EP0447673A1 - Procédé pour le blanchiment enzymatique de pâtes - Google Patents

Procédé pour le blanchiment enzymatique de pâtes Download PDF

Info

Publication number
EP0447673A1
EP0447673A1 EP90125380A EP90125380A EP0447673A1 EP 0447673 A1 EP0447673 A1 EP 0447673A1 EP 90125380 A EP90125380 A EP 90125380A EP 90125380 A EP90125380 A EP 90125380A EP 0447673 A1 EP0447673 A1 EP 0447673A1
Authority
EP
European Patent Office
Prior art keywords
bleaching
added
aqueous
containing solution
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.)
Granted
Application number
EP90125380A
Other languages
German (de)
English (en)
Other versions
EP0447673B1 (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
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 LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG und ZUM VERTRIEB VON ENZYMEN mbH filed Critical LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG und ZUM VERTRIEB VON ENZYMEN mbH
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
Expired - Lifetime legal-status Critical Current

Links

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 process for the enzymatic bleaching of cellulose.
  • Chlorine bleach is associated with major environmental problems.
  • the kappa number ie the lignin content
  • the pulp is thus brightened.
  • the object of the present invention is to provide a process for the enzymatic bleaching of cellulose which no longer has the disadvantages of the biological and chemical bleaching processes.
  • This object is achieved in that a) with the simultaneous addition of oxidizing and reducing agents and addition of salts and complexing agents to an aqueous cellulose-containing solution, a redox potential in the range between 200 and 500 mV is set, b) a bleaching reaction is started by adding lignolytic enzymes and c) the reaction is maintained with constant stirring for 15 minutes to 12 hours. This procedure prevents repolymerization of the lignin and makes depolymerization possible.
  • the redox potential is preferably between 250 and 450 mV.
  • it can be determined by means of a redox electrode and kept constant by means of a regulator and an actuator during the entire reaction time by adding oxidizing and reducing agents, salts and phenolic compounds.
  • Hydrogen peroxide, oxygen and ozone are preferably used as the oxidizing agent.
  • 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.
  • salts Mn (II) sulfate, Mn (III) acetate, Fe (II) sulfate, Ti (III) chloride, Ce (III) nitrate and Ce (IV) ammonium nitrate can be used. Salts with the elements zinc, antimony and lead are also suitable. Possibly. phenolic compounds can be added to the aqueous pulp-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 conventional 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 Pat. Nos. 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 initiated, 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)
  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
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 true EP0447673A1 (fr) 1991-09-25
EP0447673B1 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)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992020857A1 (fr) * 1991-05-17 1992-11-26 Call Hans Peter Procede a rendement ameliore pour la delignification de produits lignocellulosiques, ainsi que pour le blanchiment et le traitement d'eaux residuaires au moyen de laccases
EP0634520A1 (fr) * 1993-07-15 1995-01-18 SOLVAY (Société Anonyme) Procédé pour le blanchiment d'une pâte à papier
US5691193A (en) * 1993-02-25 1997-11-25 Pulp And Paper Research Institute Of Canada Non-chlorine bleaching of kraft pulp
WO1999009244A1 (fr) * 1997-08-14 1999-02-25 Takashi Watanabe Procede chimique de depolymerisation de la lignine
WO1999054545A1 (fr) * 1998-04-16 1999-10-28 Pulp And Paper Research Institute Of Canada Procede aux oxydases pour oxydation de pate a papier et de colorants
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

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI914780A0 (fi) * 1991-10-10 1991-10-10 Valtion Teknillinen Foerfarande foer entsymatisk behandling av lignocellulosahaltiga material, i synnerhet cellulosamassor.
EP0705327B1 (fr) * 1993-06-16 2000-04-19 CALL, Hans-Peter Dr. Systeme de blanchiment a plusieurs composants
EP0652321B1 (fr) * 1993-11-04 1998-01-21 Morton International, Inc. Blanchiment de pâte à papier chimique

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988003190A1 (fr) * 1986-10-24 1988-05-05 Call Hans Peter Procede de production de cellulose a partir de matieres premieres contenant de la lignine
EP0345715A1 (fr) * 1988-06-08 1989-12-13 International Paper Company Délignification enzymatique de matériau lignocellulosique

Family Cites Families (4)

* 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
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
US4687741A (en) * 1985-07-15 1987-08-18 Repligen Corporation Novel enzymes which catalyze the degradation and modification of lignin

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988003190A1 (fr) * 1986-10-24 1988-05-05 Call Hans Peter Procede de production de cellulose a partir de matieres premieres contenant de la lignine
EP0345715A1 (fr) * 1988-06-08 1989-12-13 International Paper Company Délignification enzymatique de matériau lignocellulosique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PAPIER, DAS. vol. 44, no. 10A, Oktober 1990, DARMSTADT DE Seiten V33 - V41; Call,H.P. et al.: "Einsatz von lignolytischen Enzymen bei der Zellstoff- und Papierherstellung (Biopulping, Biobleaching)." *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992020857A1 (fr) * 1991-05-17 1992-11-26 Call Hans Peter Procede a rendement ameliore pour la delignification de produits lignocellulosiques, ainsi que pour le blanchiment et le traitement d'eaux residuaires au moyen de laccases
US5691193A (en) * 1993-02-25 1997-11-25 Pulp And Paper Research Institute Of Canada Non-chlorine bleaching of kraft pulp
EP0634520A1 (fr) * 1993-07-15 1995-01-18 SOLVAY (Société Anonyme) Procédé pour le blanchiment d'une pâte à papier
BE1007272A3 (fr) * 1993-07-15 1995-05-09 Solvay Procede pour le blanchiment d'une pate a papier.
AU682363B2 (en) * 1993-07-15 1997-10-02 Solvay (Societe Anonyme) Process for bleaching a paper pulp
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
WO1999009244A1 (fr) * 1997-08-14 1999-02-25 Takashi Watanabe Procede chimique de depolymerisation de la lignine
US6214976B1 (en) 1997-08-14 2001-04-10 T. Watababe Chemical method for lignin depolymerization
WO1999054545A1 (fr) * 1998-04-16 1999-10-28 Pulp And Paper Research Institute Of Canada Procede aux oxydases pour oxydation de pate a papier et de colorants
US6660128B1 (en) 1998-04-16 2003-12-09 Pulp And Paper Research Institute Of Canada Oxidase process for pulp

Also Published As

Publication number Publication date
BR9106411A (pt) 1993-05-04
ES2072965T3 (es) 1995-08-01
ATE119593T1 (de) 1995-03-15
NO923601D0 (no) 1992-09-16
NO180388C (no) 1997-04-09
AU641494B2 (en) 1993-09-23
DE59008655D1 (de) 1995-04-13
EP0447673B1 (fr) 1995-03-08
HUT64119A (en) 1993-11-29
NO923601L (no) 1992-09-16
WO1991014823A1 (fr) 1991-10-03
NO180388B (no) 1996-12-30
DE4008893A1 (de) 1991-09-26
HU9202982D0 (en) 1993-01-28
DE4008893C2 (fr) 1992-09-03
FI924169A0 (fi) 1992-09-17
JPH05505857A (ja) 1993-08-26
CA2078345A1 (fr) 1991-09-21
FI924169A (fi) 1992-09-17
DK0447673T3 (da) 1995-07-24
AU7543291A (en) 1991-10-21

Similar Documents

Publication Publication Date Title
DE69012931T2 (de) Verfahren zum Bleichen und zur Delignifizierung von lignozellulosehaltigen Materialien.
DE3017712C2 (de) Verfahren zur alkalischen Extraktion von Fasermaterial enthaltenden Cellulosesuspensionen nach Behandlung mit Chlor oder Chlordioxid oder Mischungen davon
EP0327576B1 (fr) Procede de production de cellulose a partir de matieres premieres contenant de la lignine
EP0943032B1 (fr) Systeme a composants multiples pour modifier, decomposer ou blanchir la lignine ou des materiaux qui contiennent de la lignine, et son procede d'utilisation
EP2844796B1 (fr) Procédé de fabrication de pâte à papier à faible teneur en lignine à partir de matière lignocellulosique
EP0325890B1 (fr) Procédé de traitement d'une pâte cellulosique contenant de la lignine par l'ozone
DE69730233T2 (de) Verfahren zur zellstoffherstellung durch einstufiges kochen mit ameisensaüre und wäsche mit perameisensaüre
DE4137761A1 (de) Verfahren zur delignifizierung von lignocellulosehaltigem material, bleiche und behandlung von abwaessern mittels laccasen mit erweiteter wirksamkeit
EP0447673B1 (fr) Procédé pour le blanchiment enzymatique de pâtes
DE3225271A1 (de) Verfahren zum delignifizierenden bleichen von cellulosehalbstoff
EP0087553B1 (fr) Procédé de fabrication de pâtes cellulosiques semi-blanchies
DE1594861C3 (fr)
DE4129739A1 (de) Chlorfreies bleichen von papierpulpe
EP0882814B1 (fr) Système et procédé pour le fractionnement électrochimique des composés
DE3877403T2 (de) Verfahren zum bleichen von zellstoffen.
DE69100049T2 (de) Verminderung der halogenierten organischen verbindungen in den bleichereiabwaessern.
CA1122358A (fr) Methode de blanchiment absolu de la pate a papier
DE69026105T2 (de) Hochleistendes verfahren zum bleichen von zellstoff mit chlordioxyd
DE3343403A1 (de) Verfahren zum delignifizierenden bleichen eines wasserhaltigen cellulosehalbstoffes
DE69204457T2 (de) Verfahren zum bleichen und zur delignifizierung von chemischen papierzellstoffen.
DE4008894C2 (fr)
EP0512978A1 (fr) Procédé pour blanchir des matériaux contenant xylane et lignocellulose
DE4400954B4 (de) Verfahren zur Helligkeitssteigerung bei der Bleiche von Holzstoffen mit Wasserstoffperoxid
DE1203592B (de) Verfahren zum Bleichen von cellulosehaltigen Faserstoffen
DE512927C (de) Verfahren zum Aufschluss von Pflanzenfaserstoffen mit Chlorsaeure

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19901222

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17Q First examination report despatched

Effective date: 19930903

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG UND ZUM VERT

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 119593

Country of ref document: AT

Date of ref document: 19950315

Kind code of ref document: T

REF Corresponds to:

Ref document number: 59008655

Country of ref document: DE

Date of ref document: 19950413

ITF It: translation for a ep patent filed

Owner name: BARZANO' E ZANARDO ROMA S.P.A.

ET Fr: translation filed
REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950623

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2072965

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3016411

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19961201

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 19961224

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19971219

Year of fee payment: 8

Ref country code: DE

Payment date: 19971219

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971222

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19971222

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19971223

Year of fee payment: 8

Ref country code: CH

Payment date: 19971223

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19971229

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19971230

Year of fee payment: 8

Ref country code: DK

Payment date: 19971230

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971231

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19971231

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19980115

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981222

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981222

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981223

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981231

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981231

BERE Be: lapsed

Owner name: LIGNOZYM G.- ZUR HERSTELLUNG UND ZUM VERTRIEB VON

Effective date: 19981231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990701

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19981222

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990831

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19990701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991223

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20000114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051222