EP0447673B1 - Procédé pour le blanchiment enzymatique de pâtes - Google Patents

Procédé pour le blanchiment enzymatique de pâtes Download PDF

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Publication number
EP0447673B1
EP0447673B1 EP90125380A EP90125380A EP0447673B1 EP 0447673 B1 EP0447673 B1 EP 0447673B1 EP 90125380 A EP90125380 A EP 90125380A EP 90125380 A EP90125380 A EP 90125380A EP 0447673 B1 EP0447673 B1 EP 0447673B1
Authority
EP
European Patent Office
Prior art keywords
process according
aqueous solution
added
solution containing
bleaching
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
EP90125380A
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German (de)
English (en)
Other versions
EP0447673A1 (fr
Inventor
Hans-Peter Dr. Call
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.)
LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG UND ZUM VERT
Original Assignee
LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG und ZUM VERTRIEB VON ENZYMEN mbH
Lignozym GmbH
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Publication of EP0447673A1 publication Critical patent/EP0447673A1/fr
Application granted granted Critical
Publication of EP0447673B1 publication Critical patent/EP0447673B1/fr
Anticipated expiration legal-status Critical
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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
    • D21C9/1084—Bleaching ; Apparatus therefor with reducing compounds
    • 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
    • D21C9/1084—Bleaching ; Apparatus therefor with reducing compounds
    • D21C9/1089—Bleaching ; Apparatus therefor with reducing compounds with dithionites
    • 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
    • D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
    • D21C9/153—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications with ozone
    • 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 the enzymatic bleaching of cellulose.
  • DE-C-31 10 117 discloses a process for the production of cellulose from wood or other plant fiber materials, in which the lignocellulose is broken down with the help of white rot fungi.
  • the processes using microorganisms have considerable disadvantages. So far it has not been possible to achieve degradation and detachment of the lignin from its accompanying polymers (cellulose) without simultaneous growth of the microorganisms and without loss of cellulose. The simultaneous growth of the fungus leads to very long breakdown times, which can take up to several weeks.
  • Chlorine bleach is associated with major environmental problems.
  • the kappa number ie the lignin content
  • the pulp is thus brightened.
  • WO-A-88/03190 a method for removing and / or converting lignin or its degradation products from cellulose-containing material is known.
  • a redox potential between 200 and 500 mV is set by adding oxidizing agents and / or reducing agents and / or salts and / or phenolic compounds to an acidic, lignin-containing solution.
  • the lignin-degrading reaction is then started by adding enzymes.
  • a disadvantage of this process is that a satisfactory bleaching effect cannot yet be achieved by adding the specified substances.
  • the object of the present invention is to provide a process for the enzymatic bleaching of cellulose in which a) a redox potential in the range between 200 and 500 mV is set with the simultaneous addition of oxidizing and reducing agents and addition of salts to an aqueous solution, and b) a bleaching reaction is started by adding lignolytic enzymes.
  • the object is achieved in that the aqueous cellulose-containing solution as a salt copper (II) sulfate or a mixture of copper (II) sulfate with Mn (II) sulfate. Mn (II) acetate. Fe (II) sulfate. Ti (III) chloride. Ce (III) nitrate and / or Ce (IV) ammonium nitrate and complexing agents are added and the reaction is maintained with constant stirring for 15 minutes to 2 hours.
  • the redox potential is preferably between 250 and 450 mV.
  • it can be determined by means of a redox electrode and by means of a controller and an actuator during the entire reaction time by adding oxidizing and reducing agents. Salts and phenolic compounds are kept constant.
  • Hydrogen peroxide is preferably used as the oxidizing agent. Oxygen and ozone are used. Ascorbic acid, dithionite and sodium bisulfite are suitable as reducing agents.
  • Copper (II) sulfate is added to the cellulose-containing aqueous solution as the salt.
  • Ce (III) nitrate and Ce (IV) ammonium nitrate can be used. Saize also come with the elements zinc. Antimony and lead are considered.
  • phenolic compounds can be added to the aqueous cellulose-containing solution. Veratryl alcohols have proven particularly useful as such.
  • fatty acids e.g. Oleic acids
  • heme compounds e.g. Hemoglobin
  • bleaching reagents e.g. Sodium perborate
  • post-bleaching can be carried out using common bleaching agents, such as sodium hypochlorite, O2, chlorine dioxide, ozone, H2O2 and sodium ionite.
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentraacetic acid
  • aqueous cellulose-containing solution Sodium hypochlorite, sodium perborate, detergents, surfactants and polysaccharides such as glucans and xanthans are suitable as such.
  • Lignolytic enzymes are preferably used as enzymes in the method according to the invention. These include phenol oxidases, laccases and peroxidases. The effectiveness of the method can be increased by using pectinase and / or hemicellulases. Particularly suitable lignolytic enzymes are those which are obtained from the white rot fungus Phanerochaete chrysosporium. The use of such enzymes is already known from US-A-4,692,413, 4,690,895 and 4,687,741. However, according to these patents, enzymes obtained from special mutants from Phanerochaete chrysosporium are used for bleaching. According to the invention, however, this is not necessary.
  • the pH is usually between 2 and 5. A pH of 3 is particularly preferred.
  • the temperature is 20 to 60 ° C., preferably 40 ° C. If the conditions are observed, the substances mentioned are added Redox potential set from 200 to 500 mV. This is determined by the ratio of the various substances added in the reaction vessel. By appropriate measurement and control of the addition of the oxidizing and reducing agents, the salts and possibly the phenolic compounds, it can be maintained throughout the reaction time.
  • the bleaching process is started by simultaneous dosing of H2O2 and sodium bisulfite solution.
  • the redox potential of approx. 400 mV is maintained. After the process is started, it continues for 2 hours.
  • the process is controlled and regulated by means of a redox electrode and a pump control.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Paper (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Breeding Of Plants And Reproduction By Means Of Culturing (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Detergent Compositions (AREA)
  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)

Claims (23)

  1. Procéde de blanchiment enzymatique de cellulose, dans le cas duquel
    a) est ajusté un potentiel redox dans la gamme allant de 200 et 500 mV tout en ajoutant des agents d'oxydation et de réduction ainsi que des sels à une solution aqueuse et
    b) est déclenchée une réaction de blanchiment par l'addition d'enzymes lignolytiques,
    caractérisé par le fait que le sel ajouté à la solution aqueuse et contenant de la cellulose est du sulfate cuivrique ou un mélange de sulfate cuivrique et de sulfate manganeux, d'acétate manganeux, de sulfate ferreux, de trichlorure de titane, de nitrate céreux et / ou de nitrate céreux d'ammonium, que l'on additionne de surplus un complexant et que la réaction est maintenue pour une durée comprise entre 15 minutes et 2 heures tout en remuant en permanence.
  2. Procédé selon la revendication 1, caractérisé par le fait que le complexant utilisé est du éthylènediamine-tetraacide acétique (EDTA) ou bien du diéthylènetriamine - pentaacide acétique (DTPA).
  3. Procédé selon l'une des revendications 1 ou 2, caractérisé par le fait que l'on ajoute à la solution aqueuse et contenant de la cellulose des polysaccharides.
  4. Procédé selon la revendication 3, caractérisé par le fait que les polysaccharides ajoutés sont des glucanes et / ou du xanthane.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé par le fait que l'on ajoute à la solution aqueuse et contenant de la cellulose des détergents.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé par le fait que l'on ajoute à la solution aqueuse et contenant de la cellulose des agents de surface.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé par le fait que l'on ajoute à la solution aqueuse et contenant de la cellulose des acides gras.
  8. Procédé selon la revendication 7, caractérisé par le fait que les acides gras ajoutés sont des acides oléiques.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé par le fait que l'on ajoute à la solution aqueuse et contenant de la cellulose des combinaisons hèmes.
  10. Procédé selon la revendication 9, caractérisé par le fait que l'on utilise en tant que combinaison hème de la hémoglobine.
  11. Procédé selon l'une des revendications 1 à 10, caractérisé par le fait que l'on utilise en tant qu'enzymes lignolytiques des peroxydases de lignine ainsi que des laccases.
  12. Procédé selon l'une des revendications 1 à 11, caractérisé par le fait que l'on ajoute à la solution aqueuse et contenant de la cellulose de surplus des combinaisons phénoliques pour l'ajustement du potentiel redox.
  13. Procédé selon la revendication 12, caractérisé par le fait que la combinaison phénolique ajoutée est de l'acool de vératryle.
  14. Procédé selon l'une des revendications 1 à 13, caractérisé par le fait que l'on additionne en sus des enzymes lignolytiques, des pectinases ainsi que / ou des hémicellulases.
  15. Procédé selon l'une des revendications 1 à 14, caractérisé par le fait que la valeur pH est comprise entre 2 et 5.
  16. Procédé selon l'une des revendications 1 à 15, caractérisé par le fait que la valeur pH est de 3.
  17. Procédé selon l'une des revendications 1 à 16, caractérisé par le fait que la température est comprise entre 20 et 60°C.
  18. Procédé selon l'une des revendications 1 à 17, caractérisé par le fait que la température est de 40°C.
  19. Procédé selon l'une des revendications 1 à 18, caractérisé par le fait que l'on additionne à la solution réactionnelle de l'hypochlorite de sodium.
  20. Procédé selon l'une des revendications 1 à 19, caractérisé par le fait que l'on ajoute à la solution aqueuse et contenant de la cellulose en sus des réactifs de blanchiment.
  21. Procédé selon la revendication 20, caractérisé par le fait que le réactif utilisé est du peroxohydrate de métaborate de sodium.
  22. Procédé selon l'une des revendications 1 à 21, caractérisé par le fait qu'après avoir terminé la réaction, on extrait avec du NaOH ainsi que / ou du H₂SO₄.
  23. Procédé selon l'une des revendications 1 à 22, caractérisé par le fait que l'on utilise pour effectuer un deuxième blanchiment du chlorite de sodium, du chlore, du dioxyde de chlore, du O₂, de l'ozone, du H₂O₂ ainsi que du dithionite de sodium.
EP90125380A 1990-03-20 1990-12-22 Procédé pour le blanchiment enzymatique de pâtes Expired - Lifetime EP0447673B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4008893 1990-03-20
DE4008893A DE4008893A1 (de) 1990-03-20 1990-03-20 Verfahren zum enzymatischen bleichen von zellstoffen

Publications (2)

Publication Number Publication Date
EP0447673A1 EP0447673A1 (fr) 1991-09-25
EP0447673B1 true EP0447673B1 (fr) 1995-03-08

Family

ID=6402620

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90125380A Expired - Lifetime EP0447673B1 (fr) 1990-03-20 1990-12-22 Procédé pour le blanchiment enzymatique de pâtes

Country Status (13)

Country Link
EP (1) EP0447673B1 (fr)
JP (1) JPH05505857A (fr)
AT (1) ATE119593T1 (fr)
AU (1) AU641494B2 (fr)
BR (1) BR9106411A (fr)
CA (1) CA2078345A1 (fr)
DE (2) DE4008893A1 (fr)
DK (1) DK0447673T3 (fr)
ES (1) ES2072965T3 (fr)
FI (1) FI924169A (fr)
HU (1) HUT64119A (fr)
NO (1) NO180388C (fr)
WO (1) WO1991014823A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4137761A1 (de) * 1991-05-17 1992-11-19 Call Hans Peter Verfahren zur delignifizierung von lignocellulosehaltigem material, bleiche und behandlung von abwaessern mittels laccasen mit erweiteter wirksamkeit
FI914780A0 (fi) * 1991-10-10 1991-10-10 Valtion Teknillinen Foerfarande foer entsymatisk behandling av lignocellulosahaltiga material, i synnerhet cellulosamassor.
CA2115881C (fr) * 1993-02-25 2000-05-23 Michael G. Paice Methode de blanchiment sans chlore de la pate kraft
ATE169699T1 (de) * 1993-06-16 1998-08-15 Lignozym Gmbh Verfahren zur veränderung, abbau oder bleichen von lignin, ligninhaltigen materialien oder kohle
BE1007272A3 (fr) * 1993-07-15 1995-05-09 Solvay Procede pour le blanchiment d'une pate a papier.
EP0652321B1 (fr) * 1993-11-04 1998-01-21 Morton International, Inc. Blanchiment de pâte à papier chimique
DE19820947B4 (de) * 1997-05-12 2005-12-01 Call, Krimhild Enzymatisches Bleichsystem mit neuen enzymwirkungsverstärkenden Verbindungen zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder Verändern oder Abbau von Kohle sowie Verfahren unter Verwendung des Bleichsystems
EP1025305B1 (fr) * 1997-08-14 2003-11-19 Takashi Watanabe Procede chimique de depolymerisation de la lignine
AU3401799A (en) * 1998-04-16 1999-11-08 Pulp And Paper Research Institute Of Canada Oxidase process for pulp and dye oxidation

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3110117C2 (de) * 1981-03-16 1983-09-29 Adolf 5340 St. Gilgen Basler Herstellung von Cellulose aus Holz oder anderen lignocellulosehaltigen Pflanzen durch mikrobiellen Abbau der Lignocellulose
US4687741A (en) * 1985-07-15 1987-08-18 Repligen Corporation Novel enzymes which catalyze the degradation and modification of lignin
US4690895A (en) * 1985-07-15 1987-09-01 Repligen Corporation Use of rLDM™ 1-6 and other ligninolytic enzymes in the bleaching of kraft pulp
US4692413A (en) * 1985-07-15 1987-09-08 Repligen Corporation Use of rLDM™ 1-6 and other ligninolytic enzymes for the decolorization of E1 effluent
DE3636208A1 (de) * 1986-10-24 1988-05-05 Call Hans Peter Verfahren zur delignifizierung und bleichung von lignicellulosehaltigem bzw. ligninhaltigem material bzw. lignin durch enzymatische behandlung
ZA894239B (en) * 1988-06-08 1990-03-28 Int Paper Co Enzymatic delignification of lignocellulosic material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.P. Casey "Pulp and Paper; Chemistry and Chemical Technology" dritte Auflage, Band I, 1980, John Wiley & Sons, New York, Seiten 651, 652. *

Also Published As

Publication number Publication date
HU9202982D0 (en) 1993-01-28
BR9106411A (pt) 1993-05-04
JPH05505857A (ja) 1993-08-26
CA2078345A1 (fr) 1991-09-21
EP0447673A1 (fr) 1991-09-25
AU641494B2 (en) 1993-09-23
DE4008893A1 (de) 1991-09-26
FI924169A0 (fi) 1992-09-17
NO923601L (no) 1992-09-16
AU7543291A (en) 1991-10-21
HUT64119A (en) 1993-11-29
NO180388B (no) 1996-12-30
DE4008893C2 (fr) 1992-09-03
ES2072965T3 (es) 1995-08-01
DK0447673T3 (da) 1995-07-24
FI924169A (fi) 1992-09-17
ATE119593T1 (de) 1995-03-15
DE59008655D1 (de) 1995-04-13
NO923601D0 (no) 1992-09-16
WO1991014823A1 (fr) 1991-10-03
NO180388C (no) 1997-04-09

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