CN101446054B - Total-chlorine-free bleaching method of paper pulp production line with annual output of more than 50,000 tons - Google Patents
Total-chlorine-free bleaching method of paper pulp production line with annual output of more than 50,000 tons Download PDFInfo
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- CN101446054B CN101446054B CN2008102203151A CN200810220315A CN101446054B CN 101446054 B CN101446054 B CN 101446054B CN 2008102203151 A CN2008102203151 A CN 2008102203151A CN 200810220315 A CN200810220315 A CN 200810220315A CN 101446054 B CN101446054 B CN 101446054B
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- 229920001131 Pulp (paper) Polymers 0.000 title claims abstract description 86
- 238000004061 bleaching Methods 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000001301 oxygen Substances 0.000 claims abstract description 76
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 76
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000009897 hydrogen peroxide bleaching Methods 0.000 claims abstract description 29
- 239000010902 straw Substances 0.000 claims abstract description 21
- 239000002023 wood Substances 0.000 claims abstract description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 50
- 238000005406 washing Methods 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 27
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 25
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 25
- 239000003381 stabilizer Substances 0.000 claims description 25
- 238000005507 spraying Methods 0.000 claims description 24
- 239000000706 filtrate Substances 0.000 claims description 20
- 235000014676 Phragmites communis Nutrition 0.000 claims description 18
- 239000012190 activator Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
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- 239000003513 alkali Substances 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 13
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- 150000002978 peroxides Chemical class 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
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- 241000609240 Ambelania acida Species 0.000 claims description 4
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- 244000082204 Phyllostachys viridis Species 0.000 claims description 4
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- 150000003855 acyl compounds Chemical class 0.000 claims description 4
- 239000010905 bagasse Substances 0.000 claims description 4
- 239000011425 bamboo Substances 0.000 claims description 4
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 3
- 244000166124 Eucalyptus globulus Species 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
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- 241001349804 Juncus alpinoarticulatus Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 22
- 238000010009 beating Methods 0.000 abstract description 10
- 239000007844 bleaching agent Substances 0.000 abstract description 9
- 231100000419 toxicity Toxicity 0.000 abstract description 3
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- 150000004820 halides Chemical class 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 21
- 229910052801 chlorine Inorganic materials 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 21
- 238000004140 cleaning Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004076 pulp bleaching Methods 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- -1 hydrogen peroxide Chemical compound 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
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- 210000000630 fibrocyte Anatomy 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002896 organic halogen compounds Chemical class 0.000 description 3
- 239000002025 wood fiber Substances 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical group OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
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- 230000009920 chelation Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000011284 combination treatment Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
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- 229920005610 lignin Polymers 0.000 description 2
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- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- MSLRPWGRFCKNIZ-UHFFFAOYSA-J tetrasodium;hydrogen peroxide;dicarbonate Chemical compound [Na+].[Na+].[Na+].[Na+].OO.OO.OO.[O-]C([O-])=O.[O-]C([O-])=O MSLRPWGRFCKNIZ-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Abstract
The invention provides a total-chlorine-free bleaching method of paper pulp production line with annual output of more than 50,000 tons, which adopts ROP, OQP or ROQP production flow; wherein, R is pretreatment stage prior to oxygen delignification, O is oxygen delignification stage, Q is pretreatment stage prior to bleaching of hydrogen peroxide and P is pressure hydrogen peroxide bleaching stage. With low production cost, the method can bleach nonwood chemical pulp and straw/wood mixed pulp to 80-85%ISO; after bleaching, the pulp viscosity is more than 650ml/g, the beating degree is rangingfrom 20 degrees SR to 30 degrees SR, the breaking length after beating pulp and forming sheet is more than 4000m, the exhaust quantity of bleaching wastewater is 15-30m<3>, the exhaust quantity of thewastewater COD is about 17-40kg per ton of pulp, and the wastewater does not contain organic halide AOX with large toxicity any longer.
Description
Technical field
The present invention relates to a kind of method for bleaching, be specifically related to a kind of fully chlorine-free bleaching method of producing fairly large paper pulp production line more than 50,000 tons per year that is applicable to.
Background technology
Pulp and paper industry is a traditional industry in China, also is the pillar industry of China's light industry, yet along with the development of society and the renewal of technology, the problem that the paper industry of China exists also progressively displays, and generally speaking, the following aspects is arranged:
At first, paper waste is seriously polluted to environment, with statistics in 2003, the paper-making industrial waste water discharge capacity is 3,900,000,000 tons, is only second to the chemical industry manufacturing industry, accounts for 18.4% of industrial wastewater discharge total amount, and the COD discharge capacity accounts for 34.5%, be that COD discharging is maximum in all industries, and along with the ripe of alkali recovery technology and use, the pollution of paper-making effluent will mainly concentrate on middle section water (based on bleaching effluent).The bleaching process of China is based on traditional low dense chlorine bleach technology, as chlorination (C)-alkali treatment (E)-hypochlorite (H) bleaching process, it is acid that C section and E section waste water are, and the enrichment chlorion, if reuse, can impact the alkali recovery, and equipment is had very strong corrosivity, thereby can only emit, cause the environmental pollution and the wasting of resources, as adopt washing filtrate to recycle, produce slurry per ton and produce about 80m at least
3Waste water; Contain a large amount of lignin chlorination catabolites in the bleaching effluent, as chlorinatedorganic (AOX) poisonous, can be carcinogenic, and Cl content height in the bleaching effluent, be unfavorable for carrying out the biochemical oxidation processing of waste water.
Secondly, compare the country that the America and Europe waits some paper industry prosperities, the China's Forest Resources deficiency, the fibrous raw material unreasonable structure, the forest reserves that can supply with papermaking are few, the ability of national timber supply continues to descend over nearly 10 years, and the quality of the forest reserves and quantity all far can not satisfy the needs that pulping and paper-making is produced.Even the more rich country of timber resources the log situation that supply falls short of demand also occurred at present,, also begin to seek non-wood fiber raw material to substitute part timber as Canada.
The 3rd, most of scope of the enterprise with non-wood material production paper pulp is less, especially accounts for the grass raw material of non-wood raw material 2/3, because its drainability is relatively poor, the production capacity of washing and concentrator is restricted, thereby has limited the production scale of enterprise, and for a long time, pulping production line technology and equipment are more backward, the production cost height, it is lower that low dense chlorine bleach floats the back pulp brightness, easily brightness reversion, quality is difficult to satisfactory, and product lacks competitive.
Therefore, along with requirement on environmental protection is day by day strict, add increasingly sharpening of product market competition, non-wood raw pulp bleaching process and equipment are badly in need of a change, change big, the with serious pollution situation of present China Pulp Bleaching Wastewater amount.
At first, implement the policy of " vegetation is developed simultaneously, and suits measures to local conditions ", make full use of the non-wood raw material resources of China's abundant,, give full play to the lower advantage of non-wood cost of material as wheat straw, reed, bagasse, bamboo etc., can reduce product cost, strengthen product market competitiveness.
Secondly, promote the enterprises in pulp and paper industry production scale, especially the straw pulp scale of producing, because the straw pulp mill (output is below 5000 tons/year) that scale is less is owing to pollute the difficulty of handling, almost do not pollute and handle, scale promotes and can adopt ripe alkali to reclaim and advanced technologies such as bleaching, reduces the pollution of pulp and paper industry to environment greatly.
The 3rd, adopt advanced pulping bleaching technology and equipment, be reduce pollutes, improve the quality of products, energy-conservation, economize on water, set up the key of economizing type enterprise.
At present existing enterprise begins to mix part poplar slurry to improve its drainability in Straw Pulp, increased production scale (vegetation mixed pulp), but the pollution of low dense chlorine bleach can't remove, and adopting the total chlorine free bleaching technology is the final approach that addresses these problems.
According to whether containing elemental chlorine in the bleaching assistant, the bleaching production procedure can be divided into low dense chlorine bleach, element chlorine free bleaching (ECF) and total chlorine free bleaching (TCF).In order to reduce the pollution and toxic hazard of hanging down dense chlorine bleach wastewater discharge and alleviating and eliminating bleaching effluent, for energy efficient, bleaching technology obtains promptly progressive and constantly innovation, various bleaching new methods, new technology constantly is applied in the production, as the ClO 2 bleaching technology (D) that the seventies grows up for the sulfate wood pulp of bleaching difficulty and floating for last century, degree of depth oxygen delignification (0) technology that early eighties grows up in Europe, the nineties grows up is the hydrogen peroxide bleaching (P) that uses of bleaching high yield pulp, also has the ozone bleaching (Z) of immediate development, biology enzyme bleaching (X) or the like.These emerging bleaching technologies all have some common characteristic, and the bleaching efficiency height floats back pulp brightness height, and intensity is good, are fit to fairly large production (50,000 tons/year or more than), and the waste water environmental pollution that the bleaching section is discharged is less even pollution-free.The outstanding feature of ECF bleaching technology adopts ClO 2 bleaching (D) exactly, though ClO 2 bleaching has produced a small amount of organohalogen compounds, but its toxicity is very little, therefore, the ECF bleaching technology is popularized rapidly abroad, but because ECF production line investment is bigger, non-pulp bleaching to apply difficulty bigger.The TCF bleaching technology is then for adopting the not chloride bleaching assistant except that the ClO 2 bleaching agent, as hydrogen peroxide, oxygen etc., the generation of organohalogen compounds has been got rid of in the TCF bleaching fully, thereby the toxicity of waste water almost do not have, and waste water is handled through conventional water treatment process can satisfy more and more harsher environmental requirement.Therefore, the TCF bleaching is the developing direction of all bleaching technologies.Along with packaging for foodstuff, paper for daily use etc. are asked increase greatly to the needs of TCF paper pulp, TCF bleaching technology development at present abroad is rapid.
Owing to abroad seldom non-wood pulp is studied, the TCF technology that really is applied to non-pulp bleaching does not also have at present.Domestic paper making raw material is based on non-wood fiber raw material, but not having determined non-wood pulp to carry out total chlorine free bleaching, the floating property of difficulty of wood pulp needs special processing method, China once attempted the total chlorine free bleaching of Straw Pulp in the nineties, because a variety of causes finally ends in failure.For a long time, constantly research of China pulping and paper-making scientific workers, constantly exploration have obtained some very valuable achievements in research.
Patent CN1737255 discloses a kind of paper pulp cleaning and bleaching process: OHMP, this method has adopted bleaching agents such as oxygen, hydrogen peroxide, discharged waste water and pollutional load have been reduced, be suitable for producing daily the cleaning and bleaching of the chemical pulp of scale more than 50 tons, yet owing to still there is hypochlorite (H) bleaching section, waste water still contains a considerable amount of AOX and Cl
-, the wastewater treatment difficulty is big, is difficult to satisfy more and more stricter environmental requirement.
Patent CN1804210 discloses a kind of improved bleaching process of reed pulp that is used for, OXH, and CN1737255 is similar to patent, though adopted oxygen and biology enzyme to handle, because the existence of H section, the pollution problem of waste water still exists.
Patent CN101082187A discloses a kind of oxygen delignify treating method of grass group unbleached chemical pulp, can make the delignification rate of slurry reach 86～98%, but its method is to be based upon on the basis of follow-up CEH tri-stage bleaching, be high rigidity, high yield boiling, pulp hardness is still in Kappa value 14～18 behind the oxygen delignification, and such hardness is difficult to carry out the total chlorine free bleaching of follow-up higher whiteness.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of fully chlorine-free bleaching method of producing paper pulp production line more than 50,000 tons per year is provided, adopt free of contamination bleaching assistant such as oxygen, bleaching agents such as hydrogen peroxide, by pretreatment section before the oxygen delignification, the oxygen delignification section, pretreatment section and pressure hydrogen peroxide bleaching section processing procedure before hydrogen peroxide floats, realize cleaning and bleaching truly, the prepared back pulp brightness that floats reaches 80～85%ISO, viscosity is more than 650ml/g, beating degree is 20～30 ° of SR, fracture length was more than 4000m after sheet was copied in making beating, and the bleaching effluent discharging only is 15～30m
3, waste water COD discharges about 17～40kg/t slurry, and waste water is handled through conventional water treatment technology and is got final product qualified discharge.Environmental pollution is almost pollution-free, reaches the ideal standard of cleaner production.Production line investment and operating cost are lower, are specially adapted to produce per year the fairly large production line of non-wood chemical pulp more than 50,000 tons, vegetation mixed pulp.
The inventive method, the hardness of brown stock will be aspired for stability and can not be too high, and brown stock hardness Kappa value is 12～20, and whiteness is 32～42%ISO, and viscosity is greater than 900mg/l, and general at present employing continuously cooking technology all can satisfy this requirement.
The object of the invention is achieved through the following technical solutions:
A kind of fully chlorine-free bleaching method of producing paper pulp production line more than 50,000 tons per year may further comprise the steps:
Raw material through storing, get the raw materials ready, making non-wood chemical pulp or vegetation mixed pulp after the boiling, is extracted, screening process,
Described raw material comprises wheat straw, reed, bagasse, cotton stalk, waste of flax, bamboo, Chinese alpine rush, poplar, Eucalyptus or hardwood;
(1) oxygen delignification section O
The oxygen delignification section adopts single hop list tower or single hop double tower, advances tower and adds NaOH and magnesium sulfate respectively before, and the NaOH consumption is 25～40kg/t oven dry stock, and the magnesium sulfate consumption is 5～10kg/t oven dry stock, and advancing the preceding control of tower pulp density is 8～12%; Tower top pressure or second column overhead pressure are 0.4～0.5MPa, and reaction temperature is 95～105 ℃, and total reaction time is 60～90min, and flow of oxygen is 20～28kg/t oven dry stock;
After the oxygen delignification section paper pulp by cat head through discharger or directly spurt to spraying pot; The washing of paper pulp is used two wash engines series connection washings or is used the washing of connecting with a thickener of a wash engine;
The filtrate of having washed 50% is back to use this section spraying pot bottom and makes diluted pulp usefulness, and all the other fully recoverings finally enter the alkali recycle section to abstraction process;
(2) pretreatment section Q before hydrogen peroxide floats
Add pretreating agent in paper pulp, addition is 1～10kg/t oven dry stock, and the control pulp density is 3～10%, and reaction temperature is at 40～75 ℃, and the reaction time is 30～60min, and reaction pressure is a normal pressure, and pH value in reaction is 2～8; Through washing, paper pulp enters pressure hydrogen peroxide bleaching section, and the filtrate of having washed 50% is made diluted pulp usefulness at the bottom of being back to use this section tower, all the other filtrate discharges; Described pretreating agent is one or more compounds in biology enzyme, acylate or the acidic materials;
(3) pressure hydrogen peroxide bleaching section P
Adopt the hydrogen peroxide bleaching that has pressure of single hop list tower or single hop double tower, advance the preceding gas that adds earlier of tower in paper pulp, the gas addition is 6～12kg/t oven dry stock; Before advancing tower, add activator more respectively, stabilizing agent, magnesium sulfate and hydrogen peroxide, activator level is 5～10kg/t oven dry stock, stabilizing agent dosage is 25～40kg/t oven dry stock, the magnesium sulfate consumption is 5～10kg/t oven dry stock, and the hydrogen peroxide consumption is 30～40kg/t oven dry stock, and advancing the preceding control of tower pulp density is 8～12%; The tower top pressure of tower top pressure or second tower is 0.4～0.5MPa, and the reaction time is 60～90min, and reaction temperature is 95～105 ℃, and tower base stock slurry pH value is 8.5～9.5;
Described gas is compressed air, oxygen or nitrogen;
Paper pulp, is entered after a wash engine washing and floats back slurry storage tower, for machine room or the use of pulpboard workshop through discharger or directly spurt to spraying pot by cat head after the pressure hydrogen peroxide bleaching section.
Added peroxide before described oxygen delignification Duan Jinta, the peroxide addition is 10～15kg/t oven dry stock.
Described activator is one or more the compound in the acyl compounds.
Described stabilizing agent is silicon type stabilizing agent, non-silicon type stabilizing agent or both compounds.
Fully chlorine-free bleaching method of the present invention, can also form by following steps:
Raw material through storing, get the raw materials ready, making non-wood chemical pulp or vegetation mixed pulp after the boiling, is extracted, screening process,
(1) pretreatment section R before the oxygen delignification
In paper pulp, add chelating agent, biology enzyme or both compounds; Paper pulp is carried out preliminary treatment;
(2) oxygen delignification section O
The oxygen delignification section is divided into single hop list tower oxygen delignification or single hop double tower oxygen delignification, add NaOH and magnesium sulfate respectively before advancing tower, the NaOH consumption is 25～40kg/t oven dry stock, and the magnesium sulfate consumption is 5～10kg/t oven dry stock, and advancing the preceding control of tower pulp density is 8～12%; Tower top pressure or second column overhead pressure are 0.4～0.5MPa, and reaction temperature is 95～105 ℃, and total reaction time is 60～90min, and flow of oxygen is 20～28kg/t oven dry stock;
After the oxygen delignification section paper pulp by cat head through discharger or directly spurt to spraying pot; The washing of paper pulp is used two wash engines series connection washings or is used the washing of connecting with a thickener of a wash engine;
The filtrate of having washed 50% is back to use this section spraying pot bottom and makes diluted pulp usefulness, and all the other fully recoverings finally enter the alkali recycle section to abstraction process;
(3) pressure hydrogen peroxide bleaching section P
Adopt the hydrogen peroxide bleaching that has pressure of single hop list tower or single hop double tower, advance the preceding gas that adds earlier of tower in paper pulp, the gas addition is 6～12kg/t oven dry stock; Before advancing tower, add activator more respectively, stabilizing agent, magnesium sulfate and hydrogen peroxide, activator level is 5～10kg/t oven dry stock, stabilizing agent dosage is 25～40kg/t oven dry stock, the magnesium sulfate consumption is 5～10kg/t oven dry stock, and the hydrogen peroxide consumption is 30～40kg/t oven dry stock, and advancing the preceding control of tower pulp density is 8～12%; The tower top pressure of tower top pressure or second tower is 0.4～0.5MPa, and the reaction time is 60～90min, and reaction temperature is 95～105 ℃, and tower base stock slurry pH value is 8.5～9.5;
Described gas is compressed air, oxygen or nitrogen;
Paper pulp, is entered after a wash engine washing and floats back slurry storage tower, for machine room or the use of pulpboard workshop through discharger or directly spurt to spraying pot by cat head after the pressure hydrogen peroxide bleaching section.
Added peroxide before described oxygen delignification Duan Jinta, the peroxide addition is 10～15kg/t oven dry stock.
Described activator is one or more the compound in the acyl compounds.
Described stabilizing agent is silicon type stabilizing agent, non-silicon type stabilizing agent or both compounds.
Fully chlorine-free bleaching method of the present invention can also be made up of the ROQP four-stage, and R is a pretreatment section before the oxygen delignification; O is the oxygen delignification section; Hydrogen peroxide floats preceding pretreatment section Q; P is a pressure hydrogen peroxide bleaching section;
Raw material through storing, get the raw materials ready, making non-wood chemical pulp or vegetation mixed pulp after the boiling, is extracted, screening process,
(1) pretreatment section R before the oxygen delignification
In paper pulp, add chelating agent, biology enzyme or both compounds; Paper pulp is carried out preliminary treatment;
(2) oxygen delignification section O
The oxygen delignification section is divided into single hop list tower oxygen delignification or single hop double tower oxygen delignification, add NaOH and magnesium sulfate respectively before advancing tower, the NaOH consumption is 25～40kg/t oven dry stock, and the magnesium sulfate consumption is 5～10kg/t oven dry stock, and advancing the preceding control of tower pulp density is 8～12%; Tower top pressure or second column overhead pressure are 0.4～0.5MPa, and reaction temperature is 95～105 ℃, and total reaction time is 60～90min, and flow of oxygen is 20～28kg/t oven dry stock;
After the oxygen delignification section paper pulp by cat head through discharger or directly spurt to spraying pot; The washing of paper pulp is used two wash engines series connection washings or is used the washing of connecting with a thickener of a wash engine;
The filtrate of having washed 50% is back to use this section spraying pot bottom and makes diluted pulp usefulness, and all the other fully recoverings finally enter the alkali recycle section to abstraction process;
(3) pretreatment section Q before hydrogen peroxide floats
Add pretreating agent in paper pulp, addition is 1～10kg/t oven dry stock, and the control pulp density is 3～10%, and reaction temperature is at 40～75 ℃, and the reaction time is 30～60min, and reaction pressure is a normal pressure, and pH value in reaction is 2～8; Through washing, paper pulp enters pressure hydrogen peroxide bleaching section, and the filtrate of having washed 50% is made diluted pulp usefulness at the bottom of being back to use this section tower, all the other filtrate discharges; Described pretreating agent is one or more compounds in biology enzyme, acylate or the acidic materials;
(4) pressure hydrogen peroxide bleaching section P
Adopt single hop list tower or single hop double tower hydrogen peroxide bleaching with pressure, advance the preceding gas that adds earlier of tower in paper pulp, the gas addition is 6～12kg/t oven dry stock; Before advancing tower, add activator more respectively, stabilizing agent, magnesium sulfate and hydrogen peroxide, activator level is 5～10kg/t oven dry stock, stabilizing agent dosage is 25～40kg/t oven dry stock, the magnesium sulfate consumption is 5～10kg/t oven dry stock, and the hydrogen peroxide consumption is 30～40kg/t oven dry stock, and advancing the preceding control of tower pulp density is 8～12%; The tower top pressure of tower top pressure or second tower is 0.4～0.5MPa, and the reaction time is 60～90min, and reaction temperature is 95～105 ℃, and tower base stock slurry pH value is 8.5～9.5;
Described gas is compressed air, oxygen or nitrogen;
Paper pulp, is entered after a wash engine washing and floats back slurry storage tower, for machine room or the use of pulpboard workshop through discharger or directly spurt to spraying pot by cat head after the pressure hydrogen peroxide bleaching section.
Added peroxide before described oxygen delignification Duan Jinta, the peroxide addition is 10～15kg/t oven dry stock.
Described activator is one or more the compound in the acyl compounds.
Described stabilizing agent is silicon type stabilizing agent, non-silicon type stabilizing agent or both compounds.
Compare with existing dioxde pulp bleaching process, the present invention has the following advantages:
(1) the invention belongs to completely without chlorine cleaning and bleaching (TCF), almost pollution-free to environment
Because the whole adverse current reuses of oxygen delignification section waste water, and finally get back to the alkali recycle section, and also all adverse current reuses of the waste water of pressure hydrogen peroxide bleaching section, pretreatment section is discharged its filtrate of about 50% before having only hydrogen peroxide to float, (50% section reuse in addition), therefore, the discharged waste water of the present invention 15～30m that only has an appointment
3Water.The present invention has sent alkali to reclaim owing to produce the more oxygen delignification section waste water of COD, the waste water COD that pretreatment section was discharged before hydrogen peroxide floated is 17～40kg/t oven dry stock only, because whole flow process does not re-use the bleaching assistant that contains elemental chlorine, therefore, no longer contain the clastogenic organohalogen compounds AOX of intoxicating in the waste water, no longer contain Cl in the waste water
-, can handle by the Physiochemical and biochemical of routine and can satisfy harsh more environmental requirement.
(2) the invention belongs to short preface bleaching process, flow process is simple, and cost of investment is low
Than the ECF bleaching process, the present invention only uses four sections, if the R section is placed in the slurry tower of sieve back, then whole flow process has only three sections, and Operation and Maintenance is simple, and does not have equipment expensive as chlorine dioxide generator, the process equipment is all realized production domesticization at present, and equipment investment is low.
(3) adopt preprocess method targetedly, the bleaching efficiency height
Many at the tiny component of non-wood pulp (or straw pulp), the characteristics that ash content is high are promptly carried out corresponding preliminary treatment before the oxygen delignification section, the paper pulp that assurance enters oxygen delignification totally easily floats, by the biology enzyme preliminary treatment before the oxygen delignification, also can increase the infiltration of oxygen, improve the oxygen delignification effect.
Characteristic at hydroperoxidation, add corresponding pretreating agent in the hydrogen peroxide bleaching pretreatment section, can further remove metal ion harmful in the slurry, activate the reactivity of chromophoric group terminal groups simultaneously, in hydrogen peroxide, add assistant activator, strengthen the reactivity of hydrogen peroxide, thereby improve the bleaching efficiency of hydrogen peroxide from many aspects.
(4) bleaching adaptability is strong, can adapt to multiple non-wood fiber raw material and vegetation mixed pulp
The present invention must remove from office the situation of one or more mixing such as slurry, poplar slurry, eucalyptus pulp or hardwood slurry applicable to plurality of raw materials as Straw Pulp, reed pulp, bagasse pulp, cotton pulp, jute pulp, bamboo pulp, dragon.
(5) have lower operating cost and higher product quality, product has the stronger market competitiveness
The specific embodiment
Below in conjunction with embodiment the present invention is described in further detail, embodiment is only with explaining the present invention, and unrestricted the present invention, all should belong to protection scope of the present invention to the simple change of the fully chlorine-free bleaching method of non-wood chemical pulp, vegetation mixed pulp.
Embodiment 1
Daily output 150t Straw Pulp is completely without the chlorine cleaning and bleaching process
Along with popularizing of short barization of wheat straw and kind resistant to lodging, wheat straw is more and more lower as its quality of pulping and paper-making raw material, and the ash content of wheat straw and heteroproteose cell content are higher relatively in all non-wood materials, therefore, Straw Pulp carries out floating completely without chlorine, need be to the purchase of wheat straw, storage, get the raw materials ready, boiling, the strict control of washing operations such as (extractions), must not be mixed with when harvesting and storing and go mouldy, the wheat straw of rotting, the employing dry and wet stock preparation of getting the raw materials ready, wash reuse after the careless water purified treatment, extract, screening stage adopts the closed screening mode of " 4+1 " or " 4+1+1 ", " 4+1 " enters screening after referring to use four vacuum pulp washing machine series connection washings, last vacuum pulp washing machine concentrates, concentrate and " 4+1+1 " refers to add a single-screw press master after the flow process of " 4+1 " again, drop to minimum to bleaching disadvantageous tiny constituent content thereby make in the paper pulp that enters the oxygen delignification section.
To not float the Straw Pulp Hardness Control in Kappa value 14～18, whiteness is at 32～40%ISO, the total chlorine free bleaching flow process of Straw Pulp can adopt four sections of ROQP, carry out the preceding pretreatment section (R) of oxygen delignification of enzyme processing and chelation treatment combination, carry out in the middle slurry tower of R after paper pulp is washed sieve, enzyme adopts zytase, and addition is the 10kg/t oven dry stock, and paper pulp pH value is 6-8, temperature is 40-50 ℃, oxygen delignification section (O) adopts single hop list tower oxygen delignification, alkali charge 25kg/t, magnesium sulfate consumption 5kg/t, flow of oxygen is the 20kg/t oven dry stock, tower top pressure 0.4～0.5MPa, 95～100 ℃ of reaction temperatures, dwell time in the tower 60min, pulp hardness is a Kappa value 7～9 behind the delignification, whiteness is 45～50%ISO, and the pulp blowing out after reaction is finished enters spraying pot, is no more than 1h in the spraying pot time of staying, the paper pulp vacuum pulp washing machine that is pumped into two series connection washs then, filtrate about 50% is got back to the dilution of spraying pot bottom, and all the other are all got back to and extract section, finally deliver to chemical recovery system; Washing back paper pulp enters pretreatment section (Q), in the paper pulp temperature of Q section about 50～60 ℃, the Q section adds chelating agent ethylenediamine tetra-acetic acid (EDTA) and sulfuric acid, amount of chelant is the 3kg/t oven dry stock, with sulphur acid for adjusting pH value to 2～4, the intact pulp brightness of preliminary treatment increases by 1～2%ISO, and the pH value of pretreatment section wash filtrate is 3.5～6, filtrate drains 50% approximately, i.e. 15m
3, paper pulp is sent to a vacuum pulp washing machine washing after washing, because vacuum pulp washing machine pulp concentration does not satisfy follow-up hydrogen peroxide bleaching, therefore, also need to increase a concentrator, as the single-screw press master, the paper pulp after concentrating enters single hop list pressure tower hydrogen peroxide bleaching section (P); Pressure hydrogen peroxide section adopts oxygen to strengthen, advance before the tower aerating oxygen consumption 12kg/t oven dry stock in paper pulp, tower top pressure is controlled at 0.4～0.5MPa, reaction temperature is 95～100 ℃, the time of staying is 60min, paper pulp pH value is 8.5～9.5 when spurting pulp, the hydrogen peroxide consumption is the 30kg/t oven dry stock, the compound consumption of stabilizing agent acid amides and sodium metasilicate is the 25kg/t oven dry stock, the magnesium sulfate consumption is the 5kg/t oven dry stock, the activator dicyandiamide is the 5kg/t oven dry stock, floats the back pulp brightness and reaches 80～83%ISO, the about 650～700mg/l of viscosity, about 22～28 ° of SR of beating degree, making beating copies that fracture length is 6000～7000m behind the sheet, and folding strength 22～25 times is the very good bleached pulp of a kind of quality.
Embodiment 2
Daily output 300t reed pulp is completely without the chlorine cleaning and bleaching process
Reed also claims " reed " or " reed ", grass family, annual herb plant.Grow in the pond, riverbank, lakeside, water channel, roadside.China's reed aboundresources, widely distributed and concentrated.There are 14 reed main producing regions the nationwide now, and 7,500,000 mu of the long reed areas in reed base can provide 3,000,000 tons in paper grade (stock) reed.Owing to contain more tiny component in the reed, wherein major part is non-fibrocyte, these non-fibrocytes are on form, all different on materialization and the optical property with fibrocyte, its lignin, extract, ash and hemicellulose level are higher, and the glucose content and the degree of polymerization are lower, their existence has not only increased the consumption of bleaching medicine, and can reduce the bleachability energy of paper pulp, therefore, need to strengthen before the boiling get the raw materials ready and boiling after pulp washing, in the present embodiment, strict control enters the following tiny components contents of 200 orders in the bleaching system, the employing dry and wet stock preparation of getting the raw materials ready extracts, screening stage adopts the closed screening mode of " 4+1 ", enters screening after promptly using four vacuum pulp washing machines series connection washings, last vacuum pulp washing machine concentrates, and drops to minimum thereby make in the paper pulp that enters the oxygen delignification section to bleaching disadvantageous tiny constituent content.
Reed pulp total chlorine free bleaching flow process adopts ROP, and wherein R is the preceding pretreatment section (R) of oxygen delignification of enzyme processing and chelation treatment combination.Carry out in the middle slurry tower of R after paper pulp is washed sieve, enzyme adopts zytase, addition is the 5kg/t oven dry stock, chelating agent is diethylene-triamine pentaacetic acid (DTPA), addition is 1kg/t, the paper pulp temperature is 60～75 ℃, the intact paper pulp of preliminary treatment enters oxygen delignification section (O), the oxygen delignification that the oxygen delignification section adopts single hop list tower hydrogen peroxide to strengthen, alkali charge 40kg/t oven dry stock, magnesium sulfate consumption 10kg/t oven dry stock, hydrogen peroxide consumption 12kg/t slurry, flow of oxygen is the 25kg/t oven dry stock, tower top pressure 0.4～0.5MPa, 95～100 ℃ of reaction temperatures, dwell time in the tower 60min, pulp hardness is a Kappa value 7～9 behind the delignification, whiteness is 55～60%ISO, pulp blowing out after reaction is finished enters spraying pot, be no more than 1h in the spraying pot time of staying, the paper pulp vacuum pulp washing machine that is pumped into two series connection washs then, and filtrate about 50% is got back to the dilution of spraying pot bottom, all the other are all got back to and extract section, finally deliver to chemical recovery system; Washing back paper pulp direct single hop list pressure tower hydrogen peroxide bleaching section (P); Pressure hydrogen peroxide section adopts compressed air to strengthen, in paper pulp, add compressed air 6kg/t before advancing tower, tower top pressure is controlled at 0.4～0.5MPa, reaction temperature is 95～100 ℃, the time of staying is 60min, paper pulp pH value is 8.5～9.5 when spurting pulp, the hydrogen peroxide consumption is the 40kg/t oven dry stock, stabilizing agent sodium metasilicate consumption is the 40kg/t oven dry stock, magnesium sulfate is the 5kg/t oven dry stock, and chelating agent is the 1kg/t slurry, and activator dicyandiamide and cyanamide compound are the 10kg/t oven dry stock, float the back pulp brightness and reach 80～83%ISO, about 650～the 700mg/l of viscosity, about 20～24 ° of SR of beating degree, making beating copies that fracture length is 6000～7000m behind the sheet, folding strength 22～25 times is a kind of colory bleached pulp.
Embodiment 3
Daily output 300t reed, wheat straw, poplar (respectively accounting for 60%, 20%, 10%) mixed pulp completely without the chlorine cleaning and bleaching process
The vegetation mixed pulp refers generally to different material and separates boiling, and mixing, washing, screening and bleaching refer to wood pulp by mixing different proportion generally speaking improving the water filtering performance of straw pulp, thereby improve extraction rate of black liquor, increase the wash degree of paper pulp.Therefore, three kinds of raw materials are needed strict blank stock and boiling, the tiny constituent content before entering oxygen delignification below control 200 orders must not surpass 20%.
In the present embodiment, based on reed, so the total chlorine free bleaching flow process adopts OQP in the mixed pulp, the oxygen delignification that oxygen delignification section (O) adopts single hop double tower sodium carbonate peroxide to strengthen, and total residence time is 80min, first tower volume 70m
3, second tower volume is 110m
3Second column overhead pressure is 0.35～0.4MPa, alkali charge 35kg/t oven dry stock %, magnesium sulfate consumption 8kg/t oven dry stock, flow of oxygen is the 28kg/t oven dry stock, 95～105 ℃ of reaction temperatures, pulp hardness is a Kappa value 7～10 behind the delignification, whiteness is 46～50%ISO, the pulp blowing out of reaction after finishing enters spraying pot, and the paper pulp vacuum pulp washing machine that is pumped into two series connection washs then, and filtrate about 50% is got back to the dilution of spraying pot bottom, all the other are all got back to and extract section, finally deliver to chemical recovery system; Washing back paper pulp enters pretreatment section (Q), in the paper pulp temperature of Q section about 55～60 ℃, the Q section adds natrium citricum, the natrium citricum consumption is the 5kg/t oven dry stock, the pH value is transferred to 5～7, and the intact pulp brightness of preliminary treatment increases by 1～2%ISO, and the pH value of pretreatment section wash filtrate is 3.5～5, filtrate drains 50% approximately, i.e. 15～30m
3Paper pulp is sent to a vacuum pulp washing machine washing after washing, paper pulp after concentrating enters single hop double tower pressure hydrogen peroxide bleaching section (P), first tower is the stress reaction tower, roof pressure power is controlled at 0.4～0.5MPa, second tower is for falling streaming synthesis under normal pressure tower, making spraying pot simultaneously uses, in paper pulp, feed nitrogen reinforcement hydrogen peroxide bleaching before advancing first tower, nitrogen use level 9kg/t oven dry stock, first tower time of staying is 60min, second tower time of staying is about 60min equally, second Tata base stock slurry pH value is 8.5～9.5, the hydrogen peroxide consumption is the 35kg/t oven dry stock, and stabilizing agent fatty acid magnesium salt consumption is the 30kg/t oven dry stock, and activator cyanamide consumption is the 8kg/t oven dry stock, float the back pulp brightness and reach 80～82.5%ISO, about 600～the 650mg/l of viscosity, about 22～26 ° of SR of beating degree, making beating copies that fracture length is 5500～6000m behind the sheet, folding strength 22～25 times is a kind of quality mixed pulp preferably.
Claims (6)
1. a fully chlorine-free bleaching method of producing paper pulp production line more than 50,000 tons per year is characterized in that, may further comprise the steps:
Raw material through storing, get the raw materials ready, making non-wood chemical pulp or vegetation mixed pulp after the boiling, is extracted, screening process, and described raw material comprises wheat straw, reed, bagasse, cotton stalk, waste of flax, bamboo, Chinese alpine rush, poplar, Eucalyptus or hardwood;
Described boiling is to make that brown stock hardness Kappa value is 12～20, and whiteness is 32～42%ISO, and viscosity is greater than 900mg/l;
(1) oxygen delignification section
The oxygen delignification section adopts single hop list tower or single hop double tower, advances tower and adds NaOH and magnesium sulfate respectively before in paper pulp, and the NaOH consumption is 25～40kg/t oven dry stock, and the magnesium sulfate consumption is 5～10kg/t oven dry stock, and advancing the preceding control of tower pulp density is 8～12%; Tower top pressure or second column overhead pressure are 0.4～0.5MPa, and reaction temperature is 95～105 ℃, and total reaction time is 60～90min, and flow of oxygen is 20～28kg/t oven dry stock;
After the oxygen delignification section paper pulp by cat head through discharger or directly spurt to spraying pot; Wash then, washing pulp uses two wash engines series connection washings or uses the washing of connecting with a thickener of a wash engine;
The filtrate of having washed 50% is back to use this section spraying pot bottom and makes diluted pulp usefulness, and all the other fully recoverings finally enter the alkali recycle section to abstraction process;
(2) hydrogen peroxide floats preceding pretreatment section
Add pretreating agent in paper pulp, addition is 1～10kg/t oven dry stock, and the control pulp density is 3～10%, and reaction temperature is at 40～75 ℃, and the reaction time is 30～60min, and reaction pressure is a normal pressure, and pH value in reaction is 2～8; Through washing, paper pulp enters pressure hydrogen peroxide bleaching section, and the filtrate of having washed 50% is made diluted pulp usefulness at the bottom of being back to use this section tower, all the other filtrate discharges; Described pretreating agent is one or more compounds in biology enzyme, acylate or the acidic materials;
(3) pressure hydrogen peroxide bleaching section
Adopt the hydrogen peroxide bleaching that has pressure of single hop list tower or single hop double tower, advance the preceding gas that adds earlier of tower in paper pulp, the gas addition is 6～12kg/t oven dry stock; Before advancing tower, add activator more respectively, stabilizing agent, magnesium sulfate and hydrogen peroxide, activator level is 5～10kg/t oven dry stock, stabilizing agent dosage is 25～40kg/t oven dry stock, the magnesium sulfate consumption is 5～10kg/t oven dry stock, and the hydrogen peroxide consumption is 30～40kg/t oven dry stock, and advancing the preceding control of tower pulp density is 8～12%; The tower top pressure of tower top pressure or second tower is 0.4～0.5MPa, and the reaction time is 60～90min, and reaction temperature is 95～105 ℃, and tower base stock slurry pH value is 8.5～9.5;
Described gas is compressed air, oxygen or nitrogen;
Paper pulp, is entered after a wash engine washing and floats back slurry storage tower, for machine room or the use of pulpboard workshop through discharger or directly spurt to spraying pot by cat head after the pressure hydrogen peroxide bleaching section.
2. fully chlorine-free bleaching method of producing paper pulp production line more than 50,000 tons per year, it is characterized in that, may further comprise the steps: with raw material through storing, get the raw materials ready, making non-wood chemical pulp or vegetation mixed pulp after the boiling, extract, screening process, described boiling is to make that brown stock hardness Kappa value is 12～20, whiteness is 32～42%ISO, and viscosity is greater than 900mg/l;
(1) pretreatment section before the oxygen delignification
In paper pulp, add chelating agent, biology enzyme or both compounds; Paper pulp is carried out preliminary treatment;
(2) oxygen delignification section
The oxygen delignification section is divided into single hop list tower oxygen delignification or single hop double tower oxygen delignification, in paper pulp, add NaOH and magnesium sulfate respectively before advancing tower, the NaOH consumption is 25～40kg/t oven dry stock, and the magnesium sulfate consumption is 5～10kg/t oven dry stock, and advancing the preceding control of tower pulp density is 8～12%; Tower top pressure or second column overhead pressure are 0.4～0.5MPa, and reaction temperature is 95～105 ℃, and total reaction time is 60～90min, and flow of oxygen is 20～28kg/t oven dry stock;
After the oxygen delignification section paper pulp by cat head through discharger or directly spurt to spraying pot; Washing pulp uses two wash engines series connection washings or uses the washing of connecting with a thickener of a wash engine;
The filtrate of having washed 50% is back to use this section spraying pot bottom and makes diluted pulp usefulness, and all the other fully recoverings finally enter the alkali recycle section to abstraction process;
(3) pressure hydrogen peroxide bleaching section
Adopt the hydrogen peroxide bleaching that has pressure of single hop list tower or single hop double tower, advance the preceding gas that adds earlier of tower in paper pulp, the gas addition is 6～12kg/t oven dry stock; Before advancing tower, add activator more respectively, stabilizing agent, magnesium sulfate and hydrogen peroxide, activator level is that 5～10kg/t is exhausted in slurry, stabilizing agent dosage is 25～40kg/t oven dry stock, the magnesium sulfate consumption is 5～10kg/t oven dry stock, and the hydrogen peroxide consumption is 30～40kg/t oven dry stock, and advancing the preceding control of tower pulp density is 8～12%; The tower top pressure of tower top pressure or second tower is 0.4～0.5MPa, and the reaction time is 60～90min, and reaction temperature is 95～105 ℃, and tower base stock slurry pH value is 8.5～9.5;
Described gas is compressed air, oxygen or nitrogen;
Paper pulp, is entered after a wash engine washing and floats back slurry storage tower, for machine room or the use of pulpboard workshop through discharger or directly spurt to spraying pot by cat head after the pressure hydrogen peroxide bleaching section.
3. fully chlorine-free bleaching method according to claim 1 is characterized in that, pretreatment section before the increase oxygen delignification before described oxygen delignification section: add chelating agent, biology enzyme or both compounds and carry out preliminary treatment in paper pulp.
4. according to the described fully chlorine-free bleaching method of one of claim 1～3, it is characterized in that added peroxide before described oxygen delignification Duan Jinta, the peroxide addition is 10～15kg/t oven dry stock.
5. according to the described fully chlorine-free bleaching method of one of claim 1～3, it is characterized in that described activator is one or more the compound in the acyl compounds.
6. according to the described fully chlorine-free bleaching method of one of claim 1～3, it is characterized in that described stabilizing agent is silicon type stabilizing agent, non-silicon type stabilizing agent or both compounds.
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