EP1322814B8 - Procede de blanchiment de pates a papier - Google Patents

Procede de blanchiment de pates a papier Download PDF

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Publication number
EP1322814B8
EP1322814B8 EP01969897A EP01969897A EP1322814B8 EP 1322814 B8 EP1322814 B8 EP 1322814B8 EP 01969897 A EP01969897 A EP 01969897A EP 01969897 A EP01969897 A EP 01969897A EP 1322814 B8 EP1322814 B8 EP 1322814B8
Authority
EP
European Patent Office
Prior art keywords
peracids
hydrogen peroxide
acid
unbleached
pulp
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01969897A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1322814B1 (fr
EP1322814A1 (fr
Inventor
Michel Delmas
Gérard Avignon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Industrielle de la Matiere Vegetale Cie
Original Assignee
Industrielle de la Matiere Vegetale Cie
Compagnie Industrielle de la Matiere Vegetale SA CIMV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Industrielle de la Matiere Vegetale Cie, Compagnie Industrielle de la Matiere Vegetale SA CIMV filed Critical Industrielle de la Matiere Vegetale Cie
Publication of EP1322814A1 publication Critical patent/EP1322814A1/fr
Application granted granted Critical
Publication of EP1322814B1 publication Critical patent/EP1322814B1/fr
Publication of EP1322814B8 publication Critical patent/EP1322814B8/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/166—Bleaching ; Apparatus therefor with per compounds with peracids
    • 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
    • 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
    • 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
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides

Definitions

  • the invention relates to a process for bleaching paper pulps obtained from lignocellulosic raw materials, in particular vegetable materials from annual plants, agricultural by-products such as cereal straws, sugar cane or sorghum bagasse. sugar bowl, coniferous or hardwood chips, old paper etc ...
  • the invention aims to provide a process for efficient and economical bleaching of all types of paper pulp in a hydro-organic medium with a water content of less than 15% by weight so as to limit or even eliminate polluting aqueous discharges and obtain pulps paper with a whiteness index greater than 70 in just two processing steps.
  • the invention extends to bleached paper pulps produced by the process and to papers obtained from said pulps.
  • oxidizing agents which are essentially chlorine, oxygen, and their derivatives.
  • the bleaching of paper pulps proceeds by a delignification operation complementary to that carried out during the thermal and chemical treatment undergone by the plant which leads to the unbleached paper pulp.
  • This operation consists of an oxidative degradation of the colored molecules, essentially formed from fragments of more or less recombined lignins, which are deposited during cooking on the paper fibers as well as residual lignin present after cooking in the fibers.
  • Chlorine and its derivatives require considerable quantities of water, greater than 50 tonnes of water per tonne of pasta. The polluted water must then be discharged into the rivers.
  • oxygen, ozone and peroxides such as hydrogen peroxide and peracids provide a first solution with regard to pollution by chlorine and its derivatives.
  • the present invention proposes to provide a new process for bleaching paper pulp.
  • the essential objective of the invention is to provide a new whitening process which:
  • Another objective of the invention is to work under conditions of hydration of the reaction medium as low as possible so as to minimize water consumption and therefore the aqueous discharges generated by the bleaching operations.
  • the process of the invention is characterized in that it combines two successive stages of treatment which are:
  • the bleaching phase takes place essentially in the first step, corresponding to bringing the unbleached pulp into contact with the mixture of performic and peracetic acid, which are in fact powerful oxidants capable of degrading the residual lignins present at 'origin for the most part of the more or less dark brown color of unbleached pasta.
  • the acidity of the medium is buffered by the presence of acetic acid, which may explain the very slight degradation of the cellulose fibers.
  • Bleaching being carried out with an excess of peracids the solution separated from the bleached pulp is recycled to the peracid production reactor and treated with hydrogen peroxide at 50% by weight to bring the peracid concentration to the required value before to be returned to the bleaching reactor.
  • the mixture of peracetic acid and performic acid is preferably prepared by bringing acetic acid and formic acid into contact with hydrogen peroxide of concentration greater than 50% by weight.
  • a ratio of acetic acid + peracetic acid / formic acid + performic acid of the order of 9/1 by volume leads to the best results observed experimentally.
  • the solution of performic acid and acetic acid will circulate against the flow of the pasta flow and will be sent before recirculation in a reactor for bringing into contact with hydrogen peroxide so as to keep permanently an optimal high concentration in contact with the circulating dough.
  • the contact time between the peracid solution and the whitening paste will preferably be between 1 and 3 hours.
  • the preferred treatment temperature may be between 60 and 90 ° C.
  • the bleached paper pulp obtained is then deacidified by drying under vacuum.
  • the second step proceeds by bringing the deacidified paste into contact with a basic aqueous solution at a pH between 8 and 10 containing 1 to 4% by weight of hydrogen peroxide (calculated by compared to the treated dry paste).
  • Temperature . treatment will preferably be between 60 ° C and 100 ° C
  • the purpose of this operation is to finish the bleaching operation, neutralize the last acid residues and provide, after washing with demineralized water, a stable and neutral paste, even very slightly basic.
  • the invention extends to neutral or slightly basic pastes obtained by this technology which are characterized by a slight reduction in the degree of polymerization, less than that observed in conventional methods.
  • FIG. 1 illustrates the method of the invention in an optimal mode of implementation.
  • FIG. 1 illustrates the progress of the bleaching operations for unbleached pasta. Certain operations are known in themselves.
  • the originality of the process of the invention essentially lies in the production of peracids by recycling the hydro-organic phase containing the organic acids and the residual peracids, the hydration rate of which will be controlled.
  • the pasta is deacidified in a vacuum enclosure (20 to 30KP a ) brought to a temperature between 60 ° C and 85 ° C.
  • the organic acids recovered are added to the liquid phase after pressing.
  • the solution of organic acids and peracids resulting from pressing and from the deacidification operation under vacuum is dehydrated by azeotropic distillation using a solvent such as cyclohexane (azeotrope water / cyclohexane: boiling temperature: 69, 8 ° C under atmospheric pressure, water content 8.5% by weight).
  • azeotropic distillation using a solvent such as cyclohexane (azeotrope water / cyclohexane: boiling temperature: 69, 8 ° C under atmospheric pressure, water content 8.5% by weight).
  • the purpose of this distillation is to maintain the water concentration of organic acids at a value of the order of 4% by weight, before treating them with a solution of hydrogen peroxide at 50% by weight so as to raise the rate of peracids in the reactor provided for this purpose before being returned to the acid bleaching reactor.
  • the deacidified pastes are introduced into the second reactor and placed in the presence of a solution of hydrogen peroxide in a slightly basic medium (pH 8 to 10) (2% by weight of hydrogen peroxide at 100% relative to the dry paste).
  • the duration of treatment is between 1 and 3 hours for a temperature ranging from 60 to 100 ° C. This operation allows the completion of the bleaching by gaining a few points of whiteness and above all makes it possible to neutralize the pasta before washing with demineralized water. .
  • the neutral pastes separated by pressing are ready for use.
  • the washing water and that recovered during dehydration have a low organic matter content due to the presence in the bleaching phases of strong oxidants such as peracids and hydrogen peroxide. It can be entirely recycled in the production of pasta which, whatever the method used requires a certain amount of water.
  • the process of the invention in its optimal implementation therefore does not produce polluting discharges in an efficient economic framework unlike current bleaching processes.
  • the peracids are prepared by bringing acetic and formic acids into contact with hydrogen peroxide with a concentration of 50% by weight minimum (temperature 60 ° C, duration 3 hours).
  • the hydrogen peroxide concentration is of the order of 0.35 moles, per liter of mixture of organic acids.
  • the water content of the unbleached pasta is less than 10% by weight.
  • the suspension is maintained at 60 ° C for 3 hours. When the three hours have passed, the dough is filtered, manually pressed and washed with distilled water.
  • the concentration of peracids in the acids recovered is 0.2 moles per liter whereas this concentration in the starting acids was 0.3 moles per liter.
  • That of hydrogen peroxide is 0.08 moles per liter whereas this concentration was 0.15 moles per liter in the initial mixture of organic acids and peracids.
  • the recovered acids are enriched with hydrogen peroxide to serve in a new bleaching operation.
  • the liquid / solid ratio is 6/1 by weight.
  • the pasta is filtered, pressed and washed with distilled water and air dried.
  • the kappa index is less than 1
  • the degree of polymerization is 1350.
  • the whiteness index is 88.
  • the pasta After filtration of the pasta and manual pressing to recover the maximum number of acids, peracids and residual hydrogen peroxide, the pasta is degassed under vacuum in a rotary evaporator.
  • the pressure is maintained at an average value of 25 Kpa.
  • the temperature varies from 60 ° C to 80 ° C from the start to the end of the evaporative phase.
  • the pastes are brought into contact with a sodium hydroxide solution (PH 10) with a liquid / solid ratio of 7/1.
  • the processing temperature is 95 ° C.
  • the duration of treatment is 2 hours.
  • the kappa index obtained is less than 1.
  • the whiteness index is 88.
  • the degree of polymerization of the bleached pulp obtained is 1350.
  • the concentration of hydrogen peroxide is of the order of 0.35 moles per liter of mixture of organic acids.
  • the water content of the unbleached pasta is less than 10% by weight.
  • the suspension is maintained at 70 ° C for 2 hours 30 minutes.
  • the dough is then filtered, manually pressed and washed with distilled water.
  • the concentration of peracids in the acids recovered is 0.18 moles per liter while this concentration in the starting acids was 0.3 moles per liter.
  • That of hydrogen peroxide is 0.07 moles per liter while this concentration was 0.15 moles per liter in the initial mixture of organic acids and peracids.
  • the recovered acids are enriched with hydrogen peroxide to serve in a new bleaching operation.
  • the liquid / solid ratio is 6/1 by weight.
  • the pasta is filtered, pressed and washed with distilled water and air dried.
  • the kappa index is less than 1
  • the degree of polymerization of the bleached pulp obtained is 1350.
  • the whiteness index is 87.
  • the degree of whiteness of the bleached pulp obtained is 90.
  • the kappa number is less than 1.
  • the degree of polymerization is 1300.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP01969897A 2000-09-18 2001-09-14 Procede de blanchiment de pates a papier Expired - Lifetime EP1322814B8 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0011831A FR2814180B1 (fr) 2000-09-18 2000-09-18 Procede de blanchiment de pates a papier en milieu organique a hydratation controlee
FR0011831 2000-09-18
PCT/FR2001/002867 WO2002022945A1 (fr) 2000-09-18 2001-09-14 Procede de blanchiment de pates a papier

Publications (3)

Publication Number Publication Date
EP1322814A1 EP1322814A1 (fr) 2003-07-02
EP1322814B1 EP1322814B1 (fr) 2011-03-09
EP1322814B8 true EP1322814B8 (fr) 2011-05-25

Family

ID=8854374

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01969897A Expired - Lifetime EP1322814B8 (fr) 2000-09-18 2001-09-14 Procede de blanchiment de pates a papier

Country Status (14)

Country Link
US (1) US6866749B2 (xx)
EP (1) EP1322814B8 (xx)
CN (1) CN1231634C (xx)
AT (1) ATE501305T1 (xx)
AU (2) AU2001290028B2 (xx)
BR (1) BR0113955A (xx)
CA (1) CA2422610C (xx)
DE (1) DE60144190D1 (xx)
DK (1) DK1322814T3 (xx)
EA (1) EA005240B1 (xx)
ES (1) ES2360503T3 (xx)
FR (1) FR2814180B1 (xx)
PT (1) PT1322814E (xx)
WO (1) WO2002022945A1 (xx)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2885371B1 (fr) * 2005-05-03 2007-08-03 Cie Ind De La Matiere Vegetale Installation pour la mise en oeuvre d'un procede de production de pate a papier, de lignines et de sucres et procede de production au moyen d'une telle installation
FI118735B (fi) 2005-09-13 2008-02-29 Kemira Oyj Menetelmä peroksihappojen valmistamiseksi
FI119800B (fi) * 2006-11-09 2009-03-31 Kemira Oyj Menetelmä mikro-organismien kasvun estämiseksi ja mikro-organismien kasvua estävä yhdistelmä
CN102105443B (zh) 2008-03-28 2014-05-28 埃科莱布有限公司 磺基过氧羧酸、它们的制备和用作漂白剂和抗微生物剂的方法
US8871807B2 (en) 2008-03-28 2014-10-28 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US8809392B2 (en) 2008-03-28 2014-08-19 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
ES2897548T3 (es) 2010-09-14 2022-03-01 Save Foods Ltd Métodos de tratamiento de materia comestible y sustratos de la misma
US8845860B2 (en) 2010-09-16 2014-09-30 Georgia-Pacific Consumer Products Lp High brightness pulps from lignin rich waste papers
FI123052B (fi) * 2011-09-23 2012-10-15 Chempolis Oy Esikäsittelymenetelmä vesiliukoisten sokereiden tuottamiseksi lignoselluloosamateriaalista
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US20140256811A1 (en) 2013-03-05 2014-09-11 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
FR3016359B1 (fr) 2014-01-10 2022-04-29 Arkema France Compositions de peroxyde d'hydrogene pour la delignification de matiere vegetale et leurs utilisations
EP3232781A4 (en) 2014-12-18 2018-08-22 Ecolab USA Inc. Methods for forming peroxyformic acid and uses thereof
US11040902B2 (en) 2014-12-18 2021-06-22 Ecolab Usa Inc. Use of percarboxylic acids for scale prevention in treatment systems
KR20170096032A (ko) 2014-12-18 2017-08-23 에코랍 유에스에이 인코퍼레이티드 다가 알콜 폼에이트를 통한 퍼옥시폼산의 생성
CN107604731A (zh) * 2017-11-02 2018-01-19 山东东平容业达植物纤维科技有限公司 一种秸秆纤维提取过程中的漂白工艺
US11260040B2 (en) 2018-06-15 2022-03-01 Ecolab Usa Inc. On site generated performic acid compositions for teat treatment

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3005947B1 (de) * 1980-02-16 1981-01-29 Degussa Verfahren zur Bleiche von Zellstoffen mittels organischer Persaeure
ES2086183T3 (es) * 1992-07-06 1996-06-16 Solvay Interox Procedimiento para la deslignificacion de una pasta papelera quimica.
US6007678A (en) * 1992-11-27 1999-12-28 Eka Nobel Ab Process for delignification of lignocellulose-containing pulp with an organic peracid or salts thereof
DE69628029D1 (de) * 1995-06-29 2003-06-12 K Reijo Salminen Kontinuierlicher kocher
FI103899B1 (fi) * 1996-11-06 1999-10-15 Chempolis Oy Menetelmä erityisen vaalean massan valmistamiseksi

Also Published As

Publication number Publication date
CA2422610A1 (fr) 2002-03-21
DE60144190D1 (de) 2011-04-21
EA200300383A1 (ru) 2003-08-28
FR2814180B1 (fr) 2003-12-05
ES2360503T3 (es) 2011-06-06
PT1322814E (pt) 2011-05-02
CA2422610C (fr) 2009-12-01
EP1322814B1 (fr) 2011-03-09
ATE501305T1 (de) 2011-03-15
BR0113955A (pt) 2003-07-22
EP1322814A1 (fr) 2003-07-02
FR2814180A1 (fr) 2002-03-22
CN1458996A (zh) 2003-11-26
CN1231634C (zh) 2005-12-14
US6866749B2 (en) 2005-03-15
AU9002801A (en) 2002-03-26
US20040035537A1 (en) 2004-02-26
WO2002022945A1 (fr) 2002-03-21
EA005240B1 (ru) 2004-12-30
DK1322814T3 (da) 2011-06-14
AU2001290028B2 (en) 2005-12-01

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