WO1992007998A1 - Procede de blanchiment de pate - Google Patents

Procede de blanchiment de pate Download PDF

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Publication number
WO1992007998A1
WO1992007998A1 PCT/FI1991/000323 FI9100323W WO9207998A1 WO 1992007998 A1 WO1992007998 A1 WO 1992007998A1 FI 9100323 W FI9100323 W FI 9100323W WO 9207998 A1 WO9207998 A1 WO 9207998A1
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WO
WIPO (PCT)
Prior art keywords
chlorine
bleaching
pulp
treatment
enzyme
Prior art date
Application number
PCT/FI1991/000323
Other languages
English (en)
Inventor
Kari Rouvinen
Kimmo Ruohoniemi
Marja Vaheri
Original Assignee
Enso-Gutzeit Oy
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
Application filed by Enso-Gutzeit Oy filed Critical Enso-Gutzeit Oy
Publication of WO1992007998A1 publication Critical patent/WO1992007998A1/fr

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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
    • 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
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
    • 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
    • D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
    • 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

Definitions

  • the present invention relates to a method for bleaching pulp, whereby oxygen, peroxide and enzymes are used in the method.
  • Pulp from sulfate cooking in particular has a brown colour which is mainly related to residual lignin in the pulp.
  • Lignin is removed by bleaching that generally is a multistage process in which the pulp is alternately treate by oxidizing, lignin-degrading chemicals and the compounds resulting from lignin degradation are further treated by dissolving chemicals.
  • Oxidizing chemicals most generally applied are chlorine-containing compounds, while the chemicals employed for removing the degradation components typically are alkaline solutions.
  • Chlorine-containing bleaching chemicals convert in their reactions the lignin contained in the pulp into organic chlorine compounds, which are carried away along with the waste water from the bleaching process. Due to the possibl toxicity of the organic chlorine compounds contained in th waste waters of the bleaching process, these waste waters pose a problem for environmental protection; and furthermore, the waste waters of the bleaching process hav an intolerably high level of chemical oxygen demand. Because the measures taken by sulfate pulp plants for reduction of pollutant discharges to the environment have so far been mainly focused on other stages of the pulping process than bleaching, the relative proportion of bleaching in the discharges has grown steadily.
  • FI 890700, FI 892151, FI 893338, FI 900549 and FI 901711 have shown that enzymes can be effectively used for reducing the need of chlorine-based chemicals in bleaching.
  • peroxide as an improver of complete bleaching of sulfate pulp has strongly increased during the two last years. In comparison with oxygen, peroxide provides severa benefits that make peroxide a preferred alternative in a majority of cases. The most important of these benefits ar reduced need for investments, greater possibilities of energy savings and higher bleaching potential. Combination use of both these bleaching chemicals is possible, however in either the same stage or different bleaching stages.
  • the Swedish manufacturer Aspa Bruk has developed the Ligno bleaching process, in which the pulp is subjected after a pressurized pretreatment with oxygen to a treatment with EDTA (ethylene diaminetetraacetic acid) followed by a subsequent peroxide treatment.
  • EDTA ethylene diaminetetraacetic acid
  • This process makes it possible to achieve completely bleached pinewood sulfate pulp without the use of gaseous chlorine.
  • EDTA i not a biodegradable material, and its circulation in the described process has not yet been solved.
  • the invention is characterized in that the bleaching process proceeds stagewise from a pretreatment with oxygen subsequently followed by one or more treatments with hydrogen peroxide and chlorine, and that the pulp is subjected to an enzyme treatment in the process either before or after one or more of the afore-mentioned treatment stages.
  • coniferous wood pulp is subjected after the cooking to an enzyme treatment, which is subsequently followed by oxygen delignification.
  • the pulp is subjected to chlorine dioxide bleaching, subsequently followed by an enzyme treatment and peroxide treatment stage.
  • the pulp is further subjected twice to chlorine dioxide treatment.
  • the enzyme treatment is advanvatageously carried out according to the present invention over the temperature range 10...90 °C, preferably 40...80 °C and using a pH of 3.0...11.0, preferably pH 4.0...10.0.
  • the enzyme utilized can be hemicellulase, cellulase, pectinase, esterase, ligninase, phenol oxidase, lipase, or a mixture thereof.
  • the invention also concerns the application of enzymes to the reduction of chlorine contents in waste waters from the bleaching stage, said application comprising a prebleaching stage with oxygen, and a sequence of treatments performed in a desired order, said sequence comprising one or several treatments with hydrogen peroxide, chlorine and enzyme.
  • the enzyme is advantageously hemicellulase, cellulase, pectinase, esterase, ligninase, phenol oxidase or a mixtur thereof.
  • the use of the enzyme takes place essentially in the manner described for the bleaching method above.
  • pulp solids obtained from pinewood sulfate cookin (pulp solids content 30 %) was mixed with diluted xylanase enzyme (Biocon, alkaline hemicellulase) so as to achieve 10 % consistency of the mixture and xylanase activity of 5 U per 1 g of pulp solids.
  • the temperature during the enzyme treatment was held at 55 °C and the treatment time was 2 h.
  • the pulp was subjected to oxygen delignification, whereby NaOH was added to the mixture by 3 % wt. and oxygen was added so as to achieve a reaction pressure of 3 bar.
  • the reaction temperature was 95 °C and reaction time 45 min. After the treatment, the pulp was washed with 20-fold volume of water.
  • the bleaching was continued by subjecting the pulp to chlorine oxide treatment in the following conditions: 2.5 % wt. addition of chlorine dioxide, reaction temperature 70 °C and reaction time 3 h. After the treatment, the pulp was washed with 20-fold volume of water.
  • Pulpzyme hemicellulase Novo-Nordisk
  • the conditions of the enzyme treatment reaction were: Xylanase 5 U per 1 g pulp, pH 4.8, reaction time 90 min and reaction temperature 55 °C.
  • the pulp was subjected to peroxide treatment in the following conditions: 0.5 % wt. hydrogen peroxide, 1 % wt. NaOH, reaction temperature 70 °C and reaction time 2 h. After the treatment, the pulp was washed with 20-fold volume of water.
  • the pulp was twice subjected to chlorine dioxide treatment, whereby the chlorine dioxide content in the first treatment was 0.7 % and 0.3 % in the the second.
  • the reaction time in both treatments was 3 h and the reaction temperature was 70 °C. Between these treatments the pulp was washed with 20-fold volume of water.
  • Test 1 Pulp was not subjected to second enzyme treatment. Otherwise the test was similar to that described in the foregoing text (Test 3) .
  • Test 2 Pulp was not subjected to the first nor the second enzyme treatment.
  • alkaline lipase (Resinase A, Novo-Nordisk) was added to the pulp by 1 1 per 1 ton dry pulp and the mixtur was incubated for 90 min at 40 °C. The consistency of the reaction mixture was 10 % and its pH 10. After the reaction, the pulp was washed.
  • the bleaching was continued by subjecting the pulp t chlorine dioxide treatment in the following conditions: 2.5 % wt. C10 2 , reaction temperature 70 °C and reaction time 3 h. After the treatment, the pulp was washed with 20-fold volume of water.
  • Pulpzyme hemicellulase Novo-Nordisk
  • the conditions of the enzyme treatment reaction were: Xylanase 5 U per 1 pulp, pH 4.8, reaction time 90 min and reaction temperatur 55 °C.
  • the pulp was subjected to peroxide treatment in the following conditions: 0.5 % wt. hydrogen peroxide, 1 % wt. NaOH, reaction temperature 70 ° and reaction time 2 h. After the treatment, the pulp was washed with 20-fold volume of water.
  • the pulp was subjected to chlorine oxide treatme in the following conditions: 0.5 % wt. C10 2 , reaction temp erature 70 °C and reaction time 3 h. After the treatment, the pulp was washed with 20-fold volume of water.
  • Test 1 Pulp was not subjected to enzyme treatments. These stages were performed without the enzyme by adding an equal volume of water to the mixture. Otherwise the test was similar to that described in the foregoing text (Test 2) .
  • the performed tests indicate that the bleaching sequences in accordance with the present invention make it possible to attain a fully bleached product with the use of essentially lower consumptions of chlorine chemicals than those used in conventional bleaching sequences.
  • the waste water load fro conventional bleaching sequences of coniferous pulps is in the order of 4 kg (as AOX) per 1 ton pulp.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Paper (AREA)

Abstract

L'invention se rapporte à un procédé de blanchiment de pâte de cellulose, ladite invention étant caractérisée par le fait que le procédé de blanchiment progresse par étapes à partir d'un pré-traitement à l'oxygène suivi par un ou plusieurs traitement(s) au peroxyde d'hydrogène et au chlore selon un ordre voulu, et que la pâte est soumise, au cours de ce procédé, à un traitement enzymatique antérieur ou postérieur à l'étape ou aux étapes de traitement sus-mentionnée(s). Le procédé de blanchiment de l'invention permet de réduire les composés organiques toxiques dans les eaux usées provenant de l'étape de blanchiment tout en permettant de diminuer simultanément les besoins en oxygène chimique des eaux usées.
PCT/FI1991/000323 1990-11-02 1991-10-29 Procede de blanchiment de pate WO1992007998A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI905456A FI905456A (fi) 1990-11-02 1990-11-02 Foerfarande foer blekning av cellulosamassa.
FI905456 1990-11-02

Publications (1)

Publication Number Publication Date
WO1992007998A1 true WO1992007998A1 (fr) 1992-05-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI1991/000323 WO1992007998A1 (fr) 1990-11-02 1991-10-29 Procede de blanchiment de pate

Country Status (2)

Country Link
FI (1) FI905456A (fr)
WO (1) WO1992007998A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4440246A1 (de) * 1994-11-11 1996-05-15 Thueringisches Inst Textil Faserverbundwerkstoff und Verfahren zu seiner Herstellung
US5691193A (en) * 1993-02-25 1997-11-25 Pulp And Paper Research Institute Of Canada Non-chlorine bleaching of kraft pulp
WO2003048449A1 (fr) * 2001-12-03 2003-06-12 Iogen Bio-Products Corporation Etape de blanchiment comprenant l'utilisation de xylanase en association avec du peroxyde d'hydrogene, des peracides ou une combinaison de ces derniers
WO2003074780A1 (fr) * 2002-03-06 2003-09-12 Iogen Bio-Products Corporation Traitement de pate chimique par des xylanases
WO2005103372A3 (fr) * 2004-04-26 2006-03-16 Call Krimhild Systemes oxydants, reducteurs, hydrolytiques et autres systemes enzymatiques destines a l'oxydation, la reduction aux fins de revetement, de couplage et de reticulation de matieres fibreuses naturelles et artificielles, de matieres plastiques ou de matieres monomeres a polymeres naturelles et artificielles
US7320741B2 (en) 2001-01-18 2008-01-22 Iogen Bio-Products Corporation Method of xylanase treatment in a chlorine dioxide bleaching sequence

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0386888A2 (fr) * 1989-02-10 1990-09-12 ICI Canada Inc. Délignification à l'oxygène et traitement enzymatique
EP0406617A2 (fr) * 1989-06-22 1991-01-09 International Paper Company Délignification enzymatique de matériau lignocellulosique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0386888A2 (fr) * 1989-02-10 1990-09-12 ICI Canada Inc. Délignification à l'oxygène et traitement enzymatique
EP0406617A2 (fr) * 1989-06-22 1991-01-09 International Paper Company Délignification enzymatique de matériau lignocellulosique

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5691193A (en) * 1993-02-25 1997-11-25 Pulp And Paper Research Institute Of Canada Non-chlorine bleaching of kraft pulp
DE4440246A1 (de) * 1994-11-11 1996-05-15 Thueringisches Inst Textil Faserverbundwerkstoff und Verfahren zu seiner Herstellung
DE4440246C2 (de) * 1994-11-11 1998-06-04 Thueringisches Inst Textil Verfahren zur Herstellung eines biologisch abbaubaren cellulosischen Faserverbundwerkstoffs
US7320741B2 (en) 2001-01-18 2008-01-22 Iogen Bio-Products Corporation Method of xylanase treatment in a chlorine dioxide bleaching sequence
WO2003048449A1 (fr) * 2001-12-03 2003-06-12 Iogen Bio-Products Corporation Etape de blanchiment comprenant l'utilisation de xylanase en association avec du peroxyde d'hydrogene, des peracides ou une combinaison de ces derniers
WO2003074780A1 (fr) * 2002-03-06 2003-09-12 Iogen Bio-Products Corporation Traitement de pate chimique par des xylanases
CN100346030C (zh) * 2002-03-06 2007-10-31 埃欧金生物制品公司 化学纸浆的木聚糖酶处理
US7368036B2 (en) 2002-03-06 2008-05-06 Iogen Bio-Products Corporation Xylanase treatment of chemical pulp
WO2005103372A3 (fr) * 2004-04-26 2006-03-16 Call Krimhild Systemes oxydants, reducteurs, hydrolytiques et autres systemes enzymatiques destines a l'oxydation, la reduction aux fins de revetement, de couplage et de reticulation de matieres fibreuses naturelles et artificielles, de matieres plastiques ou de matieres monomeres a polymeres naturelles et artificielles

Also Published As

Publication number Publication date
FI905456A0 (fi) 1990-11-02
FI905456A (fi) 1992-05-03

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