EP0034219B2 - Verfahren zur Bleiche von Zellstoffen mittels organischer Persäure - Google Patents

Verfahren zur Bleiche von Zellstoffen mittels organischer Persäure Download PDF

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Publication number
EP0034219B2
EP0034219B2 EP80108011A EP80108011A EP0034219B2 EP 0034219 B2 EP0034219 B2 EP 0034219B2 EP 80108011 A EP80108011 A EP 80108011A EP 80108011 A EP80108011 A EP 80108011A EP 0034219 B2 EP0034219 B2 EP 0034219B2
Authority
EP
European Patent Office
Prior art keywords
peroxide
peracid
bleaching
weight
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.)
Expired
Application number
EP80108011A
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German (de)
English (en)
French (fr)
Other versions
EP0034219A1 (de
EP0034219B1 (de
Inventor
Horst Dr. Krüger
Wilhelm Dr. Berndt
Hans Ulrich Dr. Süss
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.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6094866&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0034219(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Degussa GmbH filed Critical Degussa GmbH
Priority to AT80108011T priority Critical patent/ATE1826T1/de
Publication of EP0034219A1 publication Critical patent/EP0034219A1/de
Application granted granted Critical
Publication of EP0034219B1 publication Critical patent/EP0034219B1/de
Publication of EP0034219B2 publication Critical patent/EP0034219B2/de
Expired 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

Definitions

  • the pulps obtained chemically such as those obtained from the sulfite process or the alkaline sodium or sulfate process, contain small amounts of lignin, hemicelluloses and some other components in addition to the main component cellulose.
  • the publication Tappi, Vol. 49, No. 10, (452-456) 1966 relates to the treatment of high-yield pulp and wood pulp with peracetic acid in the acidic range. This is followed by a bleaching step without intermediate washing, in which after increasing the pH to 7-8, part of the peracetic acid not used in the first stage is used to improve the brightness value.
  • Organic persauren are obtained by the classic method by reacting carboxylic acids with hydrogen peroxide.
  • carboxylic acids By mixing lower aliphatic carboxylic acids with aqueous 30-90% by weight hydrogen peroxide in the presence of acids, solutions of percarboxylic acids are formed in an equilibrium reaction (“Methodicum Chimicum •, CO Compounds, Volume 5, pages 737-739, Thieme Verlag, Stuttgart, 1975; Ullmann's Encyclopedia of Technical Chemistry, 3rd edition 1962, 13th volume, page 254; 4th edition 1979, 17th volume, page 669).
  • DE-A-2519 299 describes a process for the preparation of perpropionic acid solutions.
  • a considerable disadvantage of the process known from DE-C-2219 505 is that an equilibrium peracetic acid is used for bleaching with peracid. This is because a very large excess of carboxylic acid must be used in the preparation of the equilibrium peracid in order to shift the equilibrium as far as possible to the peracid side. The hydrogen peroxide not converted to the peracid is namely lost during the washing of the pulp following the peracid bleaching stage.
  • an equilibrium persic acid is used, in the production of which an 8 to 10-fold excess of carboxylic acid is used. Because of the amounts of carboxylic acid required for this, the known bleaching process is uneconomical.
  • the invention relates to a process for bleaching pulp using organic peracids in the acidic range and hydrogen peroxide in the alkaline range, in which a peracid which has a peracid content of 5 to 40% by weight and a hydrogen peroxide content of 10 to 50% by weight, and which is obtained from an organic carboxylic acid in a concentration of 50 to 100% by weight by reaction with hydrogen peroxide in a concentration of 30 to 90% by weight, preferably 50 to 70% by weight, in Presence of a mineral acid at a temperature between 20 and 100 ° C, preferably 50 to 80 ° C, provided that the amounts of peracid to 0.1 to 5 wt .-% and that of peroxide to 0.2 up to 3.0% by weight, based on dry cellulose, do not wash the pulp after this bleaching stage, add the amount of alkali required to carry out the alkaline bleaching stage with peroxide in the form of an aqueous solution and the bleach with peroxide without further addition of peroxide.
  • the excess peroxide remaining from the acidic peracid bleaching stage is used for the peroxide bleaching.
  • Acetic acid or propionic acid can be used as carboxylic acids.
  • the temperatures in the bleaching stages can be between 20 and 140 ° C, preferably between 40 and 90 ° C.
  • the consistency in the peracid bleaching stage can be between 5 and 30%, preferably 10 to 15%, based on dry cellulose.
  • the consistency can be 5 to 25% by weight, preferably 10 to 15% by weight, based on dry cellulose.
  • the peracid / peroxide bleaching sequence can be repeated.
  • further known bleaching stages such as hypochlorite or chlorine dioxide, can be carried out.
  • the chloride-free waste water can be evaporated after the peroxide bleaching stage and fed to the incineration. It is possible to recover the carboxylic acid used for the production of peracid during evaporation after neutralizing the waste water.
  • the process according to the invention can optionally be carried out repeatedly in a bleaching tower suitable for displacement bleaching, the displaced peracid solution being mixed with alkali and fed back to the bleaching tower for peroxide bleaching.
  • Dispensing with the washing of the pulp according to the peracid level makes it possible, after alkalization by adding a sodium hydroxide solution, to use the entire content of hydrogen peroxide in the pulp for further bleaching. This means that an equilibrium percarboxylic acid can be used economically even with a high peroxide content, or that an equilibrium does not have to be waited for.
  • variable b a mixture of H 2 0 2 and peracetic acid (1: 1) is used by the process according to the invention (variant b), which is obtained by reacting H 2 0 2 (70%) with glacial acetic acid in the presence of catalytic amounts of sulfuric acid at 60 ° C. and an hour's reaction time was obtained, only 1.25 kg of glacial acetic acid are required for bleaching 100 kg of cellulose.
  • the H 2 O 2 / peracetic acid mixture (1.6 1) required for bleaching 100 kg of cellulose is made from H 2 0 2 (50%) and glacial acetic acid in the presence of catalytic amounts of sulfuric acid at 60 ° C and a reaction time of 1 hour with only 0.88 kg of acetic acid.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
EP80108011A 1980-02-16 1980-12-18 Verfahren zur Bleiche von Zellstoffen mittels organischer Persäure Expired EP0034219B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80108011T ATE1826T1 (de) 1980-02-16 1980-12-18 Verfahren zur bleiche von zellstoffen mittels organischer persaeure.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3005947A DE3005947B1 (de) 1980-02-16 1980-02-16 Verfahren zur Bleiche von Zellstoffen mittels organischer Persaeure
DE3005947 1980-02-16

Publications (3)

Publication Number Publication Date
EP0034219A1 EP0034219A1 (de) 1981-08-26
EP0034219B1 EP0034219B1 (de) 1982-11-17
EP0034219B2 true EP0034219B2 (de) 1986-04-16

Family

ID=6094866

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80108011A Expired EP0034219B2 (de) 1980-02-16 1980-12-18 Verfahren zur Bleiche von Zellstoffen mittels organischer Persäure

Country Status (10)

Country Link
US (1) US4400237A (xx)
EP (1) EP0034219B2 (xx)
JP (1) JPS56128389A (xx)
AT (1) ATE1826T1 (xx)
BR (1) BR8100867A (xx)
CA (1) CA1144711A (xx)
DE (2) DE3005947B1 (xx)
FI (1) FI68685C (xx)
NO (1) NO155499B (xx)
ZA (1) ZA81785B (xx)

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5721591A (en) * 1980-07-11 1982-02-04 Mitsubishi Gas Chemical Co Peroxide bleaching of wood pulp
AT378016B (de) * 1982-12-02 1985-06-10 Ver Edelstahlwerke Ag Verfahren zum entfaerben und/oder bleichen von zellulosematerial, insbesondere zellstoff, und vorrichtung zur durchfuehrung des verfahrens
US4793898A (en) * 1985-02-22 1988-12-27 Oy Keskuslaboratorio - Centrallaboratorium Ab Process for bleaching organic peroxyacid cooked material with an alkaline solution of hydrogen peroxide
FI74750C (fi) * 1985-03-22 1988-03-10 Keskuslaboratorio Foerfarande foer framstaellning av blekt cellulosamassa utav ligninhaltigt raomaterial.
US4859282A (en) * 1988-04-15 1989-08-22 E. I. Du Pont De Nemours And Company Acid purification of product from alkaline peroxide processing of nonwoody lignocellulosic substrates
FR2647641B1 (fr) * 1989-06-05 1992-01-17 Atochem Procede de fabrication de pulpes vegetales blanchies
BE1004630A3 (fr) * 1990-10-17 1992-12-22 Interox Internat Sa Procede pour la preservation des caracteristiques de resistance mecanique des pates a papier chimiques.
DE4035813A1 (de) * 1990-11-10 1992-05-14 Akzo Gmbh Sauerstoffbleichung
DE4114134A1 (de) * 1991-04-30 1992-11-05 Sueddeutsche Kalkstickstoff Verfahren zur chlorfreien bleiche und delignifizierung von alkalizellstoff
DE4114135A1 (de) * 1991-04-30 1992-11-05 Sueddeutsche Kalkstickstoff Verfahren zur chlorfreien bleiche und delignifizierung von alkalizellstoff
EP0535741B1 (fr) * 1991-10-04 1998-07-08 Solvay Interox, Inc. Procédé pour l'amélioration de la sélectivité de la délignification d'une pâte à papier chimique
EP0578303B1 (fr) * 1992-07-06 1996-01-10 Solvay Interox Procédé pour la délignification d'une pâte à papier chimique
BE1006057A3 (fr) * 1992-07-06 1994-05-03 Solvay Interox Procede pour la delignification d'une pate a papier chimique.
GB2269191A (en) * 1992-07-29 1994-02-02 Solvay Interox Ltd Method of treating aqueous process liquors
US5589032A (en) * 1992-09-21 1996-12-31 North Carolina State University Process for preparing a bleaching liquor containing percarboxylic acid and caro's acid
DE69304342T3 (de) † 1992-11-27 2004-07-01 Eka Chemicals Ab Verfahren zum bleichen von lignocellulose-enthaltendem zellstoff
EP0634521A1 (en) * 1993-07-16 1995-01-18 Eka Nobel Ab Method for bleaching lignocellulose-containing fibres
FI98841C (fi) * 1994-06-20 1997-08-25 Kemira Chemicals Oy Menetelmä kemiallisen massan delignifioimiseksi
DE19516151A1 (de) 1995-05-03 1996-11-07 Sven Siegle Verfahren zur Herstellung einer Pulpe aus zellulosehaltigem Material, die Pulpe selbst und deren Verwendung
GB2304126A (en) * 1995-08-10 1997-03-12 Warwick Int Group Pulp treatment process
US5770011A (en) * 1995-11-17 1998-06-23 International Paper Company Neutral monoperoxysulfate bleaching process
FR2814180B1 (fr) * 2000-09-18 2003-12-05 Michel Delmas Procede de blanchiment de pates a papier en milieu organique a hydratation controlee
US20040200588A1 (en) * 2003-04-10 2004-10-14 Walker Jayne M.A. Method of controlling microorganisms in hydrogen peroxide pulp bleaching processes
DE602004031662D1 (de) * 2003-12-03 2011-04-14 Procter & Gamble Perhydrolase
US7754460B2 (en) * 2003-12-03 2010-07-13 Danisco Us Inc. Enzyme for the production of long chain peracid
US8476052B2 (en) * 2003-12-03 2013-07-02 Danisco Us Inc. Enzyme for the production of long chain peracid
US7297225B2 (en) * 2004-06-22 2007-11-20 Georgia-Pacific Consumer Products Lp Process for high temperature peroxide bleaching of pulp with cool discharge
FI121311B (fi) 2005-05-03 2010-09-30 M Real Oyj Menetelmä paperin- ja kartonginvalmistukseen soveltuvan mekaanisen massan valmistamiseksi
WO2007067473A2 (en) * 2005-12-06 2007-06-14 Genencor International, Inc. Perhydrolase epitopes
US20090311395A1 (en) * 2005-12-09 2009-12-17 Cervin Marguerite A ACYL Transferase Useful for Decontamination
US20080087390A1 (en) * 2006-10-11 2008-04-17 Fort James Corporation Multi-step pulp bleaching
US8845860B2 (en) 2010-09-16 2014-09-30 Georgia-Pacific Consumer Products Lp High brightness pulps from lignin rich waste papers

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2394989A (en) * 1942-03-11 1946-02-19 Bonard Claude Manufacture of cellulose
US2730444A (en) * 1950-10-10 1956-01-10 British Celanese Production of cellulose
BE633420A (xx) * 1962-07-16
DE2219505C3 (de) * 1972-04-21 1974-10-17 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt Chlorfreie Mehrstufenbleiche von Zellstoff

Also Published As

Publication number Publication date
FI68685C (fi) 1985-10-10
ATE1826T1 (de) 1982-12-15
DE3005947B1 (de) 1981-01-29
NO810057L (no) 1981-08-17
US4400237A (en) 1983-08-23
NO155499B (no) 1986-12-29
FI68685B (fi) 1985-06-28
CA1144711A (en) 1983-04-19
BR8100867A (pt) 1981-08-25
EP0034219A1 (de) 1981-08-26
FI810366L (fi) 1981-08-17
DE3061114D1 (en) 1982-12-23
JPS56128389A (en) 1981-10-07
EP0034219B1 (de) 1982-11-17
ZA81785B (en) 1982-03-31

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