EP0801170A1 - Verfahren zur Delignifizierung und/oder Bleichen eines Papierzellstoffs - Google Patents

Verfahren zur Delignifizierung und/oder Bleichen eines Papierzellstoffs Download PDF

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Publication number
EP0801170A1
EP0801170A1 EP97400799A EP97400799A EP0801170A1 EP 0801170 A1 EP0801170 A1 EP 0801170A1 EP 97400799 A EP97400799 A EP 97400799A EP 97400799 A EP97400799 A EP 97400799A EP 0801170 A1 EP0801170 A1 EP 0801170A1
Authority
EP
European Patent Office
Prior art keywords
acid
peroxyacid
treatment
less
carried out
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.)
Withdrawn
Application number
EP97400799A
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English (en)
French (fr)
Inventor
Thierry Delagoutte
Dominique Lachenal
Henry Ledon
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.)
Chemoxal SA
Original Assignee
Chemoxal SA
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
Priority claimed from FR9604628A external-priority patent/FR2747408B1/fr
Priority claimed from FR9612568A external-priority patent/FR2754550B1/fr
Application filed by Chemoxal SA filed Critical Chemoxal SA
Publication of EP0801170A1 publication Critical patent/EP0801170A1/de
Withdrawn legal-status Critical Current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
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
    • 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

Definitions

  • the invention relates to a method for improving the selectivity of the delignification and / or bleaching of a paper pulp comprising lignin, using an organic peroxyacid, in which the pulp is treated with a aqueous solution of this organic peroxyacid in the presence of an auxiliary.
  • the first step in a chemical pulp bleaching sequence is generally intended to improve the delignification of the unbleached pulp directly from the baking stage.
  • This first significant step is usually carried out on the unbleached pulp with chlorine applied in an acid medium, chlorine dioxide or by a combination of the two so as to cause a reaction with the residual lignin of the pulp and give rise to products which can be extracted from this paste by solubilization, during a subsequent treatment step.
  • chlorinated reagents are increasingly being replaced by non-chlorinated reagents, which are more favorable to the environment.
  • this process comprising the use of a step with peracetic acid in the presence of additives such as diethylenetriamine-pentaacetic acid (DTPA).
  • DTPA diethylenetriamine-pentaacetic acid
  • the paper pulp is treated with a peroxyacid in the presence of a stabilizing agent chosen from phosphonic acids and their salts, which has the effect of improving the selectivity delignification.
  • the pasta is usually bleached using one or more oxidizing substances chosen in particular from chlorine dioxide, ozone, hydrogen peroxide or peracetic acid.
  • oxidizing substances chosen in particular from chlorine dioxide, ozone, hydrogen peroxide or peracetic acid.
  • These bleaching operations are generally carried out in the presence of cellulose protective agents, in order to avoid the degradation of the latter, such as for example magnesium sulfate.
  • the subject of the present invention is a process for the delignification and / or bleaching of a paper pulp comprising at least one step of treatment with an organic peroxyacid, characterized in that said treatment is carried out in the presence of one or more several ancillary agents for protecting the viscosity of the dough chosen from the phosphorus mineral acids and their salts.
  • phosphorus mineral acids we mean acids without carbon-phosphorus bonds; mention may, for example, be made of phosphorous acid, phosphoric acid, pyrophosphoric acid and polyphosphoric acids.
  • salt of a mineral phosphorus acid is meant a phosphorus acid of which one or more of these functions acid is salified, and in particular the alkali metal salts.
  • the process which is the subject of the present invention can be implemented with any type of paper pulp, whether it be chemical, mechanical or recycled pulp, such as, for example, so-called “kraft” pulps.
  • paper pulp denotes any material containing cellulose fibers which are obtained from wood, whether it be the so-called “resinous” species such as, for example, the various varieties of pine, fir, spruce, or even the essences say "hardwood” like for example the various varieties of hornbeam, aspen, beech, birch, poplar, oak, eucalyptus, or their mixtures.
  • Pulp can also be obtained by reprocessing recovered paper such as newspapers, magazines, cardboard boxes, printing / writing papers and photocopying papers which form, among other things, office waste, listings computer, paper manufacturing “breaks”.
  • organic peroxyacid denotes percarboxylic acids or polycarboxylic acids in which at least one carboxy function is peroxidized to the percarboxylic group -C (0) -0-0H.
  • peralkanoic acids having from 1 to 10 carbon atoms
  • monoperoxyalkanedioic acids having from 1 to 10 carbon atoms
  • monoperoxyalkeneioic acids having from 1 to 10 carbon atoms
  • acids diperoxyalkanedioic having from 1 to 10 carbon atoms acids diperoxyalkanedioic having from 1 to 10 carbon atoms
  • aromatic there may be mentioned peroxybenzoic acid, monoperoxyphthalic acids, diperoxyphthalic acids or peroxynaphthoic acids.
  • the ancillary agent for protecting the viscosity of the dough is pyrophosphoric acid, sodium pyrophosphate, tripolyphosphoric acid or sodium tripolyphosphate.
  • the organic peroxyacid is chosen from performic acid, peracetic acid, 1,6-diperoxyhexanedioic acid, 1,4-monoperoxybutenedioic acid, 1,4 acid -monoperoxybutanedioic, and perbenzoic acid.
  • peracetic acid is either obtained by reaction of an aqueous solution of hydrogen peroxide with acetic acid according to the equilibrium: H 2 O 2 + CH 3 CO 2 H ⁇ ⁇ CH 3 CO 3 H + H 2 O and it is then designated by the expression peracetic acid "at equilibrium", or obtained by azeotropic distillation under reduced pressure of an aqueous mixture of hydrogen peroxide and acetic acid in the presence of an acid catalyst or d '' an equilibrium aqueous solution of peracetic acid.
  • the peroxyacid used can be either substantially pure, or preferably in aqueous solution comprising at least 4% by weight of this peroxyacid, optionally in admixture with the corresponding organic acid and / or hydrogen peroxide.
  • peracetic acid is used in aqueous solution, either as an equilibrium mixture with hydrogen peroxide and acetic acid, or obtained by azeotropic distillation.
  • the organic peroxyacid is peracetic acid in aqueous solution at least 4% by weight of said peroxyacid and in particular in equilibrium aqueous solution also comprising hydrogen peroxide such as H 2 O 2 / peracetic acid weight ratio is greater than 0.5 and in particular greater than 1.
  • This peroxyacid can also be generated in situ.
  • the peroxyacid solutions may contain at least 0.1% by weight of strong acid such as for example sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid or a mixture of these acids and at most about 3 % in weight.
  • strong acid such as for example sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid or a mixture of these acids and at most about 3 % in weight.
  • the peroxyacid can also be prepared by contacting an H 2 O 2 and acid mixture on a heterogeneous acid catalyst, for example a sulfonated polystyrene.
  • sodium silicate and / or magnesium salts or magnesium compounds such as magnesia, magnesium carbonate, magnesium sulfate or magnesium chloride.
  • the treatment with this peroxyacid will preferably be carried out in a temperature range between 20 ° C and 140 ° C in particular between 50 to 120 ° C and preferably between 70 ° and 90 ° C, but also under pressure, preferably lower or equal to approximately 10 bars, and in particular less than 5 bars.
  • the reactor can be pressurized with air or with a gas containing more than 21% oxygen, and in particular at least 80% oxygen.
  • the pH of the step of treatment with the peroxyacid can be acid, neutral or alkaline but preferably a pH between 5 and 9 and more preferably between 7 and 8.5 will be chosen.
  • the duration of the treatment will be less than 4 hours, preferably less than 2 hours and, in particular less than 60 minutes.
  • treatment with peroxyacid is first carried out at a pH between 2 and 7, in particular between 4 and 6, for less than 4 hours, in particular less than two hours, and preferably one hour or less, at a temperature between 40 and 100 ° C, then the dough is made alkaline without intermediate washing to a pH between 8 and 12, especially between 9.5 and 12 and left for less than 4 hours at a temperature between 60 and 120 ° C.
  • the treatment can be carried out in the presence of cellulose protective agents such as magnesium salts and alkali and alkaline earth silicates.
  • the delignification according to the invention using a peroxyacid generally complements the usual steps of delignification and / or bleaching of a paper pulp such as, for example, oxygen delignification with ozone or with dioxide chlorine. It is also possible to use the peracetic acid present in the bleaching liquor (residual peroxyacid) for a treatment before bleaching, for example a delignification step.
  • the peroxyacid comes from a washing solution of a subsequent step in the process for treating paper pulp.
  • a treatment is carried out, the conditions of which are summarized in table 3 below.
  • the treatment is carried out with a load of 3% by weight of peracetic acid and 3.3% of hydrogen peroxide relative to the dry paste.
  • Table 3 Conditions Treatment with 0.5% pyrophosphate Na Control (without pyrophosphate) I. Kappa Dpv I. Kappa DPv 90 °, 3 hours 10.3 1324 10.1 504 90 °, 2 hours 12.8 1300 13.8 1000 110 °, 1 hour 14.9 1224 15.6 1127
  • IK initial Kappa index
  • DP degree of polymerization
  • the dough is then divided into two portions.
  • the first portion is treated with approximately 5% sodium hydroxide so that the pH increases to 10.5, then the reaction is continued for 2 hours.
  • the second portion (control) is washed with water and then treated for 1 hour at 90 ° C with sodium hydroxide.
  • Example 7 By following a procedure analogous to Example 7, and by modifying the treatment step of the first part (test) by the additional addition of 0.2% of magnesium sulfate, the following results are obtained: Table 5 Dough before treatment 1st portion (trial) after treatment 2nd portion (trial) after treatment IK 24.8 8.6 16.7 DP 1450 1195 1409
  • the results of Examples 7 and 8 demonstrate the additional advantage of treating with peroxyacid first at acid pH and then raising the pH without intermediate washing. This increases delignification while maintaining an acceptable degree of polymerization.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
EP97400799A 1996-04-12 1997-04-08 Verfahren zur Delignifizierung und/oder Bleichen eines Papierzellstoffs Withdrawn EP0801170A1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR9604628A FR2747408B1 (fr) 1996-04-12 1996-04-12 Procede pour la delignification et/ou le blanchiment d'une pate a papier
FR9604628 1996-04-12
FR9612568A FR2754550B1 (fr) 1996-10-15 1996-10-15 Procede pour la delignification et/ou le blanchiment d'une pate a papier
FR9612568 1996-10-15

Publications (1)

Publication Number Publication Date
EP0801170A1 true EP0801170A1 (de) 1997-10-15

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Family Applications (1)

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EP97400799A Withdrawn EP0801170A1 (de) 1996-04-12 1997-04-08 Verfahren zur Delignifizierung und/oder Bleichen eines Papierzellstoffs

Country Status (4)

Country Link
EP (1) EP0801170A1 (de)
JP (1) JPH1037089A (de)
CN (1) CN1166553A (de)
CA (1) CA2202445A1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2776312A1 (fr) * 1998-03-18 1999-09-24 Air Liquide Procede de destruction des agents fluorescents contenus dans les vieux papiers par l'acide peracetique
CN101265678B (zh) * 2008-04-30 2010-12-01 江西科技师范学院 纸浆漂白中过氧化氢的稳定剂组合物
US20220412001A1 (en) * 2021-06-18 2022-12-29 Sixring Inc. Temperature-controlled delignification of biomass
US20230279453A1 (en) * 2022-03-04 2023-09-07 Sixring Inc. Improved Cellulose to Cellobiose Conversion Process

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI112958B (fi) * 1997-12-19 2004-02-13 Kemira Oyj Menetelmä kemiallisen massan valkaisemiseksi sekä valkaisuliuoksen käyttö
US8262850B2 (en) * 2003-09-23 2012-09-11 International Paper Company Chemical activation and refining of southern pine kraft fibers
CN100427676C (zh) * 2004-09-01 2008-10-22 曾繁寿 利用微波技术制备纸浆的方法
CN103145228A (zh) * 2013-03-06 2013-06-12 青岛大学 一种活性染料染色废水脱色方法
CN109736119B (zh) * 2019-02-27 2021-09-21 华南理工大学 一种纸浆漂白方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR860112A (fr) * 1938-09-14 1941-01-07 Du Pont Procédé pour le blanchiment de la paille et de matières premières similaires
FR1553704A (de) * 1966-05-31 1969-01-17
JPH04243861A (ja) * 1991-01-23 1992-08-31 Nippon Peroxide Co Ltd 過酢酸組成物の製造方法
EP0578305A1 (de) * 1992-07-06 1994-01-12 SOLVAY INTEROX (Société Anonyme) Verfahren zur Delignifizierung von chemischen Zellstoffen
RU2046869C1 (ru) * 1993-05-31 1995-10-27 Акционерное общество открытого типа "Всероссийский научно-исследовательский институт целлюлозно-бумажной промышленности" Способ получения беленой целлюлозы

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR860112A (fr) * 1938-09-14 1941-01-07 Du Pont Procédé pour le blanchiment de la paille et de matières premières similaires
FR1553704A (de) * 1966-05-31 1969-01-17
JPH04243861A (ja) * 1991-01-23 1992-08-31 Nippon Peroxide Co Ltd 過酢酸組成物の製造方法
EP0578305A1 (de) * 1992-07-06 1994-01-12 SOLVAY INTEROX (Société Anonyme) Verfahren zur Delignifizierung von chemischen Zellstoffen
RU2046869C1 (ru) * 1993-05-31 1995-10-27 Акционерное общество открытого типа "Всероссийский научно-исследовательский институт целлюлозно-бумажной промышленности" Способ получения беленой целлюлозы

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9626, Derwent World Patents Index; Class F09, AN 96-258044, XP002033276 *
PATENT ABSTRACTS OF JAPAN vol. 017, no. 017 (C - 1016) 13 January 1993 (1993-01-13) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2776312A1 (fr) * 1998-03-18 1999-09-24 Air Liquide Procede de destruction des agents fluorescents contenus dans les vieux papiers par l'acide peracetique
CN101265678B (zh) * 2008-04-30 2010-12-01 江西科技师范学院 纸浆漂白中过氧化氢的稳定剂组合物
US20220412001A1 (en) * 2021-06-18 2022-12-29 Sixring Inc. Temperature-controlled delignification of biomass
US11982051B2 (en) * 2021-06-18 2024-05-14 Sixring Inc. Temperature-controlled delignification of biomass
US20230279453A1 (en) * 2022-03-04 2023-09-07 Sixring Inc. Improved Cellulose to Cellobiose Conversion Process

Also Published As

Publication number Publication date
CA2202445A1 (en) 1997-10-12
JPH1037089A (ja) 1998-02-10
CN1166553A (zh) 1997-12-03

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