EP0019963B1 - Procédé pour la délignification et le blanchiment de pâtes cellulosiques chimiques et semi-chimiques - Google Patents

Procédé pour la délignification et le blanchiment de pâtes cellulosiques chimiques et semi-chimiques Download PDF

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Publication number
EP0019963B1
EP0019963B1 EP80200450A EP80200450A EP0019963B1 EP 0019963 B1 EP0019963 B1 EP 0019963B1 EP 80200450 A EP80200450 A EP 80200450A EP 80200450 A EP80200450 A EP 80200450A EP 0019963 B1 EP0019963 B1 EP 0019963B1
Authority
EP
European Patent Office
Prior art keywords
treatment
peroxide
process according
oxygen
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
Application number
EP80200450A
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German (de)
English (en)
French (fr)
Other versions
EP0019963A1 (fr
Inventor
Georges Papageorges
Pierre Ledoux
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.)
Solvay Chimie SA
Original Assignee
Interox 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
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=9225939&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0019963(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Interox SA filed Critical Interox SA
Priority to AT80200450T priority Critical patent/ATE2018T1/de
Publication of EP0019963A1 publication Critical patent/EP0019963A1/fr
Application granted granted Critical
Publication of EP0019963B1 publication Critical patent/EP0019963B1/fr
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
    • D21C9/1057—Multistage, with compounds cited in more than one sub-group D21C9/10, D21C9/12, D21C9/16

Definitions

  • the present invention relates to a sequential process for the delignification and bleaching of chemical and semi-chemical cellulosic pulps by the action of oxygen, further comprising a subsequent bleaching treatment with peroxide.
  • the bleaching of chemical and semi-chemical cellulose pulps intended in particular for the manufacture of paper generally requires several successive bleaching treatments, possibly interspersed with washing, dilution and / or concentration steps, in order to reach the level of residual lignin and to the desired whiteness.
  • the object of the invention is to provide a process which makes it possible to overcome the drawbacks of the known processes cited above and in particular to avoid excessive depolymerization of the cellulose in chemical and semi-chemical pastes.
  • the method according to the invention also makes it possible to produce paper pulps with good yields.
  • the pasta obtained also has a good degree of whiteness.
  • the invention relates to a process for the delignification and bleaching of chemical and semi-chemical cellulosic pulps comprising an oxygen treatment in an alkaline medium and a subsequent treatment using peroxides according to which the effluents from the peroxide treatment are at least partially recycled for oxygen treatment.
  • stage O only part of the effluents from the peroxide treatment, preferably not exceeding 80% of their weight, is recycled to the oxygen treatment. Good results have been obtained by recycling to the oxygen treatment from 5 to 70% of the weight of the effluents from the peroxide treatment (also called stage P below).
  • the oxygen treatment is generally carried out using an oxygen-containing gas such as oxygen or air. Other mixtures of oxygen-containing gases can also be used.
  • the partial pressures of oxygen can vary within wide limits. They are generally between 100 kPa and 2 MPa.
  • the temperatures are generally between 353 and 423 K and preferably between 373 and 503 K.
  • the oxygen treatment is carried out in the presence of an alkaline aqueous solution.
  • alkalis can be used for this purpose. In general, they are chosen from hydroxides, bicarbonates and carbonates of alkali metals and ammonium and their mixtures. Good results are obtained by using an alkali containing sodium hydroxide.
  • the amount of alkali used can vary within wide limits. It is generally between 0.1 and 20%, and preferably between 1 and 15% of the weight of dry pulp.
  • the density of the paste used in stage 0 is generally between 3 and 50% and preferably between 5 and 40%.
  • additives can be used in stage 0, without this being essential, such as cellulose protecting agents, sequestering agents, pH regulators, etc.
  • the total content of various additives generally does not exceed 10% of the weight of the dry paste.
  • the protective agents are generally chosen from derivatives of alkaline earth metals. These derivatives are most often alkaline earth metal salts and more particularly magnesium salts. It is thus possible to use during the oxygen treatment of carbonate, sulphate, oxide or magnesium hydroxide.
  • the oxygen treatment can be carried out in any device known per se suitable for delignification and capable of withstanding the pressures used. Various types of autoclaves can thus be used.
  • the dough After the oxygen treatment, the dough is degassed. It can be sent as is to subsequent whitening treatment.
  • the dough can also be subjected to one or more washing or dilution, and possibly concentration, stages before sending it to the subsequent bleaching treatment.
  • These various steps can be carried out in various types of apparatus known in themselves.
  • the concentrations can thus be carried out in various types of apparatus allowing the extraction of the dough such as rotary filters or various types of press.
  • Any effluents from these washing, dilution and concentration stages subsequent to stage 0 can be recycled to stage 0 and / or subjected to incineration so as to regenerate the alkali. In general, at least 10% of the weight of these effluents is sent to recovery boilers for incineration.
  • the pulp obtained can then optionally undergo intermediate bleaching treatments before being sent to the peroxide treatment. It is thus possible to subject the paste obtained from stage O, optionally after the washing, dilution or concentration steps mentioned above, to at least one intermediate treatment chosen from treatments with carboxylic peracids and ozone. However, such intermediate bleaching treatments are not essential. Good results have been obtained by sending the pulp from the oxygen treatment to the peroxide treatment, without any intermediate bleaching treatment.
  • the peroxide treatment is carried out in the presence of peroxidized compounds of various types. It is thus possible to use hydrogen peroxide, alkali metal peroxides, other inorganic peroxides, and organic peroxides, hydro-peroxides or peracids. In general, a peroxide compound chosen from hydrogen peroxide, sodium peroxide and their mixture is used. Good results are obtained using hydrogen peroxide.
  • the amount of peroxide compounds used calculated as pure hydrogen peroxide is generally between 0.1 and 10% and preferably between 0.2 and 5% of the weight of dry pulp.
  • the mixture subjected to stage P is maintained at a basic pH, generally between 9 and 13 and more often between 10 and 12.5.
  • alkalis are added to the mixture, which can be of very diverse natures.
  • hydroxides or carbonates of alkali metals, alkaline earth metals or ammonium, and more particularly sodium hydroxide are added to the mixture.
  • the amount of alkali used depends on the type of peroxide compound used and more particularly on its possible alkaline character.
  • the peroxidized compound is hydrogen peroxide, generally 0.2 to 15% by weight of alkali is added relative to the weight of dry pulp. Good results are obtained using 0.5 to 10% alkali. These amounts are reduced when the peroxidized compound contains sodium peroxide.
  • the densities of the pastes subjected to the peroxide treatment are generally between 2 and 25%.
  • the temperatures are generally between room temperature and the boiling temperature of the mixture. Good results are obtained at temperatures between 333 and 353 K.
  • additives can be used in stage O, without this being essential, such as organic or inorganic stabilizers, surfactants, complexing agents, pH regulating agents, etc.
  • magnesium salts such as magnesium sulfate and silicates such as water glass are used.
  • agents generally chosen from organic compounds containing nitrogen and / or phosphorus such as nitrilotriacetic, ethylene-diamine-tetraacetic, diethylenetriamine-pentaacetic acids and their salts, polyhyroxycarboxylic acids and their salts such as sodium poly-hydroxyacrylate and hydroxycarboxylic acids and their salts such as sodium gluconate.
  • the peroxide treatment can take place in various types of apparatus known per se, such as towers or batteries.
  • the paste resulting from the peroxide treatment is then subjected to one or more concentration stages, possibly after one or more prior dilutions.
  • Concentration can be done according to various techniques known in themselves such as spinning in a rotary filter or in various types of press. This concentration brings the dough to a density generally greater than 10%.
  • the effluents from the concentration stages following the peroxide treatment are recycled at least in part to stage 0 according to the invention. They can be returned directly to the device where the oxygen treatment is carried out, or even mixed with stage O effluents intended to be recycled there.
  • stage P The part of the effluents of stage P which is not recycled in stage 0 is advantageously recycled in stage P or also used to dilute the pulp resulting from stage P before its concentration.
  • a particularly suitable method consists in diluting the paste resulting from the peroxide treatment, in concentrating it on one or more apparatuses suitable for wringing, in collecting the effluents from these wrings which constitute the effluents of the method according to the invention, in using 30 to 95% of these effluents for the step of diluting the pulp resulting from the peroxide treatment and recycling the balance of these effluents to the oxygen treatment.
  • the devices used for wringing the dough from the peroxide treatment can also be supplied with a small amount of fresh water or an aqueous solution.
  • the quantity of water or aqueous solution used is substantially equal to the quantity of effluents from the oxygen treatment sent to the recovery boilers.
  • Stage P of the process according to the invention can, depending on the desired degree of whiteness, be subjected to one or more additional bleaching treatments. These are generally chosen from treatments with peroxide, chlorine dioxide (also called stages D), hypochlorite (also called stages H), carboxylic peracids (also called stage P / J and chlorine (called also stages C) or alkaline extractions (also called stage E) Certain specific sequences of subsequent treatments have given good results: these are the CED, CEH, CHH, CPD, CPH, DED, DHD and DPD sequences.
  • Example 2 was carried out by way of comparison in the absence of recycling.
  • Example 1 Bleaching of a pine kraft pulp
  • a pine kraft paste (initial whiteness 27.6 ° ISO, kappa index 39.6) was subjected to a treatment in five stages comprising a first oxygen treatment and a second peroxide treatment with recycling of the effluent from the peroxide stage to the oxygen stage.
  • the operating conditions are given below.
  • the percentages of the reactants are given relative to the dry paste.
  • the final viscosity of the paste from the last step measured according to the TAPPI T 230 standard is 12.0 mPa.s.
  • Example 2 Whitening of a pine kraft pulp
  • test 1 The same pine kraft pulp as that used for carrying out test 1 was subjected to a treatment in five stages comprising a first treatment with oxygen and a second treatment with peroxide without recycling of the effluent from stage with peroxide in the oxygen step.
  • the other operating conditions are identical to those of test 1.
  • the final viscosity of the paste at the end of the last step is 10.8 mPa.s.
  • the cellulose pulp therefore underwent a greater depolymerization than when the method according to the invention was used.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
EP80200450A 1979-05-25 1980-05-14 Procédé pour la délignification et le blanchiment de pâtes cellulosiques chimiques et semi-chimiques Expired EP0019963B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80200450T ATE2018T1 (de) 1979-05-25 1980-05-14 Verfahren zur delignifizierung und zum bleichen von chemischen und halbchemischen zellstoffen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7913554 1979-05-25
FR7913554A FR2457339A1 (fr) 1979-05-25 1979-05-25 Procede pour la delignification et le blanchiment de pates cellulosiques chimiques et semi-chimiques

Publications (2)

Publication Number Publication Date
EP0019963A1 EP0019963A1 (fr) 1980-12-10
EP0019963B1 true EP0019963B1 (fr) 1982-12-15

Family

ID=9225939

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80200450A Expired EP0019963B1 (fr) 1979-05-25 1980-05-14 Procédé pour la délignification et le blanchiment de pâtes cellulosiques chimiques et semi-chimiques

Country Status (6)

Country Link
US (1) US4459174A (enrdf_load_stackoverflow)
EP (1) EP0019963B1 (enrdf_load_stackoverflow)
AT (1) ATE2018T1 (enrdf_load_stackoverflow)
DE (1) DE3061330D1 (enrdf_load_stackoverflow)
ES (1) ES8102237A1 (enrdf_load_stackoverflow)
FR (1) FR2457339A1 (enrdf_load_stackoverflow)

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2566015B1 (fr) * 1984-06-15 1986-08-29 Centre Tech Ind Papier Procede de blanchiment de pate mecanique par le peroxyde d'hydrogene
DE3802401A1 (de) * 1988-01-28 1989-08-03 Degussa Verfahren zur herstellung von halbgebleichtem kraftzellstoff
US5023097A (en) * 1988-04-05 1991-06-11 Xylan, Inc. Delignification of non-woody biomass
US4842877A (en) * 1988-04-05 1989-06-27 Xylan, Inc. Delignification of non-woody biomass
US5525195A (en) * 1989-02-15 1996-06-11 Union Camp Patent Holding, Inc. Process for high consistency delignification using a low consistency alkali pretreatment
US5409570A (en) * 1989-02-15 1995-04-25 Union Camp Patent Holding, Inc. Process for ozone bleaching of oxygen delignified pulp while conveying the pulp through a reaction zone
US5085734A (en) * 1989-02-15 1992-02-04 Union Camp Patent Holding, Inc. Methods of high consistency oxygen delignification using a low consistency alkali pretreatment
US5211811A (en) * 1989-02-15 1993-05-18 Union Camp Patent Holding, Inc. Process for high consistency oxygen delignification of alkaline treated pulp followed by ozone delignification
US5188708A (en) * 1989-02-15 1993-02-23 Union Camp Patent Holding, Inc. Process for high consistency oxygen delignification followed by ozone relignification
US5217574A (en) * 1989-02-15 1993-06-08 Union Camp Patent Holdings Inc. Process for oxygen delignifying high consistency pulp by removing and recycling pressate from alkaline pulp
US5173153A (en) * 1991-01-03 1992-12-22 Union Camp Patent Holding, Inc. Process for enhanced oxygen delignification using high consistency and a split alkali addition
US5011572A (en) * 1989-05-19 1991-04-30 Fmc Corporation Two stage process for the oxygen delignification of lignocellulosic fibers with peroxide reinforcement in the first stage
ATE97179T1 (de) * 1989-06-06 1993-11-15 Eka Nobel Ab Verfahren zum bleichen von lignocellulose enthaltenden zellstoffen.
DE3923728A1 (de) * 1989-07-18 1991-01-24 Degussa Verfahren zur stabilisierung der viskositaet von zellstoffen
SE9001481L (sv) * 1990-04-23 1991-10-24 Eka Nobel Ab Reduktion av halogenorganiska foereningar i blekeriavlopp
SE466061B (sv) * 1990-04-23 1991-12-09 Eka Nobel Ab Blekning av kemisk massa genom behandling med foerst ett komplexbildande aemne och sedan ett peroxidinnehaallande aemne
US5164043A (en) * 1990-05-17 1992-11-17 Union Camp Patent Holding, Inc. Environmentally improved process for bleaching lignocellulosic materials with ozone
US5164044A (en) * 1990-05-17 1992-11-17 Union Camp Patent Holding, Inc. Environmentally improved process for bleaching lignocellulosic materials with ozone
US5441603A (en) * 1990-05-17 1995-08-15 Union Camp Patent Holding, Inc. Method for chelation of pulp prior to ozone delignification
ES2049165B1 (es) * 1990-08-10 1994-10-16 Whites Martins Gases Ind S A Procedimiento para pre-blanquear o deslignificar pasta kraft empleando oxigeno.
BE1004674A3 (fr) * 1991-03-11 1993-01-12 Interox Internat Sa Procede pour le blanchiment d'une pate a papier chimique et application de ce procede au blanchiment d'une pate kraft.
SE468355B (sv) * 1991-04-30 1992-12-21 Eka Nobel Ab Blekning av kemisk massa genom behandling med komplexbildare och ozon
US5554259A (en) * 1993-10-01 1996-09-10 Union Camp Patent Holdings, Inc. Reduction of salt scale precipitation by control of process stream Ph and salt concentration
US5672247A (en) * 1995-03-03 1997-09-30 Union Camp Patent Holding, Inc. Control scheme for rapid pulp delignification and bleaching
US5736004A (en) * 1995-03-03 1998-04-07 Union Camp Patent Holding, Inc. Control scheme for rapid pulp delignification and bleaching
US5656130A (en) * 1995-04-28 1997-08-12 Union Camp Holding, Inc. Ambient temperature pulp bleaching with peroxyacid salts
US5705216A (en) * 1995-08-11 1998-01-06 Tyson; George J. Production of hydrophobic fibers
BE1011129A4 (fr) * 1997-04-25 1999-05-04 Solvay Interox Procede continu de delignification et/ou de blanchiment de pate a papier chimique vierge ou recyclee.
CA2451444C (en) * 2001-07-17 2010-06-15 Zhi-Wei Liang Oxidative thermochemical drying process for changing hydrophilic/hydrophobic characteristics of natural organic substances
ATE386837T1 (de) * 2004-06-14 2008-03-15 Warwick Internat Group Ltd Aktivator zum zellstoffbleichen
US8138106B2 (en) 2005-09-30 2012-03-20 Rayonier Trs Holdings Inc. Cellulosic fibers with odor control characteristics
AU2008313142B2 (en) * 2007-10-17 2013-05-23 Nippon Steel & Sumikin Chemical Co., Ltd. Production methods for solubilized lignin, saccharide raw material and monosaccharide raw material, and solubilized lignin
FR2951096B1 (fr) 2009-10-09 2013-03-15 Total Sa Procede d'oxydation de composes organiques

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI45574C (fi) * 1970-05-11 1972-07-10 Kymin Oy Kymmene Ab Menetelmä selluloosapitoisten aineiden valkaisemiseksi.
CA966604A (en) * 1970-12-21 1975-04-29 Scott Paper Company Kraft pulp bleaching and recovery process
US4196043A (en) * 1970-12-21 1980-04-01 Scott Paper Company Kraft pulp bleaching and recovery process
US3719552A (en) * 1971-06-18 1973-03-06 American Cyanamid Co Bleaching of lignocellulosic materials with oxygen in the presence of a peroxide
US4372812A (en) * 1978-04-07 1983-02-08 International Paper Company Chlorine free process for bleaching lignocellulosic pulp

Also Published As

Publication number Publication date
FR2457339B1 (enrdf_load_stackoverflow) 1982-09-17
FR2457339A1 (fr) 1980-12-19
ES491799A0 (es) 1980-12-16
EP0019963A1 (fr) 1980-12-10
DE3061330D1 (en) 1983-01-20
US4459174A (en) 1984-07-10
ES8102237A1 (es) 1980-12-16
ATE2018T1 (de) 1982-12-15

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