CN1297085A - Method for use of activated ozone in bleaching paper pulp - Google Patents
Method for use of activated ozone in bleaching paper pulp Download PDFInfo
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- CN1297085A CN1297085A CN00128482A CN00128482A CN1297085A CN 1297085 A CN1297085 A CN 1297085A CN 00128482 A CN00128482 A CN 00128482A CN 00128482 A CN00128482 A CN 00128482A CN 1297085 A CN1297085 A CN 1297085A
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- 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
- D21C9/1005—Pretreatment of the pulp, e.g. degassing the pulp
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- 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
- D21C9/101—Bleaching ; Apparatus therefor in solvent medium
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- 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
- D21C9/1057—Multistage, with compounds cited in more than one sub-group D21C9/10, D21C9/12, D21C9/16
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- 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
- D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
- D21C9/14—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites
- D21C9/142—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites with ClO2/Cl2 in a multistage process involving ClO2/Cl2 exclusively
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- 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
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- 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
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
An ozone based bleaching method for bleaching lignocellulosic materials comprising a bleaching sequence of at least four sequential stages, said stages including an oxidative treatment stage, an alkaline extraction stage, an activated ozone bleaching stage, and a final bleaching stage to produce a pulp of desired final brightness. The activated ozone bleaching stage comprises the addition of an ethanol/DMSO mixture to the pulp prior to the ozone reaction.
Description
The present invention relates to a kind of method of from paper pulp, removing lignin, more specifically, relate to a kind of method of utilizing activated ozone bleaching lignin fibrous matter.
The most of paper pulp that obtain from system wood pulp process are because the existence of a small amount of lignin is furvous.In order to obtain the paper of high gloss, should in bleaching process, remove residual lignin fully.So far, mol-chloric, clorox and chlorine dioxide are the main agents that is used for the cellulose pulp bleaching, its operation such as C/DEDED, CEHDED, CEHD, CEHDH and CEHED.Pulp quality and bleaching expense are the principal elements that bleaching process is adopted in decision.But, find in waste water after the organic chloride material that pulp and paper industry has spent a large amount of effort to go to seek the new technology that these materials of reduction are discharged with waste water in recent years.
According to report, waste water is mainly derived from the bleaching process of cellulose pulp, comes from the degradation compound that mol-chloric and lignin reaction produce, referring to C.Rappe etc., " about the generation of PCDDS in the pulp bleaching process and PCDFS ", Pulp and Paper Canada, in August, 1989.
These chlorides are difficult to natural degradation, because they contain the carbon-to-carbon covalent bond.Wherein, various materials, promptly 2,3,7,8-tetrachloro-dibenzofuran (TCDF) and 2,3,7,8-tetrachloro-dibenzodioxine things such as (TCDD) be proved to be biological accumulation, genotoxic potential and environmentally harmful arranged.
For the discovery pressure that these materials produced in waste water is reacted, pulp and paper industry is being sought bleaching process, and this technology is allowed the high-quality paper pulp of production, produces the waste water that quality conforms with existing Environmental Law regulation simultaneously.Like this, bleaching process has developed into and continue to seek has reduced or get rid of mol-chloric and adopt other reagent, such as chlorine dioxide, oxygen, hydrogen peroxide, ozone, enzyme and peracid.Adopt these reagent to be directed at the bleaching process of so-called ECF (element-free chlorine) and TCF (completely without chlorine).
As if but this class is not enough to satisfy national legislation and the public concern to environment.The closed water circulation that is used for the pulp and paper industry process may can become a kind of requirement very soon.Adopt ECF and TCF operation to provide a chance, reclaim the closed water circulation that circulation realizes bleach plant by partly or entirely returning of waste water for pulp and paper industry.Some world-class kraft pulp enterprises are estimating the closed circulation operation, and its purpose is to obtain the acceptability of environmental quality and products thereof on market with rational expense.
Once did repeatedly to attempt for controlling this problem.Known after the illeffects that detects organic chloride confrontation water body organism, first measure of Cai Yonging once is to carry out after-treatment with oxygen delignification and/or to sewage.The oxygen delignification operation can be removed the residual lignin of about 40-50%, and carbohydrate is not had obvious influence.Therefore, bleach available lower reagent consumption and carry out, its result enters in the sewage that is produced less organic chloride.
An important improvement of conventional bleaching operation is the consumption that reduces the consumption of mol-chloric and increase chlorine dioxide.In most pulp factories, in first bleachery, improve this process with chlorine dioxide substituted molecule chlorine.
Been reported, the AOX in the sewage (absorbable organic chloride) level can be with oxygen delignification, replace the biological treatment of chlorine, sewage to reach obvious reduction with chlorine dioxide.The environmental pollution index that other is important can be reduced with these measures equally such as color, bod (BOD), the chemical oxygen consumption (COC) (COD) of sewage.Referring to J.W.Graves etc., " chlorine dioxide replacement, oxygen delignification and biological treatment are to the effect of bleaching factory sewage ", TappiJournal, in July, 1993.
Ozone, a kind of three oxo-compounds are a kind of strong oxidizers, and lignin is had strong reactivity.It is to realize under low denseness and high-consistency that kraft pulp is first handled, and finds once that the dissolving of ozone in fibrous suspension was the decisive factor of process.Referring to, M.Byrd etc., " ozone to the delignification and the bleaching of chemical pulp: literature review ", Tappi Journal, in March, 1992.
Relating to the work that ozone uses in ECF and TCF bleaching process is to carry out with changing used reaction denseness and added ozone dosage.Be oxygen workshop section before the ozone workshop section, medium be alkaline, is thereafter the simple alkali workshop section of coming together.Final bleaching available chlorine dioxide (ECF operation) or hydrogen peroxide (TCF operation) workshop section finish.Referring to, patent No.WO 91/18145, signs to be B.F.Gregg etc.
Equally, U.S. Patent No. 4,959,124 (Tsai) relate to step process softwood kraft pulp such as chlorine dioxide delignification (D), ozone bleaching (Z), alkali collection (E, Eo, Ep, Eo) and dissolvings.
Though technology develops to some extent, industry still needs a kind of better bleaching process, and its operating cost sewage low, that produced quality little to ambient influnence, the gained final products is close or more excellent.
There are two main shortcomings in the application of pressing the ozone of above-cited all method for bleaching.These shortcomings comprise: (1) bleaching efficiency is low low to the bleaching selectivity of paper pulp lignin with (2).The ozone bleaching definitions of efficiency is the kappa unit of number that ozone reduced of per kilogram consumption in the ozone workshop section, and it is too low usually so that can not prove that high ozone bleaching expense is rational.On the other hand, the definition of the bleaching selectivity of ozone is that its value is too low usually by the ratio of the kappa unit of number with the viscosity unit of ozone workshop section reduction, thus the damage pulp quality.Therefore, need find the alternative scheme of using ozone bleached pulp, this alternative scheme can improve the efficient and the selectivity of process.
Therefore, the object of the present invention is to provide a kind of new method, cause the gross efficiency of ozone treatment workshop section and selectivity to improve with ozone bleaching paper pulp.Its result makes the ozone-depleting that reaches target kappa number be lower than conventional ozone bleaching method.In addition, be higher than with the obtained viscosity of conventional ozone approach with the final pulp viscosity of method of the present invention through the paper pulp of ozone treatment.
Secondly, the present invention also aims to provide a kind of new method for bleaching that comprises an ozone workshop section, compare with conventional dioxde pulp bleaching process, the efficient and the selectivity of new method are higher, the ambient influnence of the sewage that produces is lower, and the quality of the final products of gained is close or more excellent.
Method with activated ozone bleaching lignin cellulosic material comprises at least by four bleaching process that go on foot.Its in succession workshop section comprise that there be activated ozone bleachery and the final bleachery that carries out down in oxidation processes workshop section, alkali workshop section, the ethanol that proper proportion is arranged and methyl-sulfoxide (DMSO) mixture.
Oxidation processes workshop section available chlorine, chlorine dioxide, ozone, hydrogen peroxide, peracid or other oxidant carry out under the condition that those skilled in the art is known.
Alkali collection workshop section can use arbitrary alkali source, and preferred NaOH carries out under the condition that pulp industry is used always.
The activated ozone bleachery comprises with inorganic acid acidifying paper pulp reaches in the scope of 1.5-5 its pH, paper pulp through acidifying is assisted mixture process with ethanol/DMSO, paper pulp ozone treatment after auxiliary processing, then use in the alkali and the paper pulp after ozone treatment, its pH value is reached in the scope of 5-10.
The activated ozone bleachery is about 15% for about 1%-in the reaction denseness, reaction temperature is carried out under about 20 ℃-Yue 90 ℃, and the reaction time is about 1-120 minute.The dosage of inorganic acid is in about 4% scope of about 0.5%-, ethanol dosage in about 20% scope of about 0.001-, DMSO dosage in about 8% scope of about 0.001-, ozone dosage in about 1.0% scope of about 0.1%-and the dosage of alkali in about 3% scope of about 0.5-.All dosage is by the dry pulp fibre weight.
Paper pulp after activated ozone is handled is then through washing and/or directly transfer to final bleaching operation, in this operation, continue to handle through one or more workshop sections with chlorine dioxide and/or hydrogen peroxide, its condition is the known normal condition of those skilled in the art, makes product reach the final mass of expection.
For purpose of the present invention, " Kappa number " means the KMnO of the 0.1N that paper pulp consumed that 1 gram parches
4The milliliter number of solution, it is relevant with the association with pulp bleaching degree.Viscosity is a kind of indirect measurement of paper cellulose chain average degree of polymerization, and it is relevant with the intensity property of paper pulp.
For the present invention, " efficient " means kappa unit's (kappa number) number (kg/t) that reduces by the used ozone of (ZE) workshop section per kilogram.
For the present invention, " selectivity " means that the percentage of kappa number is divided by the viscosity percentage that reduces by (ZE) workshop section.Paper pulp kappa numerical value, viscosity and glossiness are measured according to the Tappi standardization program.
Other purpose, feature and advantage will be showed to those skilled in the art with the description and the accompanying drawing of following preferred version.
The displaying that Fig. 1 represents method of the present invention use the operation of bleachery of the optimization pattern of activated ozone.
The present invention can finish with the activated ozone pulp treatment, and ozone treatment is carried out after oxidizer treatment and alkali extraction. After activated ozone is processed, paper pulp with chlorine dioxide and/or hydrogen peroxide bleaching until reach the glossiness of expection.
Different from the work of finishing in this field in the past, in the present invention, ozone workshop section is the mixture activation of ethanol and the methyl-sulfoxide of proper proportion with organic solvent. Ethanol/DMSO mixture plays synergy in ozone workshop section, improve the efficient of ozone and paper pulp reaction with selective.
The effect of ethanol is by increasing speed (mass unit of the kappa unit of the removal/ozone that consumes) that lignin removes with the efficient of improvement ozone bleaching. Ethanol plays free radical scavenger, and it captures some free radical in the ozone bleaching process, i.e. hydroxy and peroxide, and these free radicals promote the decomposition reaction of ozone. By capturing these free radicals, ethanol makes the loss reduction of ozone in undesirable reaction, thereby increases total process efficiency.
On the other hand, the effect of DMSO is to improve the selective of ozone workshop section by the decomposition rate (the kappa unit of the viscosity unit of loss/removal) that reduces carbohydrate. Methyl-sulfoxide (DMSO) has the inhomogeneity double action that contacts with paper pulp fiber as free radical scavenger and increase ozone. Therefore, the carbohydrate of its protection paper pulp is avoided decomposing. Known DMSO is by fracture intermolecular hydrogen bonding and the water-bound orderly with the complexing destruction of water. The change of water-bound has improved the diffusion rate that ozone enters water, and its result reduces the accumulation of ozone concentration in regional area.
(ethanol/DMSO) have unexpected effect can be worked in coordination with the efficient of improvement ozone workshop section simultaneously with selective to adopt ORGANIC SOLVENT MIXTURES in ozone workshop section. Organic solvent should add paper pulp together, in order to can obtain cooperative effect.
In addition, different from the work before in this field, in the present invention, before processing, activated ozone for oxidation and alkali extraction workshop section, then is pulp washing. Like this, ozone does not react with previous oxidized lignifying compound, and this lignin is extracted by alkali, and ozone does not also react with the paper pulp with high kappa number and high-load transition metal, their part removals in oxidation section.
According to the present invention, activated ozone more effectively and more selectively with the paper pulp reaction of low kappa number, it is few that the carrier mass of this paper pulp contains residual lignin, contained free phenol unit (or " phenol-lignin ") is few in the structure. " carrier mass " is defined as the not oxidation of bringing into paper pulp from the operation workshop section of front and the organic substance of oxidation. " phenol-lignin " is defined as the part lignin of bringing into the paper pulp that contains free phenol hydroxy. Carrier mass and phenol-lignin all are ozone bleaching workshop section efficient and selective not high reason. Low carrier mass content and the low phenol feature of the paper pulp of processing according to method of the present invention are because paper pulp was independently being processed respectively with oxidant and alkali in the workshop section before this.
The present invention shows that the activated ozone bleachery has very high efficient and selective, if used paper pulp before extracted with oxidizer treatment and through alkali.
The present invention relates to a kind of bleaching from non-wood fiber, hardwood, cork, its mixture, or the method for the ligno-ccllulose material of gained in the fiber that reclaims. The method for bleaching that proposes comprises several workshop sections, between each workshop section with among different schemes can be arranged. The present invention allows the dissimilar ligno-ccllulose material that employing obtains from dissimilar pulping process. Before method for bleaching of the present invention, this ligno-ccllulose material can be processed with oxygen. The ligno-ccllulose material of processing with oxygen in fact is better than common ligno-ccllulose material.
First workshop section of this method relates in oxidation section with a kind of oxidizer treatment paper pulp, and its purpose is to dissolve transition metal and etch and contains the free phenol unit (or phenol-lignin) brought into the paper pulp of front workshop section and the lignin of carrier mass.
Second workshop section of this method relates in alkali extraction workshop section with arbitrary alkali source pulp treatment. The purpose of this processing is extraction and the oxidized compound of the previous oxidation section of solubilization. Once imagined, the nucleophilic displacement of fluorine that is caused by alkali workshop section is the necessary condition that forms new electrophilic etch point in the residual lignin structure. Referring to, " delignification chemistry ". Outline: second portion, Gierer, January, 1982, Holzforschung (timber research).
The 3rd workshop section of this method, i.e. innovative point of the present invention, by forming with the activated ozone pulp treatment in acid medium, its condition is that the kappa number that is directed at paper pulp reduces maximum simultaneously its carbohydrate and decomposes minimum. These conditions are included in ozone reaction adds ethanol/DMSO before to paper pulp mixture. Ethanol/DMSO mixture plays synergy, causes the reaction of ozone and paper pulp lignin maximum, makes the reaction of ozone and paper pulp carbohydrate minimum.
Activated ozone is handled workshop section and is carried out under the temperature of the denseness of about 1%-about 15% and about 20 ℃-Yue 90 ℃, and reaction time, about 1-was about 120 minutes, and ozone dosage is about 1.0% (with the dry weight basis of paper pulp fiber) of about 0.1%-.Ethanol/DMSO mixture just was added to paper pulp before injecting ozone.Desirable mode is that two kinds of solvents add together as mixture.The dosage of DMSO is for changing (in paper pulp fiber weight) in about 8% scope of about 0.01%-, the agent of ethanol is in about 20% scope of about 0.01%-.After ozone added, paper pulp neutralized with a kind of suitable alkali source, and preferred NaOH makes the pH value in the scope of about 5-10.The purpose of this neutralization is to destroy the excessive acidity and the catabolite of solubilization ozone and lignin reaction.
The paper pulp of activated ozone treatment then with chlorine dioxide and/or hydrogen peroxide bleaching, makes product reach the glossiness of expection.Chlorine dioxide and hydrogen peroxide bleaching are known the professional and technical personnel.
A selection process of the present invention is shown in Fig. 1, the figure shows the bleaching process 10 of DEop (aZE) D.Unbleached paper pulp 20 is sent into middle denseness pump 30, and denseness blender 32 in entering then mixed with chlorine dioxide 62 before entering D-workshop section 34.Here all pumps and blender all belong to middle denseness.After handling in washer 36 and washing, paper pulp mixed with NaOH and hydrogen peroxide 64 before entering pump 38, mixed with oxygen 66 in blender 40 before entering Eop extraction workshop section 42 then.After washer 44 washings, paper pulp mixed with sulfuric acid 68 before entering pump 46, and it receives ethanol/DMSO mixture 70 here, enters blender 48 again, and paper pulp stands the processing of ozone 72 here.The paper pulp that activated ozone was handled mixes with NaOH 74 then, and transfers to neutralizing tower 52 to finish (aZE)-workshop section through pump 50.Paper pulp washing in washer 54 then, is handled with chlorine dioxide 76 in D-workshop section 60 to blender 58 here through pump 56 pumps again, and gained bleached pulp 78 is sent into final washer then.
The following examples will further be illustrated favourable part of the present invention:
Embodiment 1-8:
The used paper pulp of this serial embodiment is from kraft pulp factory, and in the last washing room behind oxygen delignification, the kappa number of paper pulp is 9.1, and viscosity is 36.1 mPa.s, and glossiness is 55%ISO.Embodiment 1 (reference example) adopts 0.4% ozone (in paper pulp weight) pulp treatment under 10% denseness, 30 ℃, pH2.5, then with 1.2% NaOH in 10% denseness, 60 ℃ times and 30 minutes, paper pulp is used excessive distilled water wash again.These chemically treated being combined in hereinafter are called (ZE)-workshop section.Embodiment 2 adopts embodiment 1 described same treatment, but adds 10% ethanol (in fibre weight) in ozone workshop section.Embodiment 3 finishes under the condition identical with embodiment 1, but adds 4%DMSO in ozone workshop section.Embodiment 4 is similar to embodiment 1, but adds 10% ethanol and 4%DMSO mixture in ozone workshop section.The condition of embodiment 5-8 is identical with embodiment 4, but the excursion of the dosage of ethanol/DMSO mixture is listed in table 1.The result of embodiment 1-8 is with (ZE)-workshop section efficient and selectivity and final paper pulp glossiness explanation.Kappa numerical value and viscosity that paper pulp records after (ZE)-workshop section are used for computational efficiency and selectivity.
Table 1. in advance with the hardwood kraft pulp of oxygen delignification have with additive-free condition under the characteristic of (ZE)-workshop section of carrying out.
| Embodiment # | Additive | Efficient | Selectivity | Glossiness, %ISO |
| ?1 | Additive-free (reference) | ?1.09 | ?1.28 | ?70.8 |
| ?2 | ?10％EtOH | ?1.54 | ?1.33 | ?73.0 |
| ?3 | ?4％DMSO | ?1.21 | ?1.65 | ?72.1 |
| ?4 | ?10％EtOH+4％DMSO | ?1.71 | ?1.79 | ?74.7 |
| ?5 | ?7.5％EtOH+3％DMSO | ?1.50 | ?1.61 | ?72.6 |
| ?6 | ?5.0％EtOH+2％DMSO | ?1.48 | ?1.53 | ?72.5 |
| ?7 | ?2.5％EtOH+1％DMSO | ?1.37 | ?1.44 | ?72.3 |
| ?8 | ?1.25％EtOH+0.5％DMSO?? | ?1.23 | ?1.37 | ?71.0 |
Embodiment 1 compares with 2, as can be seen, added ethanol to paper pulp and can improve the efficient of (ZE)-workshop section greatly before ozone treatment, simultaneously the selectivity of influence process a little only.On the other hand, embodiment 1 and 3 comparison shows that were added DMSO and are improved (ZE)-workshop section selectivity greatly before ozone treatment, improve efficient simultaneously a little.Embodiment 1,2,3 and embodiment 4 comparison shows that, added ethanol/DMSO mixture to paper pulp and be higher than additive in the income aspect efficient and the selectivity before ozone treatment.Infer that thus these two kinds of additives have synergy to the reaction of promoting ozone and paper pulp.Be higher than the gain (41%) of independent ethanol and the summation of the gain (11%) of DMSO separately with the efficiency gain (75%) of (the ZE)-workshop section of ethanol/DMSO mixture gained, its both additions only are 52%.Equally, the optionally increase (40%) of adopting mixture ethanol/DMSO to be brought is higher than the increase (4%) of independent employing ethanol or the increase (29%) of DMSO, and the summation that its selectivity increases only is 33%.
From embodiment 1-4 as can be seen, ethanol can effectively improve the efficient of ozone and paper pulp lignin reaction, and DMSO can reduce the etch of ozone to the paper pulp carbohydrate, thereby improves selectivity.These additive combinations all can be improved the efficient of ozone bleaching and selectivity in mixture.In addition, when these additives add as mixture, its comprehensive effect surpasses the summation of each additive individual effects, therefore, it is characterized in that, the cooperative effect between two additives has been improved the efficient and the selectivity of ozone treatment.
Be noted that and cooperative effect when estimating the paper pulp glossiness, also occurs.Adopting the glossiness gain sum of ethanol (gain 2.2%ISO) and the independent DMSO of employing (gain 1.3%ISO) gained separately is 3.5%, is lower than the glossiness that these additives add gained with form of mixtures in ozone treatment and gains, and its amount is 3.9%.
Embodiment 5-8 also shows, with ethanol/DMSO mixture in pulp treatment before the ozone treatment to the improvement of efficient, selectivity and the glossiness of (ZE)-workshop section even be significantly less than at the dosage of additive under the situation of embodiment 4 described dosage and still can remain valid.But,, adopt the gain tendency of additive agent mixture to reduce along with the reduction of its dosage.
The bleaching of chemical pulp is carried out with multiplex's section usually.(ZE)-one of the workshop section of its operation normally of workshop section.Importantly determine remain valid when whether the gain of efficient, selectivity and the glossiness that is improved in (ZE)-workshop section after ozone reaction forward direction paper pulp adds the DMSO/ alcohol mixture can use this workshop section in the operation of multiplex's section.In other words, importantly determine in ozone workshop section, to utilize this additive agent mixture to whole chemical bleaching requirement with to the influence of the pulp quality of final bleaching.This will be illustrated by the following examples 9-13.
Embodiment 9-13:
The used pulp sample of this serial embodiment is from kraft pulp factory, and in the last washing room behind oxygen delignification, the kappa number of paper pulp is 9.1, viscosity 36.1 mpa.s, and glossiness is 55%ISO.This paper pulp is bleached with five kinds of different bleaching schedules.
Embodiment 9 adopts DEopDD ECF bleaching process, and this operation is adopted (reference example) by a lot of industrial pulp mill.The one D-workshop section carries out under the condition of 10% denseness, 60 ℃ of temperature, 30 minute reaction time and final pH 3.0 (regulating with sulfuric acid).Eop-workshop section 1.1%NaOH, 0.5%O
2And 0.5%H
2O
2(in fibre weight) carries out under the condition of 90 minute reaction time and pH11.0 in 10% denseness, 200kPa pressure, 90 ℃ of temperature.The second and the 3rd D-workshop section carries out under the condition of 10% denseness, 70 ℃ of temperature, 180 minute reaction time and final pH 3.8 (regulating with NaOH).Washing between workshop section is carried out with excessive distilled water.Estimate the final glossiness and the viscosity of paper pulp according to the Tappi standardization program.
The bleaching process that embodiment 10 adopts is to utilize ozone in first workshop section of (ZE) DEopD operation.ZE-workshop section finishes under the condition of 10% denseness, 30 ℃ and pH2.5 with 0.4% ozone (in paper pulp weight), then paper pulp with 1.2% NaOH 10% denseness, 60 ℃ through processing in 30 minutes, paper pulp is used excessive distilled water wash again.The first and second D-workshop sections and Eop workshop section with example 9 described same programs and identical condition under finish.
Embodiment 11 adopts the operation identical with embodiment 10, but ozone treatment activates with ethanol/DMSO mixture.All the condition of bleachery keeps identical, but (ZE)-condition of workshop section is to have added the mixture of the DMSO of 10% ethanol/4% at ozone treatment forward direction paper pulp.
The bleaching process that embodiment 12 adopts is the ECF bleaching process that adopts ozone in the 3rd workshop section of the bleaching process of DEop (ZE) D operation.This operation is almost completely identical with embodiment 10 described operations, but (ZE)-workshop section is displaced to the 3rd workshop section from first workshop section.The program of all processes condition is identical with example 10 described maintenances.
The operation that embodiment 13 adopts is identical with embodiment 12, but adds middle ethanol/DMSO mixture to paper pulp before ozone treatment.Used described identical with embodiment 12 in different bleacheries according to the used condition of workshop section.
Table 2. ozone workshop section is with the influence of ethanol/DMSO mixture activation to the overall performance of (ZE) DEopD of the hardwood kraft pulp that is used for oxygen delignification and DEop (ZE) D operation.
| Embodiment # | Operation | Z-workshop section additive | Final glossiness, ISO | Final viscosity, mPa.s | ?????????ClO 2Consumption, % (in paper pulp weight) | ClO 2/O 3The replacement rate | |||
| ?Do | ?D1 | ?D2 | Add up to | ||||||
| ?9 | ?DEopDD | - | ?90.1 | ?15.4 | ?0.692 | ?0.725 | ?0.125 | ?1.542 | |
| ?10 | ?(ZE)DEopD | Do not have | ?90.0 | ?11.8 | ?0.381 | ?0.679 | ?- | ?1.060 | ?1.20 |
| ?11 | ?(ZE)DEopD | EtOH/ DMSO | ?90.2 | ?16.5 | ?0.381 | ?0.419 | ?- | ?0.800 | ?1.86 |
| ?12 | ?DEop(ZE)D | Do not have | ?90.0 | ?13.5 | ?0.381 | ?0.362 | ?- | ?0.742 | ?2.00 |
| ?13 | ?DEop(ZE)D | EtOH/ DMSO | ?90.1 | ?18.1 | ?0.381 | ?0.102 | ?- | ?0.482 | ?2.65 |
Embodiment 9 and 10 comparison shows that, the magnitude that using ozone reduces the demand of chlorine dioxide in first workshop section of ECF bleaching process is 1.2kg ClO
2The ozone that/kg is used.But this ozone application model is compared with the reference operation of ozone free, and ozone reduces paper pulp final viscosity (24%).On the other hand, if ozone is used for the 3rd workshop section, then ozone will improve greatly to the replacement rate of chlorine dioxide.Embodiment 9 and 12 comparison shows that the ozone that every kg is used for the 3rd workshop section replaces about 2kg chlorine dioxide.In addition, the viscosity loss that ozone treatment is brought is much smaller in this case, and the final viscosity value is only than reference example low 12%.
Therefore, there is remarkable influence the appropriate position of Z-workshop section in the bleaching sequence to its efficient and selectivity.
Other are to ozone workshop section efficient and optionally obviously improvement is by adding ethanol/DMSO mixture acquisition at ozone reaction forward direction paper pulp, and this can know from embodiment 1-8 (table 1) and find out.To point out that importantly the benefit that additive agent mixture brings can remain in the whole bleaching process.Embodiment 10 and 11 comparison shows that additive agent mixture makes ClO
2/ O
3The replacement rate be improved as 1.86 from 1.2, be about 55%, and final pulp viscosity increases about 28%.Can find same trend from comparative example 12 and 13, wherein utilize additive agent mixture to make ClO
2/ O
3The replacement rate increases by 33%, and final pulp viscosity increases by 34%.
When additive agent mixture was used for ozone workshop section (embodiment 11 and 13), in fact the final pulp viscosity of gained was higher than the viscosity of using with reference to the paper pulp gained of operation bleaching (embodiment 9).On the other hand, the total amount of used chlorine dioxide is significantly less than with reference to operation in the operation that contains activated ozone workshop section, and this is that a so-called ECF-gently bleaches, and promptly uses the good case of the ECF bleaching of low amount chlorine dioxide.
Find out obviously that from embodiment 1-13 utilize ozone to compare with conventional ozone bleaching method according to method of the present invention, its efficient and selectivity are all much higher.Simultaneously, the benefit of ozone workshop section (ZE) acquisition can run through whole bleaching process.Its result, total chlorine dioxide of bleached pulp demand will reduce greatly, and the paper pulp final viscosity will obviously increase.According to method of the present invention, adding ethanol/DMSO mixture is before ozone treatment, and the position of ozone treatment is the 3rd workshop section at bleaching process.
In order further to prove the benefit of the inventive method, the test method that embodiment 1-13 is used is applied to the ligno-ccllulose material of another type.Adopted the hardwood kraft pulp of using oxygen delignification in advance among the embodiment in front.Embodiment 14-17 adopts cork (fir pine) kraft pulp of oxygen delignification, and this paper pulp is for North America pulp factories particularly typical case.
Embodiment 14-17:
The used paper pulp of this serial embodiment obtains from softwood kraft pulp factory, paper pulp behind oxygen delignification through last washing room.The kappa number of sample is 18.9, and viscosity is 28.9mPa.s, and glossiness is 28.0%ISO.Embodiment 14 (reference example) adopts 0.3% ozone (in paper pulp weight) pulp treatment under 10% denseness, 30 ℃ and pH2.5, then carries out alkali treatment in 30 minutes with 1.2% NaOH under 10% denseness, 60 ℃, uses excessive distilled water wash paper pulp again.These two kinds of chemically treated combinations are hereinafter referred to as (ZE)-workshop section.Embodiment 15 adopts and embodiment 14 described processing much at one, but adds 10% ethanol (in fiber quality) at ozone treatment forward direction paper pulp.Embodiment 16 implements under the condition identical with embodiment 14, but adds 4%DMSO at ozone reaction forward direction paper pulp.Embodiment 17 is similar to embodiment 14, but adds 10% ethanol/4%DMSO mixture to paper pulp before ozone treatment.
The result of embodiment 14-17 is according to efficient and the selectivity and the final paper pulp glossiness explanation of (ZE)-workshop section.(ZE)-the kappa numerical value and the viscosity that record after the workshop section is used for computational efficiency value and selectivity.
Table 3. employing is having and the additive-free performance of (the ZE)-workshop section of enforcement down with the softwood kraft pulp of oxygen delignification in advance.
| Embodiment # | Additive | Efficient | Selectivity | Glossiness, ISO |
| ?14 | Additive-free (reference) | ?1.15 | ?1.27 | ?37.7 |
| ?15 | ?10％EtOH | ?1.55 | ?1.29 | ?40.1 |
| ?16 | ?4％DMSO | ?1.20 | ?1.65 | ?38.2 |
| ?17 | ?10％EtOH+4％DMSO | ?1.73 | ?1.81 | ?41.5 |
Comparison shows that between the embodiment 14 and 15 added ethanol to ozone treatment and will be improved the efficient of (ZE)-workshop section greatly, only influences the selectivity of technology simultaneously a little.On the other hand, comparison shows that between the embodiment 14 and 16, before the ozone treatment in paper pulp adds DMSO will improve the selectivity of (ZE)-workshop section greatly, improve simultaneously efficient a little.Embodiment 14,15 and 16 and comparison shows that of embodiment 17, the income of adding ethanol and DMSO to ozone workshop section is greater than single additive, imagination, these additives play synergy to improving the ozone bleaching method.The raising (50.4%) of adopting ethanol to add (ZE)-workshop section efficient that mixture obtained of DMSO is higher than independent employing ethanol (34.8%) and adopts DMSO (4.3%) profit sum separately, and both additions only are 39%.Equally, the optionally raising (42.5%) of adopting ethanol/DMSO mixture to bring be higher than that selectivity that ethanol (1.6%) or DMSO (30%) bring is separately improved and, both totals only are 31.6%.
Find out obviously that from embodiment 14-17 ethanol is effective to the efficient of improving (ZE)-workshop section, DMSO then improves the selectivity of (ZE)-workshop section.These additives are combined into mixture will make the efficient of (ZE)-workshop section and selectivity all improve.In addition, when these additives add together, the income that each additive brought surpass its single income and.Therefore, it is characterized in that this cooperative effect of these two additives improves the efficient and the selectivity of ozone treatment.
Be noted that cooperative effect appears in the evaluation of paper pulp glossiness equally.Income (0.5%ISO) sum that glossiness income (2.4%ISO) that independent ethanol brings and independent DMSO bring is 2.9%ISO, this value is lower than the glossiness income that these additives are brought with the form additive ozone treatment of mixture, and its value is 3.8%ISO.
The income of adding ethanol/DMSO mixture to the ozone workshop section of multiplex's section ECF bleaching process sees embodiment 18-22.The income of this processing with it to final pulp viscosity with reach the required total chlorine dioxide of target glossiness 90%ISO and come quantificational expression.
Embodiment 18-22:
Softwood pulp (fir pine) sample used in this serial example obtains from kraft pulp factory, and through last washing procedure, the kappa number of paper pulp is 18.9 to paper pulp behind oxygen delignification, and viscosity is 28.9mPa.s, and glossiness is 28.0%ISO.This paper pulp adopts 5 bleaching schedule bleachings.
Embodiment 18 adopts DEopDD ECF bleaching process, and this operation is the operation that a lot of industrial pulp mills adopt.The one D-workshop section reacted 30 minutes under 10% denseness, 60 ℃ of temperature, and final pH is 3.0 (regulating with sulfuric acid).Eop-workshop section is with 1.1% NaOH, 0.5% O
2, 0.5%H
2O
2(in fibre weight) reacted 90 minutes under 10% denseness, 200kPa pressure, 90 ℃ of temperature, and pH is 11.0.The second and the 3rd D-workshop section reacted 180 minutes under 10% denseness, 70 ℃ of temperature, and final pH is 3.8 (regulating with NaOH).Pulp washing between workshop section carries out with excessive distilled water.Final glossiness and the viscosity of estimating paper pulp are to make according to the Tappi standardization program.
Embodiment 19 adopts (ZE) DEopD bleaching process, and ozone is in first workshop section of process.(ZE)-workshop section finishes under 10% denseness, 30 ℃ and pH2.5 with 0.3% ozone (with the paper pulp dry weight basis), then carries out alkali treatment in 30 minutes with 1.2% NaOH under 10% denseness, 60 ℃, carries out pulp washing with excessive distilled water.The first and second D-workshop sections and Eop-workshop section with embodiment 18 described the same terms and program under carry out.
Embodiment 20 adopts the operation identical with embodiment 19, but adds 10% ethanol/4%DMSO mixture at ozone treatment forward direction paper pulp.All remaining conditions of bleaching are described identical with embodiment 19.
Embodiment 21 adopts a kind of ECF bleaching process, is DEop (ZE) D operation, and ozone is in the 3rd workshop section of bleaching process.This operation is described almost completely identical with embodiment 19, but ozone treatment is moved on to the 3rd workshop section from first workshop section of operation.The all processes condition keeps described identical with embodiment 19 with program.
Embodiment 22 adopts the operation identical with embodiment 21, but adds the mixture of 10% ethanol/4%DMSO at ozone treatment forward direction paper pulp.In this operation according to the used condition of workshop section with
Embodiment's 21 is identical.
Table 4. ozone workshop section ethanol/DMSO mixture activates the influence to the overall performance of (ZE) DEopD of the softwood kraft pulp of oxygen delignification and DEop (ZE) D operation.
| Embodiment # | Operation | Z-workshop section additive | Final glossiness, ISO | Final viscosity, mPa.s | ???????ClO 2Consumption, % (in paper pulp weight) | ClO 2/O 3The replacement rate | |||
| ?Do | ?D1 | ?D2 | Add up to | ||||||
| ?18 | ?DeopDD | ?- | ?90.0 | ?19.9 | ?1.725 | ?0.764 | ?0.191 | ?2.680 | ?- |
| ?19 | (ZE)DeopD | Do not have | ?90.1 | ?14.3 | ?1.006 | ?1.114 | ?- | ?21.120 | ?1.87 |
| ?20 | (ZE)DeopD | ?EtOH/ ?DMSO | ?90.1 | ?18.5 | ?1.006 | ?0.909 | ?- | ?1.915 | ?2.55 |
| ?21 | ?DEop(ZE)D | Do not have | ?90.1 | ?18.8 | ?1.006 | ?0.884 | ?- | ?1.890 | ?2.63 |
| ?22 | ?DEop(ZE)D | ?EtOH/ ?DMSO | ?90.0 | ?23.9 | ?1.006 | ?0.651 | ?- | ?1.657 | ?3.41 |
Embodiment 18 and 19 comparison shows that ozone is used for first workshop section of ECF bleaching process, for softwood pulp, reduce the demand of chlorine dioxide, its magnitude is 1.87kg ClO
2Ozone that/kg executes.But this application model is compared with the reference sequences of ozone free, and the pulp viscosity loss that ozone causes is about 28%.On the other hand, if ozone is used for the 3rd workshop section, then ozone will improve greatly to the replacement rate of chlorine dioxide.Embodiment 18 and 21 comparison shows that every kg ozone used in the 3rd workshop section replaces about 2.63kg chlorine dioxide.In addition, the viscosity loss that using ozone causes in the 3rd workshop section is very little, is 5% only, is lower than reference example.
Therefore, the result of softwood kraft slurry samples shows that equally there is tangible influence the appropriate position of Z-workshop section in bleaching process to the gross efficiency and the selectivity of bleaching process.
Ozone workshop section efficient and optionally obvious improvement also can reach by adding ethanol/DMSO mixture in ozone reaction forward direction softwood pulp.This can know from embodiment 14-17 and find out.Be noted that importantly these incomes remain in the whole bleaching process.Comparison shows that between the embodiment 19 and 20 adopts this additive agent mixture can make ClO
2/ O
3The replacement rate improves 36%, increase to 2.55 from 1.87, and the final viscosity of paper pulp increases by 29% approximately.Comparing embodiment 21 and 22 can be found same trend, wherein adopts additive agent mixture to make ClO
2/ O
3The replacement rate increases by 30%, and final pulp viscosity increases by 27%.If additive agent mixture joined (embodiment 22) in the paper pulp before ozone treatment, in fact then final pulp viscosity is higher than the viscosity (embodiment 18) with the paper pulp of the reference operation bleaching of ozone free.In addition, the used chlorine dioxide total amount of operation that contains activated ozone workshop section is significantly less than with reference to operation.
That concrete feature, particularly Fig. 1 of the present invention provide, only for simplicity, because each feature can make up with further feature according to the present invention.Those skilled in the art can be considered some replacement schemes, and these schemes attempt to be included within the scope of claim.
Claims (10)
1. the method for a bleaching lignin cellulosic material, it comprises the following steps:
A) phenol-lignin that transition metal dissolving, simultaneous oxidation is comprised bring into a kind of oxidizer treatment paper pulp at oxidation section and the lignin of carrier mass with ligno-ccllulose paper pulp;
B) handle this paper pulp of extraction by alkali collection, with extraction and solubilization this paper pulp from operation (a);
C) pass through to adopt the activated ozone workshop section processing of activated ozone this paper pulp from operation (b), make lignin and other coloring matter oxidation of remaining in the paper pulp, this activated ozone is handled workshop section and is comprised to paper pulp interpolation inorganic acid, ethanol/DMSO mixture and air-flow ozoniferous, then carries out the paper pulp neutralization with alkali; With
D) by the paper pulp of one or more bleacheries processing from workshop section (c), bleaching agent is selected from hydrogen peroxide and chlorine dioxide.
2. the process of claim 1 wherein in the step (c) that this step with the activated ozone pulp treatment comprises adds inorganic acid, ethanol/DMSO mixture, streams of ozone in order and is used for and excess acid or extract by the alkali of the lignin of ozone oxidation from paper pulp.
3. the method for claim 2, wherein the processing with activated ozone comprises the interpolation inorganic acid in the step (c), its dosage enough makes the pH value of paper pulp reach in the scope of 1.5-5.
4. the method for claim 2 comprises to paper pulp with the processing of activated ozone wherein and adds ethanol/DMSO mixture that its dosage is about 20% ethanol of about 0.01%-and the about 8%DMSO of about 0.01%-(with the paper pulp fiber dry weight basis).
5. the method for claim 4, wherein this ethanol/DMSO mixture is formed (with the paper pulp fiber dry weight basis) by about 10% ethanol of about 5%-and the about 4%DMSO of about 2%-.
6. the method for claim 4, wherein this ethanol/DMSO mixture prepared before being added to paper pulp.
7. the method for claim 2, wherein the step of handling with activated ozone comprises to paper pulp and adds ozone gas, its dosage is about 1.0% (with the paper pulp fiber dry weight basis) of about 0.1%-.
8. the method for claim 7, wherein the step of handling with activated ozone comprises to paper pulp and adds ozone gas, its dosage is preferably about 0.6% (with the paper pulp fiber dry weight basis) of about 0.3%-.
9. the method for claim 2, wherein the step of handling with activated ozone comprises that the paper pulp of crossing to ozone treatment adds alkali, during its dosage is enough and paper pulp, makes its pH in the scope of about 5-about 10.
10. the process of claim 1 wherein that to be used for implementation condition that the treatment step under the activated ozone comprises about 15% for about 1%-for the reaction denseness, reaction temperature be about 20 ℃-Yue 90 ℃ and reaction time are about 1 minute-Yue 120 minutes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US44332399A | 1999-11-19 | 1999-11-19 | |
| US09/443323 | 1999-11-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1297085A true CN1297085A (en) | 2001-05-30 |
Family
ID=23760340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00128482A Pending CN1297085A (en) | 1999-11-19 | 2000-11-17 | Method for use of activated ozone in bleaching paper pulp |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1101860A1 (en) |
| KR (1) | KR20010051774A (en) |
| CN (1) | CN1297085A (en) |
| BR (1) | BR0005444A (en) |
| CA (1) | CA2326311A1 (en) |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT373303B (en) * | 1981-08-06 | 1984-01-10 | Chemiefaser Lenzing Ag | METHOD FOR THE PRODUCTION OF LOW-LEVEL CELLS |
| US4959124A (en) * | 1989-05-05 | 1990-09-25 | International Paper Company | Method of bleaching kraft pulp in a DZED sequence |
| FR2692499B1 (en) * | 1992-06-22 | 1994-08-26 | Atochem Elf Sa | Process for delignification and bleaching of a lignocellulosic material. |
| US5411635A (en) * | 1993-03-22 | 1995-05-02 | The Research Foundation Of State University Of New York | Ozone/peroxymonosulfate process for delignifying a lignocellulosic material |
| FI964715A (en) * | 1996-11-26 | 1998-05-27 | Keskuslaboratorio | Method for bleaching cellulose pulp |
-
2000
- 2000-11-17 CA CA002326311A patent/CA2326311A1/en not_active Abandoned
- 2000-11-17 BR BR0005444-5A patent/BR0005444A/en not_active Application Discontinuation
- 2000-11-17 KR KR1020000068431A patent/KR20010051774A/en not_active Application Discontinuation
- 2000-11-17 CN CN00128482A patent/CN1297085A/en active Pending
- 2000-11-17 EP EP00125129A patent/EP1101860A1/en not_active Withdrawn
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20010051774A (en) | 2001-06-25 |
| BR0005444A (en) | 2001-07-03 |
| EP1101860A1 (en) | 2001-05-23 |
| CA2326311A1 (en) | 2001-05-19 |
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