EP1607519B1 - Activateur pour le blanchiment du pâte à papier - Google Patents

Activateur pour le blanchiment du pâte à papier Download PDF

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Publication number
EP1607519B1
EP1607519B1 EP04253546A EP04253546A EP1607519B1 EP 1607519 B1 EP1607519 B1 EP 1607519B1 EP 04253546 A EP04253546 A EP 04253546A EP 04253546 A EP04253546 A EP 04253546A EP 1607519 B1 EP1607519 B1 EP 1607519B1
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EP
European Patent Office
Prior art keywords
anhydride
process according
range
solution
carboxylic acid
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.)
Not-in-force
Application number
EP04253546A
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German (de)
English (en)
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EP1607519A1 (fr
Inventor
Alan Michael Marland
Alison Jane Mathews
Gary Miller
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.)
Warwick International Group Ltd
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Warwick International Group Ltd
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 to PL04253546T priority Critical patent/PL1607519T3/pl
Priority to EP04253546A priority patent/EP1607519B1/fr
Priority to DE602004011911T priority patent/DE602004011911T9/de
Priority to ES04253546T priority patent/ES2300713T3/es
Priority to PT04253546T priority patent/PT1607519E/pt
Priority to AT04253546T priority patent/ATE386837T1/de
Application filed by Warwick International Group Ltd filed Critical Warwick International Group Ltd
Priority to CA002569467A priority patent/CA2569467A1/fr
Priority to PCT/GB2005/002312 priority patent/WO2005121443A1/fr
Priority to US11/570,140 priority patent/US20070246177A1/en
Publication of EP1607519A1 publication Critical patent/EP1607519A1/fr
Application granted granted Critical
Publication of EP1607519B1 publication Critical patent/EP1607519B1/fr
Anticipated expiration legal-status Critical
Not-in-force legal-status Critical Current

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

Definitions

  • This invention relates to a process for generating a dilute solution of percarboxylic acid which is subsequently used to bleach wood or non wood pulp. More specifically, in this process the bleaching solution is formed by reaction of hydrogen peroxide with a carboxylic acid anhydride compound which behaves as a bleach activator.
  • Wood and non wood pulp are valuable raw materials in the paper industry and it is desirable that a high degree of whiteness is obtainable.
  • Oxygen based bleaching is used for pulp bleaching because of its environmental benefits and oxidising power. Hydrogen peroxide is increasingly being used in oxygen based pulp bleaching.
  • Hydrogen peroxide however, suffers from some performance disadvantages which become particularly important when an existing pulp bleaching sequence is being converted to operate with hydrogen peroxide.
  • One major problem is the fact that the degree of whiteness may be reduced compared with the use of chlorine based bleaches which significantly reduces the value of the pulp.
  • bleaching solution In order to overcome these problems work has gone into developing an alternative bleaching solution. It is proposed in various patent applications to react at least part of the hydrogen peroxide with a bleach activator thereby generating a peroxyacid based oxygen bleaching species in situ. Bleach activators contain a good leaving group such that on mixing with hydrogen peroxide, reaction takes place to give peracid species which are more effective bleaching agents than hydrogen peroxide itself.
  • EP-A-0670929 describes a method for bleaching lignocellulose containing pulp in which equilibrium peracid is generated by reacting acetic acid and hydrogen peroxide. It also suggests that in situ peracid can be generated by reaction of acelic anhydride with hydrogen peroxide directly in the bleaching stage although the equilibrium peracid is preferred and is what is used in the examples of this application. EP-A-0670928 describes an identical method. However, whilst equilibrium peracid improves the bleaching it also introduces problems of handling and dosing, peracid in the pulp plant.
  • EP456032 and GB2304126 describe the use of tetraacetylethylenediamine (TAED) as the bleach activator. Whilst this produces a very effective bleaching solution, generation of such a solution in certain circumstances may not prove to be economical for all mills. It would therefore be desirable to develop a process by which peracid can be generated in a good yield by reacting hydrogen peroxide with a more cost effective bleach activator, thus ensuring that it is more cost effective than the method of the prior art which uses TAED.
  • a bleach activator suitable for solving this problem is acetic anhydride. Whilst the use of acetic anhydride as a bleach activator to produce peracetic acid is well documented, surprisingly better performance can be delivered using peracetic acid generated from acetic anhydride as compared to preformed peracetic acid.
  • US3,227,655 discloses a process of preparing a stable concentrated aqueous solution of a bleaching agent containing monoperacetic acid for bleaching fibre materials. Hydrogen peroxide and acetic anhydride are reacted together in an aqueous medium in the presence of ammonium hydroxide.
  • the water used in step a) is of a temperature between 5°C-100°C, preferably between 10°C-50°C and more preferably between 15°C-30°C. At cooler temperatures the generation of the percarboxylic acid may be inhibited whilst at higher temperatures, although the generation would be rapid, it is anticipated that degradation of the percarboxylic acid species would be promoted.
  • Chelating agent is added to the water in step a) prior to the addition of further components and is advantageous as it ensures that any trace metals which may be present in the supply are removed. Such trace metals could potentially promote the decomposition of hydrogen peroxide.
  • a mixing step is preferably included to maximise the chelation of the trace metals.
  • the chelating agent is an aqueous phosphonic acid based chelating agent.
  • suitable phosphonic acid based chelating agents are polyamino methylene phosphonic acids such as based on ethylene diamine or diethylenetriamine.
  • Commercially available compounds of this type include Dequest SPE9505, Dequest 20605.
  • the chelating agent is Dequest SPE 9505 and/or Dequest 2066.
  • An aqueous phosphonic acid based chelating agent has been found to work best under the conditions of the method of the present invention.
  • the amount of chelating agent, eg phosphonic acid based agent, added to the water is 0.1-0.4wt%, more preferably 0.125-0.3%wt and most preferably 0.15-0.25%wt.
  • the amount of hydrogen peroxide added in step b), based on a 50% solution is a value in the range 0.5-6wt%, more preferably in the range 1.5-4.0wt% and most preferably in the range 1.75-2.5wt%.
  • the alkali is added in step c) in an amount to raise the pH of the solution from a value in the range 6-7 to a value in the range 10.5-11.5. It is important that this alkali addition occurs prior to step (d). This is because rendering the hydrogen peroxide solution of step b) alkaline promotes the formation of perhydroxyl ion with which the carboxylic acid anhydride compound preferentially reacts instead of water. If step c) was not included, the carboxylic acid anhydride compound would hydrolyse thus reducing the amount of percarboxylic acid eventually formed.
  • Suitable alkalis include potassium hydroxide, calcium hydroxide, magnesium hydroxide and sodium hydroxide.
  • the alkali is sodium hydroxide.
  • Sodium hydroxide is available as a 30w/w% or 50w/w% solution. Suitable amounts were determined by monitoring the pH.
  • the amount of sodium hydroxide added based on a 50% solution is a value in the range 0.2-3wt%, more preferably in the range 0.4-1.5wt% and most preferably in the range 0.5-1wt%.
  • step d there is a further mixing step (step d)).
  • the duration of this step is preferably at least one minute. This is important to optimise the extent of formation of the perhydroxyl ion in the subsequent steps. At present, a specific method for directly analysing whether complete formation of the perhydroxyl ion has taken place is not available. However, it is possible to obtain an indication of the extent of perhydroxyl ion formation by analysing the percentage conversion of the carboxylic acid anhydride compound to percarboxylic acid. A low percentage conversion rate may indicate incomplete formation of the perhydroxyl ion. If sufficient time is not allowed for this mixing step and the carboxylic acid anhydride compound is added prematurely then it would preferentially undergo a hydrolysis reaction with water resulting in a low percarboxylic acid generation.
  • the carboxylic acid anhydride compound is added (step e)).
  • the carboxylic acid anhydride compound added in step e) is selected from one or more of the group consisting of acetic anhydride, maleic anhydride, succinic anhydride, phthalic anhydride, malonic anhydride, benzoic anhydride and propanoic anhydride.
  • the amount of carboxylic acid anhydride compound added is in the range 0.02 - 0.6mol%, more preferably in the range 0.05 - 0.3mol% and most preferably in the range 0.075 - 0.15mol% and this addition is followed by a further important mixing step (step f)).
  • This mixing step should be allowed to occur for at least 10 minutes. This is to maximise generation of the percarboxylic acid species. It is, however, possible to accelerate the generation of the percarboxylic acid species by using amounts of alkali at the higher end of the ranges mentioned above prior to the carboxylic acid anhydride addition.
  • the carboxylic acid anhydride compound comprises acetic anhydride.
  • Acetic anhydride has a flash point of 54°C and as such is classified as flammable.
  • a compound is classified as flammable where it has a flashpoint in the range of 21 °C-55°C.
  • DSEAR Dangerous Substances and Explosive Atmosphere Regulations
  • Flammability rating also has an impact on zone classification on manufacturing plants.
  • the applicants have investigated increasing the flash point of acetic anhydride by mixing with a further carboxylic acid anhydride with a higher flashpoint. For example, maleic anhydride has a flash point of 102°C.
  • the flashpoint of acetic anhydride is modified by addition of a carboxylic acid anhydride with a higher flashpoint to form a mixture which has a flash point of 55.1 °C or higher such that it is not classified as flammable.
  • a mixture which has a flash point of 60°C or higher is formed.
  • the amount of carboxylic acid anhydride with a higher flashpoint added is such that the resulting mixture has a ratio of acetic anhydride to carboxylic acid anhydride with a higher flashpoint greater than 50:50 but less than or equal to 80:20.
  • the carboxylic acid anhydride with a higher flashpoint is maleic anhydride.
  • a 50:50 mixture of acetic anhydride: maleic anhydride is not commercially practical as, upon cooling, the maleic anhydride precipitates out of the solution.
  • the ratio of acetic anydride to maleic anhydride is 80:20.
  • the mixture consists of the acetic anhydride and further carboxylic acid anhydride with a higher flashpoint only.
  • the mixture of acetic anhydride and carboxylic acid anhydride with a higher flashpoint can then be used as the carboxylic acid anhydride compound in the method for bleaching cellulosic fibres of the invention.
  • the molar ratio of carboxylic acid anhydride compound to hydrogen peroxide added is preferably in the range 1:1 to 1:10, preferably 1:1.5 to 1:6, more preferably 1:2 to 1:4. Most preferably the molar ratio is about 1:3. In terms of the number of moles added, it is preferable that more hydrogen peroxide is required than carboxylic acid anhydride compound in order to drive the reaction to form perhydroxyl ion.
  • the resultant dilute percarboxylic acid solution formed in step f) will have a pH of approximately 5. Depending on the mill conditions, it may be necessary to increase the solution pH to suit the bleaching conditions required in the final step of the process, step g).
  • the resultant solution contains percarboxylic acid in a concentration range of 0.1-10%, more preferably 0.25-5% and most preferably 0.5-2%.
  • the final step (step g)) of the process is to contact the dilute percarboxylic acid solution with a cellulosic fibre suspension e.g formed from pulp.
  • the pulp may be any sort of pulp, including chemical and mechanical pulp and mixture thereof, including recycled material. Wood and non wood fibres can be bleached using this process.
  • the product may be used directly to form paper or board or may be fully or partially dewatered to form a pulp intermediate for eventual paper or board manufacture.
  • each of the formulations were prepared according to the method of the present invention. More specifically, fresh water at a temperature in the range from 15-30°C was treated with 0.2wt% of Dequest 2066. 2wt% of a 50% hydrogen peroxide solution was added to the stabilised water supply the pH of the resulting hydrogen peroxide solution was adjusted to a pH in the range from 10.5 to 11.5 by the addition 0.75wt% of a 50% solution of sodium hydroxide. The mixture was then mixed for a period of 1 minute to allow complete formation of the perhydroxyl ion. The bleach activator was added to this mixed solution in the amounts shown above respectively and the solution was mixed to allow complete formation of peracetic acid to give a dilute solution of peracetic acid.
  • the peracid release profile for each of formulations 1-5 was determined by taking measurements between 2 and 145 minutes. The solution temperatures were maintained at 25°C. pH profiles were also attained during the process. The results of the peracid release profile are shown in Table 1 and Figure 1 . The pH profiles attained are illustrated in Table 2 and Figure 2 .
  • the bleaching ability of the acetic anhydride derived peracetic acid solution was compared with the bleaching ability of a preformed peracetic acid. More specifically, bleaching formulation 4 was compared to a preformed commercially available peracetic acid (supplied by Aldrich), hereinafter referred to as formulation 6.
  • brown stock delignification and recycled bleaching studies were performed using brown stock and 80:20 Newsprint: MOW pulps respectively.
  • the studies were performed using a 0.1 %, 0.25% and 0.5% charge of peracetic acid (based on 100% peracetic acid) respectively at a temperature of 70°C and with a retention time of 120 minutes.
  • Formulation 4 was used at a pH in the range 8-8.5 and formulation 6 was used at a pH of 5 which represents the normal conditions under which it is used.
  • the data shows that a superior bleaching performance is achieved using acetic anhydride derived peracetic acid as compared to preformed peracetic acid.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Detergent Compositions (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (21)

  1. Procédé de blanchiment de fibres cellulosiques comprenant les étapes consistant à :
    (a) traiter une alimentation en eau douce avec un agent chélateur pour obtenir une alimentation en eau stabilisée ;
    (b) ajouter du peroxyde d'hydrogène à alimentation en eau stabilisée pour former une solution de peroxyde d'hydrogène ;
    (c) ajuster le pH de la solution de peroxyde d'hydrogène en ajoutant un alcali ;
    (d) mélanger la solution dont le pH a été ajusté, obtenue dans l'étape (c), pour permettre la formation complète d'ions perhydroxyde ;
    (e) ajouter un composé anhydride d'acide carboxylique à la solution obtenue dans l'étape (d) ;
    (f) mélanger la solution obtenue dans l'étape (e) pour permettre la formation complète d'acide percarboxylique afin d'obtenir une solution diluée d'acide percarboxylique ; et
    (g) mettre en contact la solution de peracide avec une suspension de fibres cellulosiques.
  2. Procédé selon la revendication 1, dans lequel l'alimentation en eau douce est à une température sur la gamme de 15-30°C.
  3. Procédé selon la revendication 1, dans lequel l'agent chélateur est à base d'acide phosphonique aqueux.
  4. Procédé selon la revendication 3, dans lequel l'agent chélateur à base d'acide phosphonique est du Dequest SPE9505 et/ou du Dequest 2066.
  5. Procédé selon la revendication 1, dans lequel la quantité d'agent chélateur ajoutée est sur la gamme de 0,1-0,4% en poids.
  6. Procédé selon la revendication 1, dans lequel la quantité d'agent chélateur ajoutée est sur la gamme de 0,125-0,3% en poids.
  7. Procédé selon la revendication 1, dans lequel la quantité d'agent chélateur ajoutée est sur la gamme de 0,15-0,25% en poids
  8. Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité de peroxyde d'hydrogène ajoutée rapportée à une solution à 50% est sur la gamme de 0,5-6% en poids, mieux encore sur la gamme de 1,5-4,0% en poids et tout particulièrement sur la gamme de 1,75-2,5% en poids.
  9. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'alcali est de l'hydroxyde de sodium.
  10. Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité d'alcali ajoutée est sur la gamme de 0,2-3% en poids, de préférence sur la gamme de 0,4-1,5% en poids et mieux encore sur la gamme de 0,5-1,0% en poids.
  11. Procédé selon l'une quelconque des revendications précédentes, dans lequel le pH est ajusté à une valeur sur la gamme de 10,5-11,5.
  12. Procédé selon l'une quelconque des revendications précédentes, dans lequel la durée de l'étape de mélange (d) est d'au moins 1 minute.
  13. Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité de composé anhydride d'acide carboxylique ajoutée est sur la gamme de 0,02-0,6% en mol, de préférence sur la gamme de 0,05-0,3% en mol et mieux encore sur la gamme de 0,075-0,15% en mol.
  14. Procédé selon l'une quelconque des revendications précédentes, dans lequel la durée de l'étape de mélange (f) est d'au moins 10 minutes.
  15. Procédé selon l'une quelconque des revendications précédentes, qui comprend en outre une étape d'ajustement du pH supplémentaire avant que la solution soit mise en contact avec la solution cellulosique fibreuse.
  16. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'anhydride d'acide carboxylique est choisi parmi un ou plusieurs des composés du groupe constitué par l'anhydride acétique, l'anhydride maléique, l'anhydride succinique, l'anhydride malonique, l'anhydride benzoïque et l'anhydride propanoïque.
  17. Procédé selon la revendication 16, dans lequel le composé anhydride d'acide carboxylique comprend de l'anhydride acétique.
  18. Procédé selon la revendication 17, dans lequel le composé anhydride carboxylique comprend en plus un autre anhydride d'acide carboxylique ayant un point d'éclair plus élevé et l'anhydride acétique a été mélangé au préalable avec l'autre anhydride d'acide carboxylique ayant un point d'éclair plus élevé pour former un mélange anhydride acétique/ anhydride d'acide carboxylique ayant un point d'éclair modifié, d'au moins 55,1°C.
  19. Procédé selon la revendication 18 dans lequel le rapport entre l'anhydride acétique et l'anhydride maléique dans le mélange anhydride acétique/anhydride d'acide carboxylique ayant un point d'éclair modifié est supérieur à 50:50.
  20. Procédé selon la revendication 18 dans lequel le rapport entre l'anhydride acétique et l'anhydride maléique ayant un point d'éclair plus élevé dans le mélange anhydride acétique/anhydride d'acide carboxylique ayant un point d'éclair modifié est de 80:20.
  21. Procédé selon l'une quelconque des revendications 19 à 21, dans lequel l'anhydride d'acide carboxylique ayant un point d'éclair plus élevé est l'anhydride maléique.
EP04253546A 2004-06-14 2004-06-14 Activateur pour le blanchiment du pâte à papier Not-in-force EP1607519B1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
DE602004011911T DE602004011911T9 (de) 2004-06-14 2004-06-14 Aktivator zum Zellstoffbleichen
ES04253546T ES2300713T3 (es) 2004-06-14 2004-06-14 Activador para el blanqueado de pasta de papel.
PT04253546T PT1607519E (pt) 2004-06-14 2004-06-14 Activador para branqueamento de pasta
AT04253546T ATE386837T1 (de) 2004-06-14 2004-06-14 Aktivator zum zellstoffbleichen
PL04253546T PL1607519T3 (pl) 2004-06-14 2004-06-14 Aktywator bielenia ścieru
EP04253546A EP1607519B1 (fr) 2004-06-14 2004-06-14 Activateur pour le blanchiment du pâte à papier
CA002569467A CA2569467A1 (fr) 2004-06-14 2005-06-10 Activateur pour le blanchiment de pate a papier
PCT/GB2005/002312 WO2005121443A1 (fr) 2004-06-14 2005-06-10 Activateur pour le blanchiment de pate a papier
US11/570,140 US20070246177A1 (en) 2004-06-14 2005-06-10 Activator for Pulp Bleaching

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP04253546A EP1607519B1 (fr) 2004-06-14 2004-06-14 Activateur pour le blanchiment du pâte à papier

Publications (2)

Publication Number Publication Date
EP1607519A1 EP1607519A1 (fr) 2005-12-21
EP1607519B1 true EP1607519B1 (fr) 2008-02-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP04253546A Not-in-force EP1607519B1 (fr) 2004-06-14 2004-06-14 Activateur pour le blanchiment du pâte à papier

Country Status (9)

Country Link
US (1) US20070246177A1 (fr)
EP (1) EP1607519B1 (fr)
AT (1) ATE386837T1 (fr)
CA (1) CA2569467A1 (fr)
DE (1) DE602004011911T9 (fr)
ES (1) ES2300713T3 (fr)
PL (1) PL1607519T3 (fr)
PT (1) PT1607519E (fr)
WO (1) WO2005121443A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8268122B2 (en) * 2005-12-02 2012-09-18 Akzo Nobel N.V. Process of producing high-yield pulp
DE102006028018A1 (de) * 2006-06-14 2007-12-20 Henkel Kgaa Aufhell-und/oder Färbemittel mit Estern und/oder Anhydriden
CN115702272A (zh) * 2020-06-16 2023-02-14 凯米拉公司 用于在漂白期间控制树脂的方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2377038A (en) * 1941-09-15 1945-05-29 Du Pont Manufacture of peracids
US3227655A (en) * 1957-11-25 1966-01-04 Fmc Corp Process for preparation of a bleaching agent
US4294575A (en) * 1979-01-02 1981-10-13 Monsanto Company Peroxide stabilization
FR2457339A1 (fr) * 1979-05-25 1980-12-19 Interox Procede pour la delignification et le blanchiment de pates cellulosiques chimiques et semi-chimiques
JPH04108192A (ja) * 1990-04-25 1992-04-09 Hoechst Japan Ltd パルプの漂白法
BR9307521A (pt) 1992-11-27 1999-08-31 Eka Nobel Ab Processo para a deslignificação e alvejamento de polpa contendo lignocelulose
RU2097463C1 (ru) 1992-11-27 1997-11-27 Ека Нобель Актиеболаг Способ отбеливания лигноцеллюлозосодержащей пульпы
GB2304126A (en) * 1995-08-10 1997-03-12 Warwick Int Group Pulp treatment process

Also Published As

Publication number Publication date
DE602004011911T2 (de) 2008-08-28
US20070246177A1 (en) 2007-10-25
PL1607519T3 (pl) 2008-07-31
DE602004011911T9 (de) 2009-01-02
DE602004011911D1 (de) 2008-04-03
PT1607519E (pt) 2008-04-16
EP1607519A1 (fr) 2005-12-21
ES2300713T3 (es) 2008-06-16
WO2005121443A1 (fr) 2005-12-22
ATE386837T1 (de) 2008-03-15
CA2569467A1 (fr) 2005-12-22

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