, timber, can not meet demand, and production technology falls behind, with serious pollution problem, specifically comprises the following steps:
(1) bamboo wood is cut into 10-50mm long, wide 5-20mm, adopt dry method, wet method or dry wet combined techniques to get the raw materials ready, the impurity such as removing silt particle, knot and bits, bamboo wood can be cizu, bambusa textile, Xifeng Bamboo and mixing bamboo wood.
(2) bamboo chip that step (1) obtained loads the prehydrolysis carrying out less liquor ratio in digester, and liquor ratio is 1 ﹕ 0.5-1.3, and passing into steam, to be warming up to temperature be 100-150 DEG C, and temperature retention time is 80-180min.
(3) tablet that step (2) obtains is carried out hot alkali extraction in digester, the process of extracting is acid-base neutralization on the one hand, play effect raw material being carried out to pre-preg on the other hand, the hemicellulose of stripping, low molecular weight lignin, ash content and organic solvent extract increase, " space " on fiber finer cell wall is increased, for entering of later stage cooking liquor opens passage with the stripping of product, prevent tablet inside to produce boiling incomplete phenomenon, be therefore conducive to carrying out smoothly of sulfate cooking process below.Relative to over dry material quality, concentration of lye 50-85g/L(Na
2o counts), alkali charge 6-15%(Na
2o counts), time 40-100min, temperature 100-140 DEG C, alkaline matter is caustic soda, vulcanized sodium.
(4) tablet that step (3) obtains is carried out alkaline cooking, it act as and removes lignin further, hemicellulose, ash grade non-cellulosic impurity, the primary wall of raw material destroys comparatively thorough, obtains the true qualities bamboo pulp that purity is higher, is beneficial to follow-up bleaching process simultaneously and carries out smoothly.Relative to over dry material quality, alkaline matter consumption 10-30%(Na
2o counts), temperature retention time 30-120min, temperature 130-170 DEG C, liquor ratio 1 ﹕ 3-6, sulphidity 15-30%, alkaline matter is caustic soda, vulcanized sodium.
(5) slurry step (4) obtained is sent in spraying pot, through pulp thickening, then carries out closed screening, then is concentrated slurry by washing thickener, and the mass concentration of concentrated disposed slurry is 8-16%;
Pulp density will have influence on concentration of lye, namely affect reaction rate, have influence on the consumption of steam and the size etc. of reactor simultaneously.The dense surface area that can increase between gas-liquid of suitable raising slurry, reduces thickness of liquid film, thus improves the mass transfer rate of oxygen, increase oxygen delignification reaction rate, Reaction time shorten, reduce steam consumption quantity, reduce the consumption of alkali charge and oxygen.Production all adopts high dense or in dense oxygen delignification, generally trend towards dense oxygen delignification in 8% ~ 16% more, be a simplified dehydration equipment and reactor with high concentrated phase than main advantage, equipment investment minimizing.
(6) oxygen bleaching: is added sodium hydroxide solution and magnesium salt protective agent in the slurry that step (5) is obtained, through double roller mixer preheating or directly enter stock pump standpipe, then high-shear mixer is entered, and in high-shear mixer, add oxygen and steam, enter up-flow bleaching tower again and carry out oxygen bleaching, starch dense 8-16% tower top pressure 0.3-0.6MPa, temperature 80-120 DEG C, time 20-90min, relative to over dry material quality, sodium hydroxide concentration 1-4%, magnesium salt protective agent consumption 0.1-1.0%, flow of oxygen 1.8-3.0%; Magnesium salt protective agent is magnesium carbonate, magnesium sulfate or magnesia.
The major advantage of oxygen bleaching is high-efficiency cleaning, oxygen bleaching section is placed between alkaline cooking and bleaching section, can removes on the one hand, reduce the bleaching chemical consumption of follow-up drift section by 1/3 ~ 1/2 of brown stock residual lignin; Waste liquid on the other hand after oxygen bleaching by the process of sulfate recovery system, thus realizes non-wastewater discharge, moreover oxygen bleaching section suitably can control the degree of polymerization of pulp, is beneficial to and improves pulp performance.
(7) bleach: A, chlorine dioxide are once bleached: just the slurry of step (6) gained spurts to spraying pot, then adopt vacuum pulp washing machine washing; The slurry of gained adds NaOH or sulfuric acid adjust ph, through double roller mixer preheating or directly enter middle underflow pump standpipe, then high-shear mixer is entered, and in high-shear mixer, add chlorine dioxide and steam, then enter up-flow or liter-falling streaming bleaching tower carries out ClO 2 bleaching;
Make the best endpoint pH of chlorine dioxide (delignification stages) maintain between 2-4, the effective chlorine loss of ClO 2 bleaching is less.
ClO 2 bleaching technique is: starch dense 8-16%, time 30-240min, temperature 40-95 DEG C, relative to oven dry stock quality, and Chlorine 0.8-2.0%, the consumption of NaOH or sulfuric acid is 0-0.5%;
B, EOP bleach: slurry steps A obtained adds sodium hydroxide solution and chelating agent after washing, through double roller mixer preheating or directly enter stock pump standpipe, then high-shear mixer is entered, and in high-shear mixer, add hydrogen peroxide, oxygen and steam, then enter up-flow or lifting streaming bleaching tower carries out EOP bleaching; With the alkali treatment that hydrogen peroxide and oxygen are strengthened simultaneously, remaining lignin can be removed in slurry further, pigment, ash grade impurity, reduce its consumption when being beneficial to follow-up ClO 2 bleaching, reduce organic chloride content in bleaching effluent, and reduce bleaching cost.
Wherein EOP conditions of bleaching is: starch dense 8-16%, time 30-120min, temperature 50-95 DEG C, oxygen pressure 0.1-0.3MPa, relative to oven dry stock quality, and sodium hydroxide concentration 0.5-1.5%, oxygen consuming amount 0.2-1%, hydrogen peroxide use 0.1-1.0%, chelating agent 0.1-0.5%; Described chelating agent is EDTA(ethylenediamine tetra-acetic acid) or DTPA(diethylenetriamine pentaacetic acid) or STPP(sodium phosphate trimer) or DTPMPA(diethylenetriamine penta).
C, chlorine dioxide secondary are bleached: the slurry of step B gained is added NaOH or sulfuric acid adjust ph after washing, through double roller mixer preheating or directly enter stock pump standpipe, then high-shear mixer is entered, and in high-shear mixer, add chlorine dioxide and steam, then enter up-flow or liter-falling streaming bleaching tower carries out ClO 2 bleaching; With carry out ClO 2 bleaching (D) after chlorine dioxide Homogeneous phase mixing, the endpoint pH making chlorine dioxide (section of brightening) best maintains between 3.5 ~ 4, can reduce the loss of effective chlorine.
Wherein ClO 2 bleaching condition is: starch dense 8-16%, time 60-240min, temperature 40-70 DEG C, relative to oven dry stock quality, and Chlorine 0.2-0.6%, the consumption of NaOH or sulfuric acid is respectively 0-0.5% or 0-0.5%;
(8) acid treatment: the slurry of step C gained is entered double roller mixer and adds acid and steam after washing, then enter and fall streaming bleaching tower and carry out acid treatment; The ash content in slurry and metal ion can be removed further, the whiteness improving and starch after stable drift.
Wherein acid reaction variables is: starch dense 3-5%, time 10-100min, temperature 20-80 DEG C, relative to oven dry stock quality, and sour consumption 0.2-5.0%, pH value 1.5-4.5.Acid can be hydrochloric acid, sulfuric acid or sulfurous acid.
Further prioritization scheme, also added hydrogen peroxide and chelating agent during the oxygen bleaching of step (6), and the object of interpolation is can reinforced-oxygen bleaching, improves the selective of oxygen delignification.Relative to over dry material quality, hydrogen peroxide use 0.2-2.0%, amount of chelant 0.1-0.5%, described chelating agent is EDTA(ethylenediamine tetra-acetic acid) or DTPA(diethylenetriamine pentaacetic acid) or STPP(sodium phosphate trimer) or DTPMPA(diethylenetriamine penta).
Equally, further prioritization scheme, peroxy acid is also added during the ClO 2 bleaching of step (8), its main purpose adds a small amount of peroxy acid in chlorine dioxide drift section, whiteness can be improved, also can reduce Chlorine, reduce organic chloride content in bleaching effluent, and reduce bleaching cost.Relative to over dry material quality, peroxy acid consumption 0.2-1%, described peroxy acid is Peracetic Acid, peroxosulphuric, mixing peroxy acid;
Embodiment 1
(1) bamboo wood is directly cut into 10-50mm long, wide 5-20mm, adopts dry method, through impurity such as deduster removing silt particle, knot and bits, send into digester after dedusting and carry out prehydrolysis process, liquor ratio is 1 ﹕ 0.5, and temperature is 150 DEG C, and temperature retention time is 80min;
(2) be hydrolyzed disposed slurry and carry out hot alkali extraction, relative to over dry material quality, alkali charge 6%(Na
2o counts), concentration of lye 85g/L(Na
2o counts), time 100min, temperature 140 DEG C;
(3) slurry after extracting carries out kraft cooking, relative to over dry material quality, and alkali charge 30%(Na
2o counts), temperature retention time 30min, temperature 130 DEG C, liquor ratio 1 ﹕ 4, sulphidity 15%;
(4) slurry after boiling carries out O
pd
0e
oP(P
axd
1) A bleaching, bleaching technology condition is respectively: O
pnamely bleaching enters middle underflow pump standpipe, dense high-shear mixer in then entering after double roller mixer preheating, and in add oxygen and steam in dense high-shear mixer, then enter up-flow bleaching tower; Technical conditions, starch dense 8%, tower top pressure 0.6MPa, temperature 100 DEG C, time 20min, relative to over dry material quality, and sodium hydroxide concentration 3%, magnesium carbonate consumption 0.1%, flow of oxygen 1.8%, hydrogen peroxide use 0.2%, DTPA consumption 0.1%; D
0the slurry bleached by previous step gained spurts to spraying pot, then adopts vacuum pulp washing machine washing; The slurry of gained adds NaOH or sulfuric acid adjust ph is 3, through double roller mixer preheating or directly enter middle underflow pump standpipe, then dense high-shear mixer in entering, and in add chlorine dioxide and steam in dense high-shear mixer, then enter up-flow bleaching tower and carry out, starch dense 16%, time 100min, temperature 50 C, relative to oven dry stock quality, Chlorine 2.0%, NaOH 0.5%; E
oPthe slurry that bleaching technology obtains by steps A adds sodium hydroxide solution and chelating agent after washing, through double roller mixer preheating or directly enter middle underflow pump standpipe, then dense high-shear mixer in entering, and in add hydrogen peroxide, oxygen and steam in dense high-shear mixer, enter lifting streaming bleaching tower again: starch dense 8%, time 120min, temperature 70 C, oxygen pressure 0.1MPa, relative to oven dry stock quality, sodium hydroxide concentration 0.9%, oxygen consuming amount 0.2%, hydrogen peroxide use 0.4%, DTPMPA 0.2%; P
axd
1the slurry bleached by gained adds NaOH or sulfuric acid adjust ph is 4 after washing, through double roller mixer preheating or directly enter middle underflow pump standpipe, then dense high-shear mixer in entering, and in add chlorine dioxide and steam in dense high-shear mixer, then enter and rise-fall streaming bleaching tower and carry out ClO 2 bleaching; Technical conditions are: starch dense 10%, time 60min, temperature 70 C, relative to oven dry stock quality, and Chlorine 0.2%, sulfuric acid dosage is respectively 0.1%, Peracetic Acid consumption 1%; The slurry of A process and gained enters double roller mixer and adds acid and steam after washing, through conveying worm conveying, then enters and falls streaming bleaching tower and carry out acid reaction variables and be: starch dense 3%, time 100min, temperature 20 DEG C, relative to oven dry stock quality, hydrochloric acid consumption 2%.
Gained bamboo pulp performance indications are: the degree of polymerization 2530, whiteness 88.6%ISO, а-cellulose 98.1%, ash content 0.08%, Fe ion 14ppm, S
181.11%, S
102.24%, (S
10-S
18) 1.13%.
Embodiment 2
(1) bamboo wood is directly cut into 10-50mm long, wide 5-20mm, adopts wet method, after grass washing machine, wash away surface impurity and enter boiling vessel after removing excessive moisture and carry out prehydrolysis process, liquor ratio is 1 ﹕ 1.3, and temperature is 130 DEG C, and temperature retention time is 180min;
(2) be hydrolyzed disposed slurry and carry out hot alkali extraction, relative to over dry material quality, alkali charge 15%(Na
2o counts), concentration of lye 80g/L(Na
2o counts), time 40min, temperature 100 DEG C;
(3) slurry after extracting carries out soda cooking, relative to over dry material quality, and alkali charge 15%(Na
2o counts), temperature retention time 120min, temperature 160 DEG C, liquor ratio 1 ﹕ 3;
(4) slurry after boiling carries out O
pd
0e
oP(P
axd
1) A bleaching, bleaching process is as embodiment 1, and bleaching technology condition is respectively: O
pbleaching technology condition, starches dense 16%, tower top pressure 0.4MPa, temperature 80 DEG C, time 90min, relative to over dry material quality, and sodium hydroxide concentration 4%, magnesium sulfate consumption 1%, flow of oxygen 3%, hydrogen peroxide use 2%, DTPMPA consumption 0.5%; D
0bleaching technology condition, starches dense 8%, time 30min, temperature 95 DEG C, relative to oven dry stock quality, and Chlorine 1.0%, sulfuric acid dosage 0.4%; E
oPbleaching technology condition: starch dense 16%, time 30min, temperature 95 DEG C, oxygen pressure 0.3MPa, relative to oven dry stock quality, sodium hydroxide concentration 1.5%, oxygen consuming amount 0.2%, hydrogen peroxide use 0.1%, EDTA 0.5%; P
axd
1bleaching technology condition is: starch dense 8%, time 100min, temperature 40 DEG C, relative to oven dry stock quality, and Chlorine 0.4%, sodium hydroxide concentration 0.2%, mixing peroxy acid consumption 0.2%; A treatment conditions are: starch dense 5%, time 10min, temperature 80 DEG C, relative to oven dry stock quality, and sulfurous acid consumption 0.2%.
Gained bamboo pulp performance indications are: the degree of polymerization 2100, whiteness 88.1%ISO, а-cellulose 96.4%, ash content 0.08%, Fe ion 21ppm, S
182.10%, S
103.74%, (S
10-S
18) 1.64%.
Embodiment 3
(1) bamboo wood is directly cut into 10-50mm long, wide 5-20mm, adopts dry wet combined techniques to get the raw materials ready, first after deduster dedusting, then after grass washing machine washs and removes excessive moisture, enter boiling vessel carry out prehydrolysis process, liquor ratio is 1 ﹕ 1.0, temperature is 100 DEG C, and temperature retention time is 120min;
(2) be hydrolyzed disposed slurry and carry out boiling hot alkali extraction, relative to over dry material quality, alkali charge 12%(Na
2o counts), concentration of lye 50g/L(Na
2o counts), time 60min, temperature 120 DEG C;
(3) slurry after extracting carries out kraft cooking, relative to over dry material quality, and alkali charge 10%(Na
2o counts), temperature retention time 120min, temperature 170 DEG C, liquor ratio 1 ﹕ 6, sulphidity 30%;
(4) slurry after boiling carries out O
pd
0e
oP(P
axd
1) A bleaching, bleaching process is as embodiment 1, and bleaching technology condition is respectively: O
pbleaching technology condition, starches dense 10%, tower top pressure 0.3MPa, temperature 120 DEG C, time 20min, relative to over dry material quality, and sodium hydroxide concentration 1%, magnesia consumption 0.5%, flow of oxygen 2%, hydrogen peroxide use 0.2%, STPP consumption 0.2%; D
0bleaching technology condition, starches dense 10%, time 240min, temperature 40 DEG C, relative to oven dry stock quality, and Chlorine 0.8%, the consumption 0.5% of sulfuric acid; E
oPbleaching technology condition: starch dense 10%, time 60min, temperature 50 C, oxygen pressure 0.2MPa, relative to oven dry stock quality, sodium hydroxide concentration 0.5%, oxygen consuming amount 1%, hydrogen peroxide use 1.0%, STPP 0.1%; P
axd
1bleaching technology condition is: starch dense 16%, time 240min, temperature 50 C, relative to oven dry stock quality, and Chlorine 0.6%, sodium hydroxide concentration is respectively 0.3%, peroxosulphuric consumption 0.2%; A treatment conditions are: starch dense 3%, time 10min, temperature 30 DEG C, relative to oven dry stock quality, and sulfuric acid dosage 5%.
Gained bamboo pulp performance indications are: the degree of polymerization 2627, whiteness 89.8%ISO, а-cellulose 97.8%, ash content 0.05%, Fe ion 12ppm, S
180.93%, S
101.91%, (S
10-S
18) 0.98%.
Inexpensive reproducible bamboo wood is again utilized to produce high added value, the bamboo pulp of high polymerization degree, the completely new approach of dissolving pulp prepared by the bamboo wood that utilizes of an exploitation applicable China's national situation, not only can make full use of the bamboo timber resource of China's abundant, and the production requirement of multiple dissolving pulp product can be met, a research field in the ascendant for researcher, if can realize, not only solve cotton linter, the natural materials such as timber are subject to the constraint of arable land and cost to cause the problem of limits throughput, and to have made in the production field of dissolving pulp a kind of new raw material of sustainable regeneration newly many again, while ensuring the quality of products, production cost reduces greatly, have much wide market prospects.
The present invention adopts oxygen delignification-chlorine dioxide (delignification stages)-alkali treatment-chlorine dioxide (section of brightening)-acid-treated five sections of bleachings, after can making drift, pulp brightness reaches the simple CEH bleached pulp whiteness of (90 ± 2) %ISO(mono-is 70%ISO or following whiteness), wherein oxygen delignification section, alkali treatment section and acid treatment section are total chlorine free bleaching section, and bleaching effluent is never containing organic chloride (AOX); ClO 2 bleaching is efficient bleaching technology, delignification selective stronger, bleaching efficiency is high, and the yield of bleached pulp is high, intensity good, retention of whiteness is good, also has antisepsis and sterilization effect, reduce the generation of rotten slurry, under same effective chlorine consumption, the organic chloride that ClO 2 bleaching produces is only 1/5 of Chlorinated Bleaching, considerably reduces that toxicity is large, organic chloride content that can be carcinogenic, reduce wastewater treatment expense, therefore O
pd
0e
oP(P
axd
1) A replaces traditional C EH(chlorination-alkali treatment-hypochlorite) three sections of drifts, the problem that traditional bleaching effluent amount is large, pollutional load heavy, difficulty of governance is large is not only solved from source, and it is poor to solve tradition bleaching delignification selectivity, pulp yield and the larger problem of loss of strength after the drift caused.As can be seen here, low (or nothing) of the present invention pollutes the needs that bleaching technology is environmental protection, can produce the bamboo pulp of high polymerization degree high-purity high whiteness simultaneously, meet the production requirement of multiple dissolving pulp product, have higher economic value added.
Claims (8)
1. a free pulping method for high polymerization degree bamboo pulp, is characterized in that: comprise the following steps:
(1) material prepares: bamboo wood is cut into 10-50mm long, wide 5-20mm, gets the raw materials ready with dry method, wet method or dry wet combined techniques, removing impurity;
(2) prehydrolysis: bamboo chip step (1) obtained carries out the prehydrolysis of little liquor ratio in digester, liquor ratio is 1 ﹕ 0.5-1.3, temperature 100-150 DEG C, time 80-180min;
(3) hot alkali extraction: be that the tablet that the heat alkali liquid of 100-140 DEG C adds in step (2) after hydrolysis carries out hot alkali extraction by temperature, relative to over dry material quality, alkali lye mass concentration 50-85g/L, alkali charge 6-15%, time 40-100min;
(4) alkaline cooking: add alkaline matter in the tablet after step (3) hot alkali extraction and carry out alkaline cooking, relative to over dry material quality, the alkaline matter consumption 10-30% in alkaline cooking, time 30-120min, temperature 130-170 DEG C, liquor ratio 1 ﹕ 3-6, sulphidity 15-30%;
(5) concentrated: to be concentrated at spraying pot pulp thickening, screening and thickener by the slurry that step (4) obtains, the mass concentration of concentrated disposed slurry is 8-16%;
(6) oxygen bleaching: is added sodium hydroxide solution and magnesium salt protective agent in the slurry that step (5) is obtained, through preheating or directly enter stock pump standpipe, then enter high-shear mixer and add oxygen and steam, then entering bleaching tower and carry out oxygen bleaching, tower top pressure 0.3-0.6MPa, temperature 80-120 DEG C, time 20-90min, relative to over dry material quality, sodium hydroxide concentration 1-4%, magnesium salt protective agent consumption 0.1-1.0%, flow of oxygen 1.8-3.0%;
(7) bleach:
A, chlorine dioxide are once bleached: add NaOH or sulfuric acid adjust ph by after the slurry washing of step (6) gained, through preheating or directly enter stock pump standpipe, then enter shear mixer and add chlorine dioxide and steam, then entering bleaching tower and carry out ClO 2 bleaching;
Wherein starch dense 8-16%, time 30-240min, temperature 40-95 DEG C, relative to oven dry stock quality, Chlorine 0.8-2.0%, the consumption of NaOH or sulfuric acid is 0-0.5%;
B, EOP bleach: slurry steps A obtained adds sodium hydroxide solution and chelating agent after washing, through preheating or directly enter stock pump standpipe, then enter shear mixer and add hydrogen peroxide, oxygen and steam, then entering bleaching tower and carry out EOP bleaching;
Wherein starch dense 8-16%, time 30-120min, temperature 50-95 DEG C, oxygen pressure 0.1-0.3MPa, relative to oven dry stock quality, sodium hydroxide concentration 0.5-1.5%, oxygen consuming amount 0.2-1%, hydrogen peroxide use 0.1-1.0%, chelating agent 0.1-0.5%;
C, chlorine dioxide secondary are bleached: the slurry of step B gained is added NaOH or sulfuric acid adjust ph after washing, through preheating or directly enter stock pump standpipe, then enter shear mixer and add chlorine dioxide and steam, then entering bleaching tower and carry out ClO 2 bleaching;
Wherein starch dense 8-16%, time 60-240min, temperature 40-70 DEG C, relative to oven dry stock quality, Chlorine 0.2-0.6%, the consumption of NaOH or sulfuric acid is 0-0.5%;
(8) acid treatment: the slurry of step C gained is entered double roller mixer and adds acid and steam after washing, through conveying worm conveying, then enters bleaching tower and carries out acid treatment;
Wherein starch dense 3-5%, time 10-100min, temperature 20-80 DEG C, relative to oven dry stock quality, sour consumption 0.2-5.0%, pH value 1.5-4.5; Described acid is hydrochloric acid, sulfuric acid or sulfurous acid.
2. the free pulping method of a kind of high polymerization degree bamboo pulp according to claim 1, it is characterized in that: during the oxygen bleaching of step (6), also added hydrogen peroxide and chelating agent, relative to over dry material quality, hydrogen peroxide use 0.2-2.0%, amount of chelant 0.1-0.5%.
3. according to the free pulping method of a kind of high polymerization degree bamboo pulp described in claim 1 or 2, it is characterized in that: described chelating agent is ethylenediamine tetra-acetic acid, diethylenetriamine pentaacetic acid, sodium phosphate trimer or diethylenetriamine penta.
4. the free pulping method of a kind of high polymerization degree bamboo pulp according to claim 1, is characterized in that: step (3) is caustic soda, vulcanized sodium with alkaline matter described in (4).
5. the free pulping method of a kind of high polymerization degree bamboo pulp according to claim 1, is characterized in that: described in step (6), magnesium salt protective agent is magnesium carbonate, magnesium sulfate or magnesia.
6. the free pulping method of a kind of high polymerization degree bamboo pulp according to claim 1, is characterized in that: also added peroxy acid during the ClO 2 bleaching of step (8), relative to over dry material quality, and peroxy acid consumption 0.2-1%.
7. the free pulping method of a kind of high polymerization degree bamboo pulp according to claim 6, is characterized in that: described peroxy acid is Peracetic Acid, peroxosulphuric, mixing peroxy acid.
8. the free pulping method of a kind of high polymerization degree bamboo pulp according to claim 1, is characterized in that: in step (7), in step A, pH value is 2-4, and in step C, pH value is 3.5-4.
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| CN103726377B (en) * | 2014-01-21 | 2016-04-06 | 四川理工学院 | A kind of free pulping method of low polymerization degree bamboo pulp |
| CN104790241B (en) * | 2015-05-12 | 2016-08-17 | 四川理工学院 | A kind of clean method for preparing of high-purity high-quality bamboo wood dissolving pulp |
| CN105063782B (en) * | 2015-09-15 | 2017-08-11 | 阜宁澳洋科技有限责任公司 | A kind of high-purity viscose rayon and preparation method thereof |
| FR3062138B1 (en) | 2017-01-23 | 2019-06-07 | Centre Technique De L'industrie Des Papiers, Cartons Et Celluloses | PROCESS FOR WHITENING A PAPER PULP |
| CN107237197B (en) * | 2017-07-21 | 2018-11-09 | 齐鲁工业大学 | A kind of wood dissolving pulp deashing agent and process for deashing |
| CN112012034B (en) * | 2019-05-31 | 2022-08-05 | 河北吉藁化纤有限责任公司 | Preparation method of bamboo pulp, bamboo pulp and fiber |
| CN110240253B (en) * | 2019-07-23 | 2021-11-02 | 大连民族大学 | Method for treating refined cotton black liquor by using residual alkali waste heat |
| CN112127193A (en) * | 2020-09-25 | 2020-12-25 | 福建省青山纸业股份有限公司 | Production process for improving quality index of dissolving pulp by using bleaching process |
| CN114277598A (en) * | 2021-03-30 | 2022-04-05 | 赣南师范大学 | Preparation method of hollow and porous hybrid cells and bamboo dissolving pulp |
| CN113201961A (en) * | 2021-05-20 | 2021-08-03 | 四川工商职业技术学院 | Preparation method of bamboo dissolving pulp |
| CN114687234B (en) * | 2022-03-31 | 2023-06-16 | 华南理工大学 | Method for preparing fluff pulp by utilizing bamboo and fluff pulp prepared by same |
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| DE19751174C2 (en) * | 1997-11-19 | 2001-07-26 | Voith Paper Patent Gmbh | Process for increasing the whiteness of paper pulp |
| CN1786335A (en) * | 2005-12-09 | 2006-06-14 | 华南理工大学 | Process for bleaching wheat straw grass pulp by alkaline method |
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