EP0327576A1 - Procede de production de cellulose a partir de matieres premieres contenant de la lignine. - Google Patents

Procede de production de cellulose a partir de matieres premieres contenant de la lignine.

Info

Publication number
EP0327576A1
EP0327576A1 EP87907315A EP87907315A EP0327576A1 EP 0327576 A1 EP0327576 A1 EP 0327576A1 EP 87907315 A EP87907315 A EP 87907315A EP 87907315 A EP87907315 A EP 87907315A EP 0327576 A1 EP0327576 A1 EP 0327576A1
Authority
EP
European Patent Office
Prior art keywords
lignin
enzymes
reaction
phenolic compounds
reducing agents
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
EP87907315A
Other languages
German (de)
English (en)
Other versions
EP0327576B1 (fr
Inventor
Hans-Peter 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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to AT87907315T priority Critical patent/ATE86318T1/de
Publication of EP0327576A1 publication Critical patent/EP0327576A1/fr
Application granted granted Critical
Publication of EP0327576B1 publication Critical patent/EP0327576B1/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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/228—Automation of the pulping processes
    • 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

Definitions

  • the invention relates to a method and a plant for the removal and / or conversion of lignin from lignooellulose-containing material.
  • the lingocellulose-containing material such as wood or annual plants, must be freed from the lignin, since this considerably improves the mechanical and physicochemical properties of the paper made from the cellulose.
  • Conventional processes work with high pressures and temperatures using environmentally harmful chemicals.
  • German Patent 3110117 discloses a process for the production of cellulose from wood or other plant fiber materials, in which the lignocellulose is produced using
  • the object of the present invention is to provide a method and a plant for removing and / or converting lignin from lignocellulose-containing material, in which the disadvantages of the use of microorganisms, enzymes and chemicals shown above are avoided.
  • This object is achieved in that a redox potential in the range of 200-500 mV is set by adding one or more oxidizing and / or reducing agents and / or salts and / or phenolic compounds to an acidic aqueous solution of the lignin-containing raw materials, then by adding enzymes, microorganisms, animal or plant cells started a lignin-degrading reaction with simultaneous bleaching, the reaction in a value oscillating around a constant redox potential value, constant temperature, constant pH value and with constant stirring for several hours.
  • the redox potential is preferably 250 to 350 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 / or reducing agents and / or salts and / or phenolic compounds and / or organic acids.
  • Hydrogen peroxide, oxygen and ozone are preferably used as the oxidizing agent.
  • Ascorbic acid, dithionite and sodium bisulfite are suitable as reducing agents.
  • MnSO 4 and / or FeCl 2 is preferably suitable as the salt.
  • Veratryl alcohol can be used as the phenolic compound. Lactic acid, for example, is suitable as the organic acid.
  • Lignolytic enzymes are preferably used as enzymes in the method according to the invention. These preferably include phenol oxidases, lallases and peroxidases.
  • the effectiveness of the method according to the invention can be increased by adding pectinases and / or hemicellulases.
  • those enzymes can be used which are obtained from the white rot fungus Phanerochaete chrysosporium. If necessary, Phanerochaete chrysosporium itself can also be added for the degradation process.
  • the pH in the process according to the invention is between 2 and 5. A pH of 3 is particularly preferred.
  • the temperature is 20 to 60 ° C.
  • the reaction is preferably carried out at 40 ° C. If the stated conditions of the process according to the invention are observed, a redox potential of 250-350 mV can be set! As a result, the lignin content of wheat straw (approx. 18% lignin content) can be reduced to almost 0%. Spruce wood (about 28-30% lignin content) can be broken down to similar end values. Surprisingly, these results can be achieved in 2 to 6 hours, in many cases even within 2 hours. This does not include the physical and / or chemical pretreatment that is particularly necessary when using wood or annual plants.
  • the redox potential is set by the ratio of the various substances added in the reaction vessel.
  • Addition of the oxidizing and reducing agents, the salts and the phenolic compounds can maintain a certain redox potential throughout the course of the reaction.
  • the aim of operating the redox system set in this way is to prevent repolymerization of the lignin.
  • the process also has a significant bleaching effect during the degradation and / or conversion reaction, which allows it to be done with significantly less pollution Bleach to work.
  • the method according to the invention is therefore also suitable as a bleaching or post-bending method for various processes.
  • the process can therefore also be used for the biological bleaching and biological wastewater treatment of pulp industry wastewater and other wastewater.
  • the method can be used wherever decolorization and detoxification of waste water is to be achieved.
  • Another advantage of the process according to the invention is the possibility of continuous process control.
  • the process can be carried out particularly economically if the used enzymes are reprocessed and returned to the reaction process. This goal can be achieved with the help of affinity chromatography.
  • the enzyme is passed over a separation column, purified there and returned to the reaction process.
  • the enzyme purification is carried out in the separation column by means of affinity chromatography.
  • new specific types of ligands have been developed, which are used together with the corresponding enzyme technology know-how.
  • ligands are described in patent application PCT / EP 87/00214.
  • phenolic compounds can be used here.
  • Protein-specific ligands are also suitable. Tannin is an example.
  • the method also relates to a plant for removing and / or converting lignin or its
  • Degradation products made from lignocellulose-containing material This consists of a reactor, a device for adding microorganisms or enzymes, a device for adding oxidizing agents, reducing agents, salts or phenolic compounds, a drain for the converted raw material, used oxidizing agents, reducing agents, Salts, phenolic compounds, enzymes and microorganisms, a device for the separation of dissolved and undissolved substances, a column for affinity chromatography, in which enzymes are reprocessed for the lignin degradation reaction and a reflux for the return of the reprocessed enzymes to the reactor. Filters or thickeners, for example, can be used as the device for separating dissolved and undissolved substances.
  • Microorganisms or enzymes are added to the reactor via the inflow 7.
  • the microorganisms or enzymes can optionally also be immobilized in the reactor.
  • Conventional fillers and carriers can be used for the immobilization.
  • Oxidizing agents, reducing agents, salts or phenolic compounds can be metered in via the inflow 4.
  • the dosage can be controlled depending on the respective redox potential.
  • a redox electrode must be attached to the reactor (not shown in the picture), by means of which the redox potential is continuously determined. By connecting to an appropriate control system, the redox potential can then be kept constant during the entire course of the reaction.
  • the raw materials are also added via the feed line 7.
  • Lignin and waste water containing lignin can also be treated in the plant according to the invention.
  • the lignin is broken down in the reactor with the aid of lignolytic enzymes or microorganisms. Enzymes which come from the fungus Phanerochaete chrysosporium are particularly suitable. Microorganisms are particularly suitable as cell-free and hemicellulase-free mutants. In particular, mutants of Phenerochaeta Chrysosporium can be used.
  • the converted raw material flows out of the reactor via the drain 8 together with the used chemicals, microorganisms or enzymes.
  • the mixture of substances is passed, for example, through a filter 3, where .solved and undissolved substances are separated from one another.
  • the enzyme-containing solution is passed through a chromatography column 2. This column works on the principle of affinity chromatography. Here the enzymes are reprocessed and then fed back to the reaction process via line 5.
  • the substances separated from the enzymes are discharged via line 6.
  • Special enzyme-specific ligands are used for affinity chromatography, especially phenolic compounds! Protein-specific ligands, in particular tannin, can also be used.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Paper (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
  • Audible-Bandwidth Dynamoelectric Transducers Other Than Pickups (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Un procédé et un appareil servent à transformer et/ou à extraire de la lignine ou ses produits de décomposition à partir de matériaux contenant de la lignine-cellulose. A cet effet, on maintient un potentiel redox compris ente 200 et 500 mV en ajoutant des agents oxydants et/ou réducteurs et/ou des sels et/ou des composés phénoliques à une solution acide aqueuse des matières premières contenant de la lignine. On fait démarrer la réaction de décomposition de la lignine en même temps que le blanchiment en ajoutant des enzymes, des micro-organismes, des cellules animales ou végétales. On maintient la reßction pendant plusieurs heures à un potentiel redox oscillant autour d'une valeur constante, à une température constante et sous agitation constante.
EP87907315A 1986-10-24 1987-10-24 Procede de production de cellulose a partir de matieres premieres contenant de la lignine Expired - Lifetime EP0327576B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87907315T ATE86318T1 (de) 1986-10-24 1987-10-24 Verfahren zur herstellung von zellstoff aus ligninhaltigen rohstoffen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3636208 1986-10-24
DE19863636208 DE3636208A1 (de) 1986-10-24 1986-10-24 Verfahren zur delignifizierung und bleichung von lignicellulosehaltigem bzw. ligninhaltigem material bzw. lignin durch enzymatische behandlung

Publications (2)

Publication Number Publication Date
EP0327576A1 true EP0327576A1 (fr) 1989-08-16
EP0327576B1 EP0327576B1 (fr) 1993-03-03

Family

ID=6312392

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87907315A Expired - Lifetime EP0327576B1 (fr) 1986-10-24 1987-10-24 Procede de production de cellulose a partir de matieres premieres contenant de la lignine

Country Status (11)

Country Link
EP (1) EP0327576B1 (fr)
JP (1) JPH0718108B2 (fr)
AT (1) ATE86318T1 (fr)
AU (1) AU605215B2 (fr)
BR (1) BR8707844A (fr)
DE (2) DE3636208A1 (fr)
DK (1) DK170810B1 (fr)
FI (1) FI95289C (fr)
HU (2) HU202938B (fr)
NO (1) NO175104C (fr)
WO (1) WO1988003190A1 (fr)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA894239B (en) * 1988-06-08 1990-03-28 Int Paper Co Enzymatic delignification of lignocellulosic material
FI88316C (fi) * 1989-07-10 1993-04-26 Enso Gutzeit Oy Foerfarande foer blekning av cellulosamassa
FI904456A0 (fi) * 1989-09-12 1990-09-10 Sandoz Ag Foerfarande foer blekning av cellulosa.
NZ235983A (en) * 1989-11-08 1993-01-27 Novo Nordisk As Process for hydrolysis of resins in lignocellulosic pulp using enzymes simultaneously with peroxy bleaching; ctmp fluff-pulp and absorbent articles produced therefrom
FI895501A (fi) * 1989-11-17 1991-05-18 Enso Gutzeit Oy Foerfarande foer tillverkning av massa.
FI92414B (fi) * 1989-11-27 1994-07-29 Enso Gutzeit Oy Menetelmä massan valmistamiseksi
FI85389C (fi) * 1989-12-12 1992-04-10 Enso Gutzeit Oy Foerfarande foer tillverkning av massa.
FI900544A (fi) * 1990-02-02 1991-08-03 Enso Gutzeit Oy Tutkimuskeskus Foerfarande foer tillverkning av massa.
DE4008894A1 (de) * 1990-03-20 1991-09-26 Call Hans Peter Verfahren zur altpapieraufbereitung mit enzymatischer druckfarbenentfernung
DE4008893A1 (de) * 1990-03-20 1991-09-26 Call Hans Peter Verfahren zum enzymatischen bleichen von zellstoffen
DK249990D0 (da) * 1990-10-17 1990-10-17 Novo Nordisk As Fremgangsmaade til enzymatisk pulpbehandling
EP0486125A1 (fr) * 1990-11-13 1992-05-20 JAPAN PULP & PAPER RESEARCH INSTITUTE, INC. Composition lignocellulolytique, procédé pour sa fabrication et son application
FI905954A (fi) * 1990-12-03 1992-06-04 Enso Gutzeit Oy Foerfarande foer blekning av cellulosamassa.
JPH04240287A (ja) * 1991-01-21 1992-08-27 Kobe Steel Ltd パルプの漂白方法
FI93230C (fi) * 1991-03-22 1995-03-10 Genencor Int Europ Menetelmä mekaanisen massan pihkavaikeuksien vähentämiseksi
AT400153B (de) * 1991-05-02 1995-10-25 Voest Alpine Ind Anlagen Verfahren zum bleichen von xylan- und lignocellulosehältigen materialien
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
JP3262646B2 (ja) * 1993-07-09 2002-03-04 日本製紙株式会社 パルプの漂白方法
SE505980C2 (sv) * 1993-12-23 1997-10-27 Bim Kemi Ab Sätt att förhindra peroxidnedbrytande enzymer vid blekning med väteperoxid
PT879318E (pt) * 1996-02-08 2002-07-31 Novozymes As Processo para aumentar a carga negativa de um material lignocelulosico e um material lignocelulosico modificado com uma densidade de carga aumentada
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
US6942754B2 (en) 1999-03-23 2005-09-13 Oji Paper Co., Ltd. Process for producing xylooligosaccharide from lignocellulose pulp
US6824646B2 (en) 1999-03-23 2004-11-30 Oji Paper Co., Ltd. Process for oxygen bleaching and enzyme treating lignocellulosic pulp with liquid treatment and recovery

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1262117B (de) * 1964-05-05 1968-02-29 Aschaffenburger Zellstoffwerke Verfahren zur Kontrolle der Bleiche mit Chlordioxyd
FR1524581A (fr) * 1966-05-25 1968-05-10 Solvay Procédé de réglage de la blancheur d'une pâte cellulosique traitée par le peroxyde d'hydrogène ou un produit similaire
CA1232850A (fr) * 1985-01-17 1988-02-16 Albert D. Friesen Purification de la superoxyde-dismutase

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8803190A1 *

Also Published As

Publication number Publication date
BR8707844A (pt) 1989-10-03
HU202938B (en) 1991-04-29
FI95289B (fi) 1995-09-29
DK170810B1 (da) 1996-01-22
DK344888D0 (da) 1988-06-23
DE3784515D1 (de) 1993-04-08
DE3636208A1 (de) 1988-05-05
WO1988003190A1 (fr) 1988-05-05
ATE86318T1 (de) 1993-03-15
FI95289C (fi) 1996-01-10
JPH02500990A (ja) 1990-04-05
HUT50894A (en) 1990-03-28
FI891909A (fi) 1989-04-21
AU605215B2 (en) 1991-01-10
DK344888A (da) 1988-06-23
NO175104C (no) 1994-08-31
JPH0718108B2 (ja) 1995-03-01
AU8230387A (en) 1988-05-25
EP0327576B1 (fr) 1993-03-03
NO175104B (no) 1994-05-24
FI891909A0 (fi) 1989-04-21
NO882808L (no) 1988-06-24
NO882808D0 (no) 1988-06-24

Similar Documents

Publication Publication Date Title
EP0327576B1 (fr) Procede de production de cellulose a partir de matieres premieres contenant de la lignine
WO1992020857A1 (fr) 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
DE69026731T2 (de) Ein Komplex von Fasermaterial und Pilzen und Verfahren zu seiner Herstellung
WO1998026127A1 (fr) Systeme a composants multiples pour modifier, decomposer ou blanchir la lignine, des materiaux qui contiennent de la lignine ou des substances similaires, et son procede d'utilisation
DE10158120A1 (de) Verfahren zum Abtrennen von Xylose aus xylanreichen Lignocellulosen, insbesondere Holz
EP0441113B1 (fr) Procédé exempt de chlore pour le blanchiment de pâte cellulosique
US5203964A (en) Process for producing cellulose from lignin containing raw materials using an enzyme or microorganism while monitoring and maintaining the redox potential
DE4129739A1 (de) Chlorfreies bleichen von papierpulpe
EP0447673B1 (fr) Procédé pour le blanchiment enzymatique de pâtes
DE69015294T2 (de) Bleichen von Holzstoff mit Enzymen.
EP0325731A1 (fr) Procédé de fabrication de pâte cellulosique Kraft semi-blanchie
WO2003025280A1 (fr) Procede pour separer des hemicelluloses d'une biomasse renfermant des hemicelluloses
DE4008894C2 (fr)
EP3911609B1 (fr) Procédé de purification, à l'aide d'enzymes, d'eau de processus circulant dans une usine de traitement des déchets de papier
DE69729215T2 (de) Sauerstoffbehandlung von filtraten aus einer bleichanlage
DE69212529T2 (de) Behandlung von alkalisch behandeltem Papierzellstoff
US20060177921A1 (en) Method for removing unsaturated uronic acid in chemical pulp for papermaking
AT394865B (de) Verfahren zur herstellung einer xylanase-reichen und cellulase-armen enzymloesung
EP0512978A1 (fr) Procédé pour blanchir des matériaux contenant xylane et lignocellulose
DE3822628A1 (de) Verfahren zur behandlung von lignin zur gewinnung von aldehyden und/oder phenolsaeuren
WO2002029155A1 (fr) Procede de production d'holocellulose par delignification de biomasse contenant de la lignocellulose
Ramaswamy Biotechnology application in waste utilization and pollution abatement
DE3247594A1 (de) Verfahren zum bleichen von ligninhaltigem cellulosehalbstoff
WO1998005818A1 (fr) Systeme a plusieurs composants pour modifier, decomposer ou blanchir de la lignine, des materiaux contenant de la lignine ou des substances analogues et procede permettant de l'utiliser
EP0503304A1 (fr) Procédé pour la délignification de matière première contenant de la cellulose

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: 19890424

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19901228

ITTA It: last paid annual fee
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 FR GB IT LI LU NL SE

REF Corresponds to:

Ref document number: 86318

Country of ref document: AT

Date of ref document: 19930315

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3784515

Country of ref document: DE

Date of ref document: 19930408

ITF It: translation for a ep patent filed

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

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

Effective date: 19930517

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
EAL Se: european patent in force in sweden

Ref document number: 87907315.3

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

Ref country code: AT

Payment date: 19971028

Year of fee payment: 11

Ref country code: DE

Payment date: 19971028

Year of fee payment: 11

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

Ref country code: NL

Payment date: 19971030

Year of fee payment: 11

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

Ref country code: CH

Payment date: 19971121

Year of fee payment: 11

Ref country code: GB

Payment date: 19971121

Year of fee payment: 11

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

Ref country code: BE

Payment date: 19971127

Year of fee payment: 11

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

Ref country code: LU

Payment date: 19971128

Year of fee payment: 11

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: 19981024

Ref country code: AT

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

Effective date: 19981024

Ref country code: LU

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

Effective date: 19981024

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: 19981031

Ref country code: CH

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

Effective date: 19981031

Ref country code: BE

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

Effective date: 19981031

BERE Be: lapsed

Owner name: CALL HANS-PETER

Effective date: 19981031

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

Ref country code: FR

Payment date: 19990430

Year of fee payment: 12

Ref country code: SE

Payment date: 19990430

Year of fee payment: 12

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: 19990501

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 19981024

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

Effective date: 19990501

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: 19990803

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

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19991030

EUG Se: european patent has lapsed

Ref document number: 87907315.3

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: 20000630

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: 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: 20051024