CN101426975B - Process for treating a cellulose-lignin pulp - Google Patents
Process for treating a cellulose-lignin pulp Download PDFInfo
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- CN101426975B CN101426975B CN2006800468212A CN200680046821A CN101426975B CN 101426975 B CN101426975 B CN 101426975B CN 2006800468212 A CN2006800468212 A CN 2006800468212A CN 200680046821 A CN200680046821 A CN 200680046821A CN 101426975 B CN101426975 B CN 101426975B
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- ozone
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- delignification
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- 238000000034 method Methods 0.000 title claims abstract description 52
- 229920005610 lignin Polymers 0.000 title abstract description 28
- 230000008569 process Effects 0.000 title abstract description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 89
- 150000002978 peroxides Chemical class 0.000 claims abstract description 10
- 229920001131 Pulp (paper) Polymers 0.000 claims description 62
- 239000002738 chelating agent Substances 0.000 claims description 26
- 238000004061 bleaching Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- -1 phosphonate ester Chemical class 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims 2
- 239000007844 bleaching agent Substances 0.000 abstract description 7
- 239000013522 chelant Substances 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 30
- 150000003254 radicals Chemical class 0.000 description 20
- 238000004537 pulping Methods 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229910021654 trace metal Inorganic materials 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 229920003043 Cellulose fiber Polymers 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 239000011121 hardwood Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 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
- 241000196324 Embryophyta Species 0.000 description 2
- 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 description 2
- 235000005018 Pinus echinata Nutrition 0.000 description 2
- 241001236219 Pinus echinata Species 0.000 description 2
- 235000017339 Pinus palustris Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000001912 cyanamides Chemical class 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 201000010260 leiomyoma Diseases 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229910021655 trace metal ion Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
- D21C9/153—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications with ozone
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1026—Other features in bleaching processes
- D21C9/1042—Use of chelating agents
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
Abstract
A process of treating a cellulose-lignin pulp. In an ozone stage, the pulp is contacted with ozone to bleach and delignify the pulp. The ozone stage is conducted without the addition of a peroxide bleaching agent. A chelant is introduced into the ozone stage to improve selectivity of the delignification.
Description
Background technology
The present invention relates generally to for example processing method of wood pulp of the processing method of cellulose-lignin material and particularly cellulose-lignin pulp.
Timber contains two kinds of key components: plain part of fibrous fabric and non-fiber lignin part.The polymeric chain that forms the plain part of fibrous fabric is to arrange each other and form firm association key with adjacent chain.Lignin is the three dimensional polymeric material of bonding cellulose fibre and also is distributed within the fiber itself.
Timber is converted into paper pulp for using in the paper mill.Paper pulp comprises and can be deposited on then and form a piece of paper on the screen cloth by slurryization or the lumber fibre that is suspended.The pulping technique that two kinds of main types are arranged: machinery pulping and chemical pulping.In machinery pulping, timber physically is divided into filament.In chemical pulping, wood chip uses the chemical solution boiling with dissolving part lignin, thereby and is removed.Normally used chemical pulping method comprises: (a) sulfate pulping, (b) sulfite pulping and (c) soda pulping.Sulfate pulping the most generally uses, and is included in boiling wood chip in the aqueous solution of NaOH and vulcanized sodium.Usually the wood pulp that will be produced in pulping process is separated into fibroid material (mass) and washing.
Wood pulp is a dark colour after pulping process, and reason is to contain the residual lignin of not removing during the boiling in the wood pulp, is formed chromophoric group by chemical modification at residual lignin described in the pulping process.For the color that alleviates paper pulp so that make it be suitable for the production of blank sheet of paper, need be by using delignification's material and removing residual lignin by adopting bleaching that any residual lignin is chemically converted into leuco-compounds.
Usually, the delignification of wood pulp and bleaching are carried out with elemental chlorine.Although chlorine is very effective bleaching agent, contain the accessory substance of these technologies generations of a large amount of conducts and the chloride that produces from the emission of chlorine bleach technology.Therefore the easy corrosion processing equipment of these chlorides require to use expensive material in the structure of bleaching equipment.In addition, the organic potentiality ambient influnence of chlorination in the worry emission.
For fear of these shortcomings, paper industry has attempted reducing or eliminating delignification and the bleaching that elemental chlorine is used for wood pulp.In this respect, carried out making great efforts with the exploitation bleaching process, chloro-containing reagent is replaced in this bleaching process, is for example replaced by the oxygen for bleached pulp.The use of the oxygen amount of the feasible elemental chlorine that uses really reduces significantly.Yet for the problem that runs into elemental chlorine, the use of oxygen usually is not satisfied fully technical scheme.Oxygen is not the optionally delignification agent the same with elemental chlorine, and it not only carries out delignification to paper pulp, and the cellulose fibre of degraded and weakening paper pulp.Equally, oxygen delignification remains some remaining lignin usually in paper pulp, and this remaining lignin must be removed to obtain the fully paper pulp of bleaching by chlorine bleach, therefore uses relevant worry still to exist with chlorine.
If ozone delignification and bleaching that can wood pulp be set to turn round effectively, then it is a kind of method that is very beneficial for industry.Ozone has very high oxidation potential, and is considered to have the potentiality that becomes very effective delignification agent.By allowing the other sealing (additional closure) of delignification-method for bleaching, ozone might can help industry.Because ozone stage do not add any harmful ion in black liquor recovery stream, so, its washing effluent can with the existing stage upstream (counter-currently) use.By these means, the fuel of recovery boiler will increase, and will reduce from the pollutant of water.Therefore, think that using the driving force of ozone is enhancement of environment.
Stop to use the former of ozone and can not satisfy the selectivity requirement because ozone has shown, in the dense stage dense or high dense equally effective not as low, and require low relatively temperature.If ozone will be accepted by paper industry, then must improve delignified selectivity.Present system does not produce the paper pulp that satisfies the industry pulp strength needs.Dense and restriction higher temperature can be resolved round in the use, but the elimination of these restrictions will make the application more attractive of ozone certainly.Because bleachery (bleach plant) is dense in being, be debatable so the low dense or high dense stage is retrofited.Low temperature is debatable especially for the closed system of the bleaching equipment in modern times for ozone stage.
The process reform of having attempted improving ozone bleaching comprises the optimization of pH, concentration and temperature.This technology improves under low pH.Low dense or high dense than in dense good.Low temperature will improve technology.Yet neither one makes this technology satisfy industrial requirement in these process reforms.
Several patents discloses the application of ozone in pulping process or delignification-bleaching process.For example, the United States Patent (USP) 6,258,207 of Pan discloses the method that a kind of purpose is non-xyloid material is carried out slurrying.This method was made of three stages: sour chelation stage; Then chelating is the alkaline peroxide stage, and this stage can or cannot be enhanced with ozone or peracetic acid; It then is the final stage of machinery pulping.This method is at grass, for example hemp and straw.
People's such as Hammer United States Patent (USP) 5,034,096 discloses a kind of use peroxide, oxygen and/or ozone and interpolation cyanamide or cyanamide salt and cellulose-containing material has been bleached and delignified method.When this method comprised peroxide as bleaching agent, this method comprised that also a kind of stabilizing agent or complex compound form agent (complex former) to avoid peroxide breakdown.If the heavy metallic salt in the cellulose was removed by washing the fibre is plain, then can omit the interpolation that stabilizing agent or complex compound form agent before bleaching.
People's such as Hurter United States Patent (USP) 6,302,997 discloses a kind of method that only is only applicable to non-wood matter kind.This method looks that being included in the ozone stage front carries out sour chelating, washs between them or does not wash.
People's such as Fahlgren United States Patent (USP) 5,593,544 is applicable to any cellulose fibre in small, broken bits.This method is handled by the sequestering agent (sequestering agent) before oxygen " boiling " stage.At least a portion chelation filtrate must be removed before oxygen step.Then be hydrogen peroxide bleaching after this oxygen stage, it can contain peracetic acid or ozone.Do not mention peroxide-ozone stage use chelating.
Summary of the invention
The present invention relates to method that cellulose-lignin pulp is handled.In ozone stage, paper pulp is contacted so that paper pulp is bleached and delignification with ozone.This ozone stage is not added under the peroxide bleaches and is carried out.Chelating agent is incorporated in the ozone stage to improve delignified selectivity.
In specific embodiment, the present invention relates to handle the method for wood pulp.In ozone stage, paper pulp is contacted so that paper pulp is bleached and delignification with ozone.This ozone stage produces hydrogen peroxide.Be incorporated in the ozone stage chelating agent with the trace metal in the chelating paper pulp and reduce the decomposition of hydrogen peroxide, improve delignified selectivity thus.
In another specific embodiment, the present invention relates to handle existing (prior) method of cellulose-lignin pulp, in the method,, paper pulp is contacted so that paper pulp is bleached and delignification with ozone in ozone stage.Ozone stage produces hydrogen peroxide, this hydrogen peroxide decomposes and produce first free radical, and the decomposition of this first free radical activated ozone and produce second free radical.First and second free radicals cause cellulosic degraded.The present invention improves existing method by chelating agent being incorporated in the ozone stage with the decomposition that reduces hydrogen peroxide, reduces the generation of first free radical thus.Successively, it reduces the activation of ozone decomposition and the generation of second free radical.The generation of first and second free radicals of this minimizing improves delignified selectivity by reducing cellulosic degraded.
Detailed Description Of The Invention
The present invention relates to the ozone bleaching of cellulose-lignin pulp and the method for delignified improvement.This method is applicable to the paper pulp of being made by lignocellulosic material of any kind of, for example paper pulp of being made by the different types of plant that mainly contains cellulose and lignin.In preferred embodiments, paper pulp is wood pulp.More particularly, in some embodiments, wood pulp is chemical pulp or regenerated paper pulp.This method is suitable for having the paper pulp of any concentration usually.In some embodiments, when paper pulp comprised the suspension of cellulose-lignin material in water, this paper pulp had by the concentration of the weight of paper pulp about 0.2% to the scope of the cellulose-lignin material of about 50% concentration.
This paper pulp is contacted with ozone so that paper pulp is bleached and delignification, be referred to herein as " ozone stage " during this.Ozone is applied to paper pulp in any suitable manner.Typically, paper pulp is fed in the reactor and is enough to paper pulp bleached with delignified mode with ozone ozone is injected in the reactor.
The bleaching of paper pulp and delignification do not add peroxide bleaches in ozone stage and carry out.In preferred embodiments, ozone is unique bleaching/delignification agent of using during this method.Yet this does not get rid of the peroxide that may form as accessory substance during this method.The bleaching of paper pulp and delignification can also not add cyanamide or cyanamide salt and carry out.
Ozone bleaching and delignified method are according to the present invention, improve by chelating agent is incorporated into ozone stage together with ozone and paper pulp.The introducing of chelating agent improves the delignified selectivity of paper pulp, so that ozone is bleached the cellulose fibre of not degrading significantly with delignification and weakening paper pulp to paper pulp.Any suitable chelating agent may be used to the present invention, phosphonate ester chelating agent for example, ethylenediamine tetra-acetic acid (EDTA), and/or diethylene-triamine pentaacetic acid (DTPA).The phosphonate ester chelating agent is preferred for the present invention usually.Some limiting examples of phosphonate ester chelating agent are by Solutia Inc., St.Louis, Missouri make based on hydroxy ethylene-1, the 1-di 2 ethylhexyl phosphonic acid
2010 series.
Chelating agent can be incorporated in the paper pulp with any suitable amount.Usually, paper pulp during ozone stage (for example comprises cellulose-lignin material, lumber fibre) suspension in water, and chelating agent is incorporated in the paper pulp to about 100 times amount (by weight) with about 1 of total trace metal, be more particularly about 10 to about 50 times.
Delignified selectivity does not improve with there being comparing with quadrat method of chelating agent.Preferably, it is about at least 10% that selectivity is enhanced, and more preferably at least about 20%.Selectivity can be to define in any suitable manner.For example, selectivity may be defined as Δ K/ Δ V, and wherein Δ K is the variation of measuring delignified Kappa number, and Δ V is the viscosity change that characterizes the carbohydrate depolymerization.Perhaps, selectivity may be defined as Δ K/ Δ V, and wherein Δ K is as using potassium permanganate KMnO
4Test in the variation of the delignified permanganate number of measurement measured.These selectivity definition and correlation test are known in paper industry.
Ozone bleaching of the present invention and delignification's method can use any suitable process conditions to carry out.For example, in some embodiments, paper pulp and ozone reaction about 1 second, perhaps about more specifically 10 seconds were to about 10 minutes to about 5 hours time range.In some embodiments, paper pulp and ozone are about 20 ℃ of extremely about 90 ℃ temperature range reactions, perhaps about more specifically 20 ℃ to about 35 ℃.In some embodiments, paper pulp and ozone is in the reaction of 1 to about 7 pH value scope, and perhaps more specifically from about 2 to about 6.
The paper pulp of handling in this method can comprise trace metal in suspension, described chelating agent can play the chelating trace metal.This method can comprise other step before ozone stage, promptly be determined at the kind of trace metal in the paper pulp and/or the amount of trace metal, selected the amount of the type of chelating agent and/or chelating agent with the coupling trace metal based on the mensuration of trace metal then.The pH value of ozone stage can also be regulated according to the kind and the amount of trace metal.
Though do not plan to limit, think to relate to following mechanism in the selectivity of the improvement that produces by method of the present invention by theory.Ozone delignification produce as with the hydrogen peroxide of lignin reaction's accessory substance.Under the common acid condition of ozone stage, hydrogen peroxide decomposes and produce several free radicals, the great majority of this free radical ground of not making any distinction between reacts with lignin or paper pulp fast.If there is trace metal contamination, then this decomposition of hydrogen peroxide is faster with the spot, and tends to produce the more disadvantageous free radical of cellulose degradation.Think that the decomposition of hydrogen peroxide under acid condition can stop by adding chelating agent in ozone stage.By preventing hydrogen peroxide decomposes, harmful free radical can not produce.Any trace metal ion of the decomposition that causes hydrogen peroxide that the interpolation of chelating agent also should chelating exists.Consider that destructive free radical is the popular theory of the accessory substance of ozone and lignin reaction in the pulp industry, improving selectivity in ozone stage by stable peroxide hydrogen is surprising discovery.
And, for destructive free radical, think and compare with the decomposition of hydrogen peroxide, may there be another even bigger source.If there is suitable activator, ozone also will resolve into the free radical of very activated non-selectivity.Free radical from hydrogen peroxide decomposes is the activator that ozone resolves into free radical.Once you begin, this circulation is that the ozone up to whole of controlling oneself is depleted.The free radical that produced by ozone and hydrogen peroxide decomposes is very activated and non-selectivity.Therefore, the traditional theory that ozone and lignin reaction produce free radical looks on final result it is correct, but has ignored controlled important intermediate steps.Traditional theory is that free radical is the direct result of lignin and ozone reaction, and because target is to make ozone and lignin reaction, so the generation of harmful free radical can not stop.Yet among the present invention, by the decomposition of stable peroxide hydrogen, we have stoped ozone to resolve into the initiation step of free radical, and this should make ozone delignification more effective and more selective.Therefore, think that method of the present invention is novel in surprising.
Experiment
First group of experiment relates to northern mixed hardwood kraft pulp.Second group of experiment relates to the southern pine kraft pulp.Before applying, ozone in the laboratory, two kinds of thick slurries are carried out oxygen delignification.Two kinds of paper pulp one is ozonisation under than 40% bigger concentration exceptionally.
The results are shown in the following Table A of hardwood experiments.
Table A
The ozone treatment of north mixed hardwood
| Sample | Permanganate number | % delignification | Ozone-depleting | The ISO whiteness | Viscosity, cps. | Selectivity Δ K/ Δ V |
| Thick slurry | 11.2 | |||||
| Oxygen delignification | 6.3 | 43.75 | ?58.23 | 17.6 | ||
| Ozone control | 3.5 | 44.44 | 0.506 | ?73.96 | 12.7 | 0.58 |
| Ozone and chelating agent | 3.4 | 46.03 | 0.506 | ?74.35 | 14.5 | 0.93 |
All experiment is to apply 0.70% ozone and carry out in the rotavapor reactor.Chelating agent (
2010) apply with 2.6% the remarkable high rate that applies.The selectivity term is that the variation of permanganate number is divided by viscosity change.Use permanganate number to be because it is a kind of more accurate test for low lignin pulp for this paper pulp.Think that it is extraordinary optionally increasing.
The experimental result of cork is shown among the following table B.
Table B
The southern pine ozone treatment
| Sample | Kappa number | % delignification | Ozone-depleting | The ISO whiteness | Viscosity, cps. | Selectivity Δ K/ Δ V |
| Thick slurry | 47.7 | |||||
| Oxygen delignification | 19.9 | 58.28 | 28.32 | 17 | ||
| Ozone control | 15.0 | 24.67 | 0.53 | 36.67 | 12.3 | ?1.06 |
| Ozone w/ 75ppm Ch. | 14.1 | 28.90 | 0.42 | 37.09 | 12.3 | ?1.24 |
| Ozone w/ 150ppm Ch. | 14.0 | 29.58 | 0.43 | 38.26 | 12.1 | ?1.22 |
| Ozone w/ 225ppm Ch. | 14.3 | 27.92 | 0.42 | 39.19 | 12.5 | ?1.25 |
| Ozone control | 14.6 | 26.71 | 0.41 | 37.53 | 12.0 | ?1.07 |
| Ozone w/ 750ppm Ch. | 16.0 | 19.40 | 0.12 | 34.34 | 14.5 | ?1.59 |
| Ozone control | 14.5 | 27.36 | 0.50 | 37.31 | 12.0 | ?1.11 |
Whole operations apply 0.65% ozone and carry out.Because the problem that the rotavapor reactor has, all experiment is carried out in 2 liters of hand flasks.Because experiment needs to add the chelating agent of a large amount of volumes for 750ppm, so concentration is reduced to 28.3%.Lower concentration might be the lower reason of consumption rate.Better mixing might help to increase the consumption of ozone.And ozone applies also little with expectation than target.Selectivity is improved the same with hardwood experiments not big, but it remains great.
The experiment of use 750ppm chelating agent also comprises the chelating agent of remarkable high dose.Afterwards, we recognized that two experiments may be subjected to the pollution of a large amount of relatively copper.Copper is considered to the metal that causes that hydrogen peroxide decomposes is the most harmful.Therefore, we very fortunately have some very the chelating agent of high dose be used for two groups of experiments.Think in order to optimize this method, preferably with chelating agent and metal pollutant coupling.
According to the regulation of patent statute, principle of the present invention and mode of operation are described in the mode of embodiment preferred.Yet, it must be understood that the present invention can also not break away from its essence or scope ground and implement except described in detail.
Claims (7)
1. the method that wood pulp is handled, this method comprises:
In ozone stage, paper pulp is contacted with ozone so that paper pulp is bleached and delignification, do not add peroxide bleaches; With
The phosphonate ester chelating agent is incorporated into ozone stage to improve delignified selectivity.
2. the described method of claim 1, wherein delignified selectivity is compared with the same procedure that does not have chelating agent and has been improved at least 10%.
3. the described method of claim 1, wherein the reaction time of paper pulp and ozone is in the scope in 1 second to 5 hour.
4. the described method of claim 1, wherein the reaction time is the scope from 10 seconds to 10 minute.
5. the described method of claim 1 wherein makes paper pulp and ozone reaction under the temperature of 20 ℃ to 90 ℃ scope.
6. the described method of claim 1 wherein makes paper pulp and ozone reaction under the pH of 1 to 7 scope.
7. the described method of claim 1 is wherein bleached and delignification as unique bleaching/delignification agent with ozone.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/300,126 | 2005-12-14 | ||
| US11/300,126 US20070131364A1 (en) | 2005-12-14 | 2005-12-14 | Process for treating a cellulose-lignin pulp |
| PCT/US2006/047416 WO2007070527A2 (en) | 2005-12-14 | 2006-12-12 | Process for treating a cellulose-lignin pulp |
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| Publication Number | Publication Date |
|---|---|
| CN101426975A CN101426975A (en) | 2009-05-06 |
| CN101426975B true CN101426975B (en) | 2011-09-21 |
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| CN2006800468212A Expired - Fee Related CN101426975B (en) | 2005-12-14 | 2006-12-12 | Process for treating a cellulose-lignin pulp |
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| US (1) | US20070131364A1 (en) |
| EP (1) | EP1979532A4 (en) |
| JP (1) | JP2009520120A (en) |
| CN (1) | CN101426975B (en) |
| AU (1) | AU2006326561B8 (en) |
| BR (1) | BRPI0619948A2 (en) |
| CA (1) | CA2633540A1 (en) |
| NO (1) | NO20082756L (en) |
| WO (1) | WO2007070527A2 (en) |
| ZA (1) | ZA200804881B (en) |
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| SG174772A1 (en) * | 2006-09-11 | 2011-10-28 | Curis Inc | Multi-functional small molecules as anti-proliferative agents |
| JP2015521694A (en) | 2012-06-13 | 2015-07-30 | ユニバーシティー オブ メイン システム ボード オブ トラスティーズ | Energy efficient method for producing nanocellulose fibers |
| CN106283794B (en) * | 2016-11-02 | 2017-11-21 | 江南大学 | A kind of method that flaxen fiber lignin is removed using ozone |
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| US4238282A (en) * | 1979-07-23 | 1980-12-09 | Nalco Chemical Company | Chemical treatments in bleaching stages which increase pulp brightness |
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|---|---|---|---|---|
| US4119486A (en) * | 1975-08-14 | 1978-10-10 | Westvaco Corporation | Process for bleaching wood pulp with ozone in the presence of a cationic surfactant |
| DE3544398A1 (en) * | 1985-12-16 | 1987-06-19 | Sueddeutsche Kalkstickstoff | METHOD FOR THE BLEACHING AND DELIGNIFICATION OF CELLULAR-BASED PRODUCTS |
| US5188708A (en) * | 1989-02-15 | 1993-02-23 | Union Camp Patent Holding, Inc. | Process for high consistency oxygen delignification followed by ozone relignification |
| US5164043A (en) * | 1990-05-17 | 1992-11-17 | Union Camp Patent Holding, Inc. | Environmentally improved process for bleaching lignocellulosic materials with ozone |
| US5164044A (en) * | 1990-05-17 | 1992-11-17 | Union Camp Patent Holding, Inc. | Environmentally improved process for bleaching lignocellulosic materials with ozone |
| EP0565625A1 (en) * | 1991-01-03 | 1993-10-20 | Union Camp Patent Holding, Inc. | Chlorine-free process for bleaching lignocellulosic pulp |
| SE468355B (en) * | 1991-04-30 | 1992-12-21 | Eka Nobel Ab | CHEMISTRY OF CHEMICAL MASS THROUGH TREATMENT WITH COMPLEX PICTURES AND OZONE |
| US5364503A (en) * | 1992-02-20 | 1994-11-15 | Macmillan Bloedel Limited | Nitric oxide treatment for ozone bleaching |
| BE1006057A3 (en) * | 1992-07-06 | 1994-05-03 | Solvay Interox | Method for delignification of chemical pulp. |
| EP0665912B1 (en) * | 1992-10-23 | 1998-02-11 | Macmillan Bloedel Limited | Improved ozone bleaching |
| US5364506A (en) * | 1993-04-28 | 1994-11-15 | The Board Of Trustees Of The Leland Stanford Junior University | Method and apparatus for partial oxidation of methane and cogeneration of electrical energy |
| SE500616C2 (en) * | 1993-06-08 | 1994-07-25 | Kvaerner Pulping Tech | Bleaching of chemical pulp with peroxide at overpressure |
| SE502667C2 (en) * | 1993-07-12 | 1995-12-04 | Kvaerner Pulping Tech | Treatment of fiber material with complexing agents before cooking |
| US5662803A (en) * | 1996-04-09 | 1997-09-02 | Nalco Chemical Company | Stabilizers for additives in aqueous systems containing ozone |
| CA2189724A1 (en) * | 1996-07-08 | 1998-01-09 | Suezone Chow | Method of pulping |
| WO1998011295A1 (en) * | 1996-09-11 | 1998-03-19 | Solvay Interox (Societe Anonyme) | Method for bleaching paper pulp |
| ES2209420T3 (en) * | 1998-04-17 | 2004-06-16 | Alberta Research Council, Inc. | LIGNOCELLULOSIC PULP PRODUCTION METHOD FROM NON-WOOD SPECIES. |
| SE514947C2 (en) * | 1998-09-09 | 2001-05-21 | Valmet Fibertech Ab | Bleaching of pulp with ozone including oxalic acid addition |
| US6302997B1 (en) * | 1999-08-30 | 2001-10-16 | North Carolina State University | Process for producing a pulp suitable for papermaking from nonwood fibrous materials |
| US7396974B2 (en) * | 2002-02-08 | 2008-07-08 | University Of Maine | Oxidation using a non-enzymatic free radical system mediated by redox cycling chelators |
| DE10320618A1 (en) * | 2003-05-08 | 2004-11-18 | Papierfabrik Albbruck Gmbh & Co. Kg | Process for bleaching fibrous materials |
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2005
- 2005-12-14 US US11/300,126 patent/US20070131364A1/en not_active Abandoned
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2006
- 2006-12-12 WO PCT/US2006/047416 patent/WO2007070527A2/en active Application Filing
- 2006-12-12 CA CA002633540A patent/CA2633540A1/en not_active Abandoned
- 2006-12-12 AU AU2006326561A patent/AU2006326561B8/en not_active Ceased
- 2006-12-12 EP EP06839344A patent/EP1979532A4/en not_active Withdrawn
- 2006-12-12 BR BRPI0619948-8A patent/BRPI0619948A2/en not_active IP Right Cessation
- 2006-12-12 CN CN2006800468212A patent/CN101426975B/en not_active Expired - Fee Related
- 2006-12-12 JP JP2008545747A patent/JP2009520120A/en active Pending
-
2008
- 2008-06-04 ZA ZA200804881A patent/ZA200804881B/en unknown
- 2008-06-18 NO NO20082756A patent/NO20082756L/en not_active Application Discontinuation
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| US4238282A (en) * | 1979-07-23 | 1980-12-09 | Nalco Chemical Company | Chemical treatments in bleaching stages which increase pulp brightness |
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Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0619948A2 (en) | 2011-10-25 |
| AU2006326561B8 (en) | 2011-04-07 |
| CN101426975A (en) | 2009-05-06 |
| WO2007070527A3 (en) | 2008-11-13 |
| US20070131364A1 (en) | 2007-06-14 |
| EP1979532A2 (en) | 2008-10-15 |
| AU2006326561B2 (en) | 2011-03-17 |
| ZA200804881B (en) | 2009-03-25 |
| WO2007070527A2 (en) | 2007-06-21 |
| JP2009520120A (en) | 2009-05-21 |
| CA2633540A1 (en) | 2007-06-21 |
| AU2006326561A1 (en) | 2007-06-21 |
| NO20082756L (en) | 2008-08-11 |
| EP1979532A4 (en) | 2011-09-28 |
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