EP0728239B1 - Verfahren zum wasserstoffperoxydbleichen von einem hochausbeute-zellstoff - Google Patents

Verfahren zum wasserstoffperoxydbleichen von einem hochausbeute-zellstoff Download PDF

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Publication number
EP0728239B1
EP0728239B1 EP95900797A EP95900797A EP0728239B1 EP 0728239 B1 EP0728239 B1 EP 0728239B1 EP 95900797 A EP95900797 A EP 95900797A EP 95900797 A EP95900797 A EP 95900797A EP 0728239 B1 EP0728239 B1 EP 0728239B1
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EP
European Patent Office
Prior art keywords
process according
pulp
alcohol
reaction medium
hydrogen peroxide
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
EP95900797A
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English (en)
French (fr)
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EP0728239A1 (de
Inventor
Michel Devic
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.)
Arkema France SA
Original Assignee
Elf Atochem SA
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Filing date
Publication date
Application filed by Elf Atochem SA filed Critical Elf Atochem SA
Publication of EP0728239A1 publication Critical patent/EP0728239A1/de
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Publication of EP0728239B1 publication Critical patent/EP0728239B1/de
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
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
    • 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
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes

Definitions

  • the present invention relates to the bleaching of high-yield paper pulps with hydrogen peroxide.
  • wood chips are subjected to separate or associated actions of mechanical, chemical or thermal origin.
  • Chemical pulps are obtained by chemical defibration of wood. Their yield is generally less than 50%.
  • yield is meant the weight of the pulp in the dry state relative to the weight of the starting lignocellulosic material in the dry state, for example wood chips in the dry state.
  • Mechanical type pulps are produced by mechanical defibration of wood chips, for example in a grinding wheel shredder or a disc shredder or refiner.
  • the yield is generally equal to or greater than 85%.
  • the mechanical characteristics of these pastes in particular the resistance to rupture, to tearing and to bursting, are poor.
  • thermomechanical pasta TMP
  • TMP thermomechanical pasta
  • the wood chips were also treated with a sodium sulfite solution at acidic or basic pH depending on the nature of the wood.
  • the pulps obtained also called chemical-mechanical pulps (CMP), have good mechanical characteristics.
  • This latter treatment consists in cooking the lignocellulosic material, carried out at a temperature equal to or greater than 100 ° C., under saturated steam pressure, in the presence of sodium sulfite or sodium bisulfite.
  • CTMP pastes have mechanical resistance is improved, the yield remaining equal to or greater than 85% and more often than not, at least equal to approximately 90% and therefore similar to that of purely mechanical origins.
  • a high-yield paper pulp is defined as being a pulp obtained by defibering the wood and various treatments with a yield equal to or greater than 85%.
  • the consistency (weight of dry matter relative to the total weight of the pulp) of the bleaching medium must be relatively high from 15 to 20% and even 30% to obtain effective bleaching.
  • the bleaching temperature should generally be between 60 ° C and 80 ° C.
  • WO-A-93 19245 describes a process for bleaching a high-yield paper pulp with an aqueous solution containing hydrogen peroxide, sodium carbonate and chelating agents.
  • JP-A-4,065,592 discloses a process for deinking paper according to which the paper to be recycled or the paper pulp is subjected to a treatment with an alcohol-alkaline solution containing hydrogen peroxide. After removing the ink, the paste is bleached with a hydrosulfite solution.
  • the present invention makes it possible to avoid the drawbacks set out below or at least some of them.
  • said ratio is from 0.01 to 0.1.
  • the use of such a reaction medium makes it possible to carry out bleaching without sodium silicate.
  • bleaching can be carried out without complexing metals such as DTPA.
  • the residual bleaching liquid recoverable by filtration of the pulp can be purified by distillation and the residue from this distillation can be easily incinerated. This treatment of the residual liquid avoids the rejection of aqueous bleaching effluent.
  • the ratio by weight of the alcohol to the weight of the pulp considered in the dry state is from 1 to approximately 50.
  • the consistency can vary between very large limits ranging from 50% to approximately 2%.
  • the alcohol is chosen from methanol and ethanol. These two alcohols are available industrially in large quantities and easily evaporated or distilled for their recovery.
  • an activator of hydrogen peroxide capable of being oxidized in the medium into a peroxidant is added to the reaction medium, during its formation or during the reaction.
  • This activator can be a nitrile of general formula R-CN in which R is an alkyl or aryl group. It is assumed that this nitrile leads to an iminoperacid of general formula:
  • the alkyl group is preferably a lower alkyl chosen from methyl, ethyl and propyl.
  • the aryl group is preferably phenyl.
  • the activator can also be a mineral or organic acid or one of its salts, capable of being oxidized in the medium to a peracid or one of its salts.
  • the acid is preferably chosen from acetic acid, boric acid and boric anhydride (B 2 O 3 ).
  • the reaction medium also contains an alkaline agent.
  • bleaching is more effective in the presence of such an agent.
  • this agent is chosen from sodium hydroxide, sodium carbonate, potassium carbonate.
  • the reaction medium is maintained at a temperature of 20 ° C. to 80 ° C.
  • the most preferred temperature range is 50 to 60 ° C.
  • the reaction medium formed is filtered to obtain a solid and a filtrate, then the solid thus collected is washed with water to give a wet paste. whitened.
  • the high-yield paper pulp is washed beforehand with alcohol to reduce or even eliminate a large part of its water content before using this pulp thus washed to form the bleaching reaction medium.
  • the hydrogen peroxide used is a solution of pure H 2 O 2 in water at a content ranging from 10 to 70% by weight.
  • the sodium hydroxide solution in water can contain from 40 g to 700 g of pure NaOH per liter.
  • the activator is generally used in an amount of 1 to 50%.
  • the soda can be added all at once with the other reagents or else added little by little during the bleaching so as to keep the pH constant.
  • the apparent pH is measured with a CHEMTRIX pH meter fitted with an INGOLD ref glass electrode. 9823.
  • the dough is filtered and washed with water.
  • the filtrates are combined and the residual hydrogen peroxide is assayed to determine the amount by weight relative to the amount by weight of initial pulp considered in the dry state: 1.4%.
  • the washed dough is neutralized with sulfur dioxide at a pH equal to 5.5 and the whiteness of the dough is measured according to ISO standard, ie 75 ° ISO.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (14)

  1. Verfahren zum Bleichen eines in hoher Ausbeute erhaltenen Papierzellstoffs mit Wasserstoffperoxid, dadurch gekennzeichnet, daß ein heterogenes Reaktionsmedium erzeugt wird, das den Zellstoff, einen Alkohol und Wasserstoffperoxid in wäßriger Lösung enthält, wobei das Gewichtsverhältnis der Gesamtmenge an Wasser des Mediums zum Alkohol 0,001 bis 0,5 beträgt.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Gewichtsverhältnis 0,01 bis 0,1 beträgt.
  3. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß das Verhältnis des Gewichts des Alkohols zum Gewicht des trockenen Zellstoffs 1 bis 50 beträgt.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Alkohol unter Methanol und Ethanol ausgewählt wird.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß zu dem Reaktionsmedium während seiner Erzeugung oder während der Reaktion ein Aktivierungsmittel von Wasserstoffperoxid gegeben wird, das in dem Medium zu einem Peroxid oxidiert werden kann.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß das Aktivierungsmittel ein Nitril der allgemeinen Formel R-CN ist, in der R eine Alkyl- oder Arylgruppe darstellt.
  7. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß das Aktivierungsmittel eine anorganische oder organische Säure ist.
  8. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die Gruppe R unter Methyl, Ethyl und Phenyl ausgewählt wird.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Reaktionsmedium außerdem ein alkalisches Mittel enthält.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß das alkalische Mittel unter Natriumhydroxid, Natriumcarbonat und Kaliumcarbonat ausgewählt wird.
  11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Temperatur des Reaktionsmediums bei 20 bis 80 °C gehalten wird.
  12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß die Temperatur 50 bis 60 °C beträgt.
  13. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß das gebildete Reaktionsmedium filtriert wird, um einen Feststoff und ein Filtrat zu erhalten, wonach der so gewonnene Feststoff unter Erhalt eines feuchten, gebleichten Zellstoffs mit Wasser gewaschen wird.
  14. Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß der in hoher Ausbeute erhaltene Papierzellstoff vorab mit einem Alkohol gewaschen wird, um seinen Wassergehalt größtenteils zu verringern oder das Wasser sogar zu entfernen, bevor dieser so gewaschene Zellstoff bei der Erzeugung des Bleichreaktionsmediums verwendet wird.
EP95900797A 1993-11-10 1994-11-07 Verfahren zum wasserstoffperoxydbleichen von einem hochausbeute-zellstoff Expired - Lifetime EP0728239B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9313446A FR2712313B1 (fr) 1993-11-10 1993-11-10 Procédé de blanchiment d'une pâte à papier à haut rendement par le peroxyde d'hydrogène.
FR9313446 1993-11-10
PCT/FR1994/001286 WO1995013421A1 (fr) 1993-11-10 1994-11-07 Procede de blanchiment par le peroxyde d'hydrogene d'une pate a papier a haut rendement

Publications (2)

Publication Number Publication Date
EP0728239A1 EP0728239A1 (de) 1996-08-28
EP0728239B1 true EP0728239B1 (de) 1997-08-13

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP95900797A Expired - Lifetime EP0728239B1 (de) 1993-11-10 1994-11-07 Verfahren zum wasserstoffperoxydbleichen von einem hochausbeute-zellstoff

Country Status (9)

Country Link
EP (1) EP0728239B1 (de)
JP (1) JPH09504841A (de)
CN (1) CN1139466A (de)
AT (1) ATE156877T1 (de)
AU (1) AU8147394A (de)
CA (1) CA2176030A1 (de)
DE (1) DE69405006T2 (de)
FR (1) FR2712313B1 (de)
WO (1) WO1995013421A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1055737C (zh) * 1996-01-15 2000-08-23 南京林业大学 纸浆多段漂白碱处理段单线态氧强化漂白配方和工艺
IT1290070B1 (it) * 1997-03-13 1998-10-19 3V Sigma Spa Composizioni per la sbianca della carta
CN1107140C (zh) * 1998-05-14 2003-04-30 华南理工大学 中小型纸厂用中浓度纸浆过氧化氢漂白方法
CN106012627B (zh) * 2016-05-24 2018-05-04 中国林业科学研究院林产化学工业研究所 一种利用醇类溶剂制备竹材高白度漂白化机浆的方法
CN108642943B (zh) * 2018-04-03 2021-03-19 中国林业科学研究院林产化学工业研究所 一种制备高白度高强度桉木化学机械浆的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2951371B2 (ja) * 1990-07-03 1999-09-20 株式会社日本紙パルプ研究所 古紙の脱墨法
CA2063351C (en) * 1992-03-18 1996-08-13 Stanley Alan Heimburger Process for bleaching hardwood pulp

Also Published As

Publication number Publication date
EP0728239A1 (de) 1996-08-28
CN1139466A (zh) 1997-01-01
CA2176030A1 (fr) 1995-05-18
DE69405006T2 (de) 1998-01-15
FR2712313A1 (fr) 1995-05-19
WO1995013421A1 (fr) 1995-05-18
ATE156877T1 (de) 1997-08-15
JPH09504841A (ja) 1997-05-13
AU8147394A (en) 1995-05-29
FR2712313B1 (fr) 1995-12-15
DE69405006D1 (de) 1997-09-18

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