EP0327576B1 - Process for producing cellulose from lignin-containing raw materials - Google Patents

Process for producing cellulose from lignin-containing raw materials Download PDF

Info

Publication number
EP0327576B1
EP0327576B1 EP87907315A EP87907315A EP0327576B1 EP 0327576 B1 EP0327576 B1 EP 0327576B1 EP 87907315 A EP87907315 A EP 87907315A EP 87907315 A EP87907315 A EP 87907315A EP 0327576 B1 EP0327576 B1 EP 0327576B1
Authority
EP
European Patent Office
Prior art keywords
lignin
process according
reaction
redox potential
enzyme
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
EP87907315A
Other languages
German (de)
French (fr)
Other versions
EP0327576A1 (en
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.)
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/en
Publication of EP0327576A1 publication Critical patent/EP0327576A1/en
Application granted granted Critical
Publication of EP0327576B1 publication Critical patent/EP0327576B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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 for removing and / or converting lignin from lignocellulose-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 produced from the cellulose.
  • Conventional processes work with high pressures and temperatures using environmentally harmful chemicals.
  • P.J. Harvey et al examined the role of radical cations in the breakdown of lignin. They have observed that veratryl alcohol can act as a mediator in the in-vivo process for lignin degradation using Phanerochaete chrysosporium (Abstract Bulletin of the Institute of Paper Chemistry, Volume 57, No. 7, January 1987, Appieton, Wisconsin, USA) P.J. Harvey et al: "Lignin-degrading enzymes and the role of radical cations in lignin biodegradation", see page 958, summary 8575, & STFI / SPCI Int. Conf. Biotechnol. Pulp & Paper Ind.
  • Phanerochaete chrysosporium produces a peroxidase, which causes the oxidation of manganese (II) to manganese (III).
  • the manganese (III) in turn causes the oxidation of the lignin molecules.
  • Mn peroxidase production plays a crucial role in the degradation of lignin.
  • “Paszczgnski, A. et al .:” Composition of Ligninase-l and Peroxidase-M2 from the White-Red Fungus Phanerochaete chrysosporium. Arch. Biochem. Biophys. Vol. 244. No. 2 "that the addition of reducing agents inhibits the Mn-dependent peroxidase of Phanerochaete chrysosporium. Dithionite, on the other hand, acts as an activator.
  • veratryl alcohol only serves to promote the formation of lignin-degrading enzymes.
  • the present invention has now set itself the task of a method for removing and / or converting lignin or its degradation products from lignocellulose-containing material with the aid of lignolytic enzymes obtained, in which the disadvantages of the use of microorganisms, enzymes and chemicals shown above are avoided, to provide.
  • This object is achieved in that a) by adding oxidizing agents, reducing agents, salts and phenolic compounds to an aqueous solution of the lignin-containing raw materials, a redox potential in the range from 200 to 500 mV is set, b) subsequently adding a lignin-degrading reaction by adding the lignolytic enzymes simultaneous bleaching started, c) the reaction at a value between 200 and 500 mV, constant temperature between 20 and 60 ° C, constant pH between 2 and 5 and maintained with constant stirring for 2 to 6 hours d) the redox potential is continuously determined by means of a redox electrode and by means of a regulator and actuator during the entire reaction by adding oxidizing agents. Reducing agents, salts, phenolic compounds and organic acids are kept between 200 and 500 mV and e) after the end of the reaction, the enzyme is passed over a separation column, purified there and returned to the reaction process.
  • the redox potential is preferably 250 to 350 mV. Hydrogen peroxide, oxygen and ozone are preferably used as the oxidizing agent. Ascorbic acid, dithionite and sodium bisulfite are suitable as reducing agents. MnSO4 and / or FeCl2 is preferably suitable as the salt. Veratryl alcohol can be used as the phenolic compound. The organic acid comes e.g. Lactic acid into consideration.
  • Lignolytic enzymes are preferably used as enzymes in the method according to the invention. These preferably include phenol oxidases, laccases and peroxidases.
  • the effectiveness of the method according to the invention can be increased by adding pectinases and / or hemicellulases.
  • 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.
  • a redox potential of 250-350 mV can be set.
  • 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.
  • 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. By measuring and controlling the addition of the oxidizing and reducing agents, the salts, the phenolic compounds and organic acids, a certain redox potential can be maintained throughout the course of the reaction.
  • the aim of the operation of the redox system set in this way is to intercept the radicals arising in the oxidation reaction and thus to prevent the 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 process according to the invention is therefore also suitable as a bleaching or post-bleaching process 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.
  • affinity chromatography For this purpose, new specific types of ligands have been developed, which are used together with the corresponding enzyme technology know-how.
  • phenolic compounds can be used here.
  • Protein-specific ligands are also suitable. Tannin is an example.
  • 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.
  • chemically and / or physically pretreated straw and wood come into consideration.
  • 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.
  • Particularly suitable enzymes are those which have been obtained from the fungus Phanerochaete chrysosporium. Cellulase- and hemicellulase-free mutants are particularly suitable as microorganisms.
  • mutants of Phanerochaete 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 dissolved 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, in particular phenolic compounds are used for affinity chromatography. Protein-specific ligands, in particular tannin, can also be used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Paper (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Processing Of Solid Wastes (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)

Abstract

A process and apparatus for transforming and/or extracting lignin or its decomposition products from lignin-cellulosic materials. For this purpose, a redox potential in the 200-500 mV range is set by adding oxidizing and/or reducing agents and/or salts and/or phenolic compounds to an acid aqueous solution of the lignin-containing raw materials. The lignin-decomposing reaction is initiated with bleaching by adding enzymes, micro-organisms, animal or vegetable cells. The reaction is maintained for several hours at a redox potential value oscillating around a constant value, at a constant temperature and with constant agitation.

Description

Die Erfindung betrifft ein Verfahren zur Entfernung und/oder Umwandlung von Lignin aus lignocellulosehaltigem Material.The invention relates to a method for removing and / or converting lignin from lignocellulose-containing material.

Zur Herstellung von Zellstoff oder zellstoffähnlichem Material muß das lingozellulosehaltige Material, wie Holz oder Einjahrespflanzen, vom Lignin befreit werden, da sich dadurch die mechanischen und physikalisch-chemischen Eigenschaften des aus dem Zellstoff hergestellten Papiers erheblich verbessern. Herkömmliche Verfahren arbeiten mit hohen Drücken und Temperaturen unter Einsatz von umweltbelastenden Chemikalien.For the production of cellulose or cellulose-like 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 produced from the cellulose. Conventional processes work with high pressures and temperatures using environmentally harmful chemicals.

Die bisher bekannten biologischen Verfahren zur Zellstoffherstellung arbeiten mit Mikroorganismen, insbesondere mit Pilzen. So ist aus der DE-C- 3110117 ein Verfahren zur Gewinnung von Zellulose aus Holz oder anderen Pflanzenfasernmaterialien bekannt, bei dem die Lignozellulose mit Hilfe von Weißfäulepilzen angebaut wird. Die mit Mikroorganismen arbeitenden Verfahren haben jedoch erhebliche Nachteile. So ist es bislang nicht möglich, ohne gleichzeitiges Wachstum der jeweiligen Mikroorganismen einen Abbau und ein Loslösen des Lignins von seinen Begleitpolymeren (Zellulose) zu erreichen. Durch das gleichzeitige Wachstum des Pilzes treten sehr lange Abbauzeiten auf, die bis zu mehreren Wochen dauern können.The biological processes known to date for the production of cellulose work with microorganisms, in particular with fungi. DE-C-3110117 discloses a process for the production of cellulose from wood or other plant fiber materials, in which the lignocellulose is grown with the help of white rot fungi. However, the processes using microorganisms have considerable disadvantages. So far, it has not been possible to break down and detach the lignin from its companion polymers (cellulose) without simultaneous growth of the respective microorganisms. Through simultaneous growth of the fungus occur very long breakdown times, which can take up to several weeks.

In den letzten Jahren sind wegen der dargestellten Schwierigkeiten des Einsatzes von Mikroorganismen verstärkt die Verwendungsmöglichkeiten für isolierte Enzymsysteme untersucht worden. Insbesondere wurden die Enzyme des Weißfäulepilzes Phanerochaete chrysosporium untersucht und in vielen Einzelheiten aufgeklärt. So ist aus "Biotechnology in the Pulp and Paper Industry, 3. International Conference, Stockholm 1986" bekannt, daß beim Abbau von Lignin ohne geeignete Enzymsysteme das Gleichgewicht der Reaktion auf der Polymerisationsseite liegt.In recent years, the potential uses for isolated enzyme systems have been increasingly investigated because of the difficulties presented with the use of microorganisms. In particular, the enzymes of the white rot fungus Phanerochaete chrysosporium were examined and elucidated in many details. It is known from "Biotechnology in the Pulp and Paper Industry, 3rd International Conference, Stockholm 1986" that when lignin is broken down without suitable enzyme systems, the equilibrium of the reaction lies on the polymerization side.

Ferner haben P.J. Harvey et al die Rolle von Radikalkationen beim Abbau von Lignin untersucht. Hierbei haben sie beobachtet, daß Veratrylalkohol als Mediator beim In-Vivo-Verfahren zum Ligninabbau mittels Phanerochaete chrysosporium wirken kann (Abstract Bulletin of the Institute of Paper Chemistry, Band 57, Nr. 7, January 1987, Appieton, Wisconsin, USA) P.J. Harvey et al: "Lignin-degrading enzymes and the role of radical cations in lignin biodegradation", siehe Seite 958, Zusammenfassung 8575, & STFI/SPCI Int. Conf. Biotechnol. Pulp & Paper Ind. (Stockholm) 3rd: 11-12 (June 16-19, 1986)). Ebenso ist bekannt, daß Fettsäuren Einfluß auf Phanerochaete chrysosporium haben. So wurde die ligninaseproduktion mittels Phanerochaete chrysosporium beim Zusatz von Tween 80 beobachtet (Abstract Bulletin of the Institute of Paper Chemistry, Band 57, Nr. 7, January 1987, (Appleton, Wisconsin, USA) M. Asther et al.: "Production of ligninolytic enzymes of Phanerochaete chrysosporium INA-12 in submerged agitated cultures", siehe Seiten 956-957, Zusammenfassung 8558, & STFI/SPCI Int. Conf. Biotechnol. Pulp & Paper Ind. (Stockholm), 3rd: 152-153 (June 16-19, 1986)).P.J. Harvey et al examined the role of radical cations in the breakdown of lignin. They have observed that veratryl alcohol can act as a mediator in the in-vivo process for lignin degradation using Phanerochaete chrysosporium (Abstract Bulletin of the Institute of Paper Chemistry, Volume 57, No. 7, January 1987, Appieton, Wisconsin, USA) P.J. Harvey et al: "Lignin-degrading enzymes and the role of radical cations in lignin biodegradation", see page 958, summary 8575, & STFI / SPCI Int. Conf. Biotechnol. Pulp & Paper Ind. (Stockholm) 3rd: 11-12 (June 16-19, 1986)). It is also known that fatty acids have an influence on Phanerochaete chrysosporium. For example, ligninase production using Phanerochaete chrysosporium was observed when Tween 80 was added (Abstract Bulletin of the Institute of Paper Chemistry, Volume 57, No. 7, January 1987, (Appleton, Wisconsin, USA) M. Asther et al .: "Production of ligninolytic enzymes of Phanerochaete chrysosporium INA-12 in submerged agitated cultures ", see pages 956-957, abstract 8558, & STFI / SPCI Int. Conf. Biotechnol. Pulp & Paper Ind. (Stockholm), 3rd: 152-153 (June 16 -19, 1986)).

Darüber hinaus hat man sich mit der Rolle von Mangan beim Ligninabbau befaßt (Abstract Bulletin of the Institute of Paper Chemistry, Band 57, Nr. 7, January 1987 (Appleton, Wisconsin, USA) V.-B. Huynh et al.: "Oxidation of lignin model compounds by a manganese-dependent enzyme from Phanerochaete chrysosporium as compared to chemically generated Mn(III)" siehe Seite 959, Zusammenfassung 8578, & STFI/SPCI Int. Conf. Biotechnol. Pulp & Paper Ind. (Stockholm), 3rd.: 42-45 (June 16-19, 1986). Hierbei wurde festgestellt, daß Phanerochaete chrysosporium eine Peroxidase produziert, welche die Oxidation von Mangan (II) zu Mangan (III) bewirkt. Das Mangan (III) bewirkt wiederum die Oxidation der Ligninmoleküle. D.h., die Mn-Peroxidaseproduktion spielt eine entscheidende Rolle bei dem Ligninabbau. Auf der anderen Seite wird in "Paszczgnski, A. et al.: "Composition of Ligninase-l and Peroxidase-M₂ from the White-Rot Fungus Phanerochaete chrysosporium. Arch. Biochem. Biophys. Vol. 244. Nr. 2" beschrieben, daß bei Zusatz von Reduktionsmitteln die Mn-abhängige Peroxidase von Phanerochaete chrysosporium gehemmt wird. Dithionit wirkt dagegen als Aktivator.In addition, the role of manganese in lignin degradation has been addressed (Abstract Bulletin of the Institute of Paper Chemistry, Volume 57, No. 7, January 1987 (Appleton, Wisconsin, USA) V.-B. Huynh et al .: " Oxidation of lignin model compounds by a manganese-dependent enzyme from Phanerochaete chrysosporium as compared to chemically generated Mn (III) "see page 959, Summary 8578, & STFI / SPCI Int. Conf. Biotechnol. Pulp & Paper Ind. (Stockholm), 3rd .: 42-45 (June 16-19, 1986). It was found that Phanerochaete chrysosporium produces a peroxidase, which causes the oxidation of manganese (II) to manganese (III). The manganese (III) in turn causes the oxidation of the lignin molecules. This means that Mn peroxidase production plays a crucial role in the degradation of lignin. On the other hand in "Paszczgnski, A. et al .:" Composition of Ligninase-l and Peroxidase-M₂ from the White-Red Fungus Phanerochaete chrysosporium. Arch. Biochem. Biophys. Vol. 244. No. 2 "that the addition of reducing agents inhibits the Mn-dependent peroxidase of Phanerochaete chrysosporium. Dithionite, on the other hand, acts as an activator.

Dokumente, die im Zusammenhang mit der 3. Internationalen Biotechnologischen Konferenz in Stockholm, 1986 veröffentlicht wurden (vgl. Recherchenbericht und Beschreibung dieser Anmeldung, Seite 2, Zeilen 4-14), insbesondere die Beitrage von M. Leisola u.a. "Production and characterization of ligninolytic enzymes of Phanerochaete Chrysosporium" und von M. Asther u.a. "Production of ligninolytic enzymes of Phanerochaete Chrysosporium INA-12 in submerged agitated cultures" zeigen weiterhin die Verwendung von Veratrylalkohol.Documents published in connection with the 3rd International Biotechnological Conference in Stockholm, 1986 (see search report and description of this application, page 2, lines 4-14), in particular the contributions by M. Leisola and others. "Production and characterization of ligninolytic enzymes of Phanerochaete Chrysosporium" and by M. Asther et al. "Production of ligninolytic enzymes of Phanerochaete Chrysosporium INA-12 in submerged agitated cultures" continue to show the use of veratryl alcohol.

Hier dient Veratrylalkohol jedoch nur dazu, die Bildung von ligninabbauenden Enzymen zu fördern.Here, however, veratryl alcohol only serves to promote the formation of lignin-degrading enzymes.

Die vorliegende Erfindung hat sich nunmehr die Aufgabe gestellt, ein Verfahren zur Entfernung und/oder Umwandlung von Lignin oder dessen Abbauprodukten aus lignocellulosehaltigem Material mit Hilfe von gewonnenen lignolytischen Enzymen, bei denen die oben aufgezeigten Nachteile des Einsatzes von Mikroorganismen, Enzymen und Chemikalien vermieden werden, zur Verfügung zu stellen.The present invention has now set itself the task of a method for removing and / or converting lignin or its degradation products from lignocellulose-containing material with the aid of lignolytic enzymes obtained, in which the disadvantages of the use of microorganisms, enzymes and chemicals shown above are avoided, to provide.

Diese Aufgabe wird dadurch gelöst, daß a) durch Zusatz von Oxidationsmitteln, Reduktionsmitteln, Salzen und phenolischen Verbindungen zu einer wässrigen Lösung der ligninhaltigen Rohstoffe ein Redoxpotential im Bereich von 200 bis 500 mV eingestellt, b) anschließend durch Zugabe der lignolytischen Enzyme eine ligninabbauende Reaktion mit gleichzeitiger Bleichung gestartet, c) die Reaktion bei dem Wert zwischen 200 und 500 mV, konstanter Temperatur zwischen 20 und 60 °C, konstantem pH-Wert zwischen 2 und 5 und unter ständigem Rühren über 2 bis 6 Stunden aufrechterhalten wird d) das Redoxpotential fortwährend mittels einer Redoxelektrode ermittelt und mittels eines Reglers und Stellgliedes während der gesamten Reaktion durch Zugabe von Oxidationsmitteln. Reduktionsmitteln, Salzen, phenolischen Verbindungen und organischen Säuren zwischen 200 und 500 mV gehalten wird und e) nach Abschluß der Reaktion das Enzym über eine Trennsäule geleitet, dort gereinigt und wieder in den Reaktionsprozeß zurückgeführt wird.This object is achieved in that a) by adding oxidizing agents, reducing agents, salts and phenolic compounds to an aqueous solution of the lignin-containing raw materials, a redox potential in the range from 200 to 500 mV is set, b) subsequently adding a lignin-degrading reaction by adding the lignolytic enzymes simultaneous bleaching started, c) the reaction at a value between 200 and 500 mV, constant temperature between 20 and 60 ° C, constant pH between 2 and 5 and maintained with constant stirring for 2 to 6 hours d) the redox potential is continuously determined by means of a redox electrode and by means of a regulator and actuator during the entire reaction by adding oxidizing agents. Reducing agents, salts, phenolic compounds and organic acids are kept between 200 and 500 mV and e) after the end of the reaction, the enzyme is passed over a separation column, purified there and returned to the reaction process.

Das Redoxpotential liegt vorzugsweise bei 250 bis 350 mV. Als Oxidationsmittel werden vorzugsweise Wasserstoffperoxid, Sauersoff und Ozon eingesetzt. Als Reduktionsmittel kommen Ascorbinsäure, Dithionit und Natrium-Bisulfit in Frage. Als Salz ist vorzugsweise MnSO₄ und/oder FeCl₂ geeignet. Als phenolische Verbindung kann Veratrylalkohol verwendet werden. Als organische Säure kommt z.B. Milchsäure in Betracht.The redox potential is preferably 250 to 350 mV. Hydrogen peroxide, oxygen and ozone are preferably used as the oxidizing agent. Ascorbic acid, dithionite and sodium bisulfite are suitable as reducing agents. MnSO₄ and / or FeCl₂ is preferably suitable as the salt. Veratryl alcohol can be used as the phenolic compound. The organic acid comes e.g. Lactic acid into consideration.

Als Enzyme werden bei dem erfindungsgemäßen Verfahren vorzugsweise lignolytische Enzyme eingesetzt. Vorzugsweise zählen hierzu Phenoloxidasen, Laccasen und Peroxidasen. Die Wirksamkeit des erfindungsgemäßen Verfahrens kann durch Zusatz von Pectinasen und/oder Hemicellulasen erhöht werden. Erfindungsgemäß können insbesondere solche Enzyme verwendet werden, die aus dem Weißfäulepilz Phanerochaete chrysosporium gewonnen werden. Gegebenenfalls kann auch Phanerochaete chrysosporium selbst für den Abbauprozeß zugesetzt werden.Lignolytic enzymes are preferably used as enzymes in the method according to the invention. These preferably include phenol oxidases, laccases and peroxidases. The effectiveness of the method according to the invention can be increased by adding pectinases and / or hemicellulases. According to the invention, it is possible in particular to use enzymes which are obtained from the white rot fungus Phanerochaete chrysosporium. If necessary, Phanerochaete chrysosporium itself can also be added for the degradation process.

Der pH-Wert liegt bei dem erfindungsgemäßen Verfahren zwischen 2 und 5. Besonders bevorzugt wird ein pH-Wert von 3. Die Temperatur beträgt 20 bis 60o C. Vorzugsweise wird die Reaktion bei 40o C durchgeführt.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.

Wenn die dargelegten Bedingungen des erfindungsgemäßen Verfahrens eingehalten werden, gelingt es, ein Redoxpotential von 250 - 350 mV einzustellen. Hierdurch läßt sich beispielsweise bei Weizenstroh (ca: 18 % Ligningehalt) der Ligningehalt auf nahezu 0 % abbauen. Fichtenholzschliff (etwa 28-30 % Ligningehalt) läßt sich auf ähnliche Endwerte abbauen. Diese Ergebnisse können überraschenderweise in 2 bis 6 Stunden, in vielen Fällen sogar innerhalb von 2 Stunden erreicht werden. Hierbei wird nicht die physikalische und/oder chemische Vorbehandlung eingerechnet, die insbesondere bei Einsatz von Holz oder Einjahrespflanzen notwendig ist.If the stated conditions of the method 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.

Das Redoxpotential wird durch das Verhältnis der verschiedenen zugesetzten Stoffe im Reaktionsgefäß eingestellt. Durch entsprechende Messung und Regelung der Zugabe der Oxidations und Redukionsmittel, der Salze, der phenolischen Verbindungen und organischen Säuren kann ein bestimmtes Redoxpotential während des gesamten Reaktionsverlaufs aufrechterhalten werden. Ziel des Betriebes des so eingestellten Redox-Systems ist das Abfangen der bei der Oxidationsreaktion anfallenden Radikale und so die Verhinderung der Repolymerisation des Lignins.The redox potential is set by the ratio of the various substances added in the reaction vessel. By measuring and controlling the addition of the oxidizing and reducing agents, the salts, the phenolic compounds and organic acids, a certain redox potential can be maintained throughout the course of the reaction. The aim of the operation of the redox system set in this way is to intercept the radicals arising in the oxidation reaction and thus to prevent the repolymerization of the lignin.

Mit diesem biologischen Abbauprinzip ist es erstmals gelungen, ein Ligninentferungsverfahren zu entwickeln, daß in sehr kurzer Zeit (2 bis 6 Stunden) bei physiologischen Temperaturen (40o C) ohne Druck und mit geringsten Chemikalienzugaben kostengünstig und vor allem umweltschonend arbeitet. Ein weiterer Vorteil ist die hohe Ausbeute an Zellstoff bzw. zellstoffähnlichem Material. Bei Einjahrespflanzen beträgt die Ausbeute etwa 80 % und bei Holz ca. 70 % bezogen auf die Trockenmasse nach der Vorbehandlung.With this biodegradation principle, it was possible for the first time to develop a lignin removal process that works in a very short time (2 to 6 hours) at physiological temperatures (40 o C) without pressure and with the smallest addition of chemicals and, above all, environmentally friendly. Another advantage is the high yield of cellulose or cellulose-like material. The yield for annual plants is about 80% and for wood about 70% based on the dry matter after pretreatment.

Das Verfahren hat während des Abbau- und/oder der Umwandlungsreaktion auch eine erhebliche Bleichwirkung, die es gestattet, mit wesentlich weniger umweltbelastenden Bleichmitteln zu arbeiten. Das erfindungsgemäße Verfahren ist daher auch als Bleich- oder Nachbleichverfahren für verschiedene Prozesse geeignet. Daher kann das Verfahren auch für die biologische Bleichung und biologische Abwasserbehandlung von Zellstoffindustrieabwässern und anderen Abwässern eingesetzt werden. Insbesondere kann das Verfahren überall dort verwendet werden, wo eine Entfärbung und Entgiftung von Abwässern erreicht werden soll.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 process according to the invention is therefore also suitable as a bleaching or post-bleaching process 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. In particular, the method can be used wherever decolorization and detoxification of waste water is to be achieved.

Ein weiterer Vorteil des erfindungsgemäßen Verfahrens ist die Möglichkeit der kontinuierlichen Verfahrensführung. Besonders wirtschaftlich kann das Verfahren durchgeführt werden, wenn die verbrauchten Enzyme wiederaufbereitet und in den Reaktionsprozeß zurückgeführt werden. Dieses Ziel laßt sich mit Hilfe der Affinitätschromatographie erreichen. Hierbei wird nach Abschluß der Reaktion das Enzym über eine Trennsäule geleitet, dort gereinigt und wieder in den Reaktionsprozeß zurückgeführt. Die Enzymreinigung wird in der Trennsäule mittels Affinitätschromatographie durchgeführt. Hierfür wurden neue spezifische Ligandentypen entwickelt, die zusammen mit dem entsprechenden enzymtechnologischen Know-how benutzt werden.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. After the reaction has ended, 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. For this purpose, new specific types of ligands have been developed, which are used together with the corresponding enzyme technology know-how.

Vorliegend können beispielsweise phenolische Verbindungen eingesetzt werden. Ebenso kommen proteinspezifische Liganden in Betracht. Als Beispiel sei Tannin genannt.For example, phenolic compounds can be used here. Protein-specific ligands are also suitable. Tannin is an example.

Im Folgenden wird unter Bezugnahme auf die Figur die Anlage zur Ausführung des erfindungsgemäßen Verfahrens näher erläutert. Über den Zufluß 7 werden Mikroorganismen oder Enzyme in den Reaktor gegeben. In dem Reaktor können die Mikroorganismen oder Enzyme ggf. auch immobilisiert werden. Für die Immobilisierung können übliche Füll- und Trägerstoff verwendet werden. Über den Zufluß 4 können Oxidations-, Redukionsmittel, Salze oder phenolische Verbindungen zudosiert werden. Die Dosierung kann in Abhängigkeit von dem jeweiligen Redoxpotential gesteuert werden. Hierzu ist am Reaktor eine Redoxelektrode anzubringen (im Bild nicht dargestellt), mittels derer fortwährend das Redoxpotential ermittelt wird. Durch Verbindung mit einer entsprechenden Regelanlage kann dann das Redoxpotential während des gesamten Reaktionsablaufs konstant gehalten werden. Über die Zuleitung 7 werden ferner die Rohstoffe zugegeben. Hierbei kann es sich um ligninhaltige Stoffe jeglicher Art handeln. Insbesondere kommen chemisch und/oder physikalisch vorbehandeltes Stroh und Holz in Betracht. Ebenso können aber auch ligninhaltige Ablaugen und Abwässer in der erfindungsgemäßen Anlage behandelt werden. In dem Reaktor wird das Lignin mit Hilfe von lignolytischen Enzymen oder von Mikroorganismen abgebaut. Als Enzyme kommen insbesondere solche in Betracht, die aus dem Pilz Phanerochaete chrysosporium gewonnen worden sind. Als Mikroorganismen sind insbesondere cellulase- und hemicellulasefreie Mutanten geeignet.The system for carrying out the method according to the invention is explained in more detail below with reference to the figure. 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. For this purpose, 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. This can be any kind of lignin-containing substances. In particular, chemically and / or physically pretreated straw and wood come into consideration. 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. Particularly suitable enzymes are those which have been obtained from the fungus Phanerochaete chrysosporium. Cellulase- and hemicellulase-free mutants are particularly suitable as microorganisms.

Insbesondere sind Mutanten von Phanerochaete chrysosporium einsetzbar. Nach Abschluß des Ligninabbaues fließt der umgesetzte Rohstoff über den Abfluß 8 zusammen mit den verbrauchten Chemikalien, Mikroorganismen bzw. Enzymen aus dem Reaktor ab. Das Stoffgemisch wird beispielsweise über einen Filter 3 geleitet, wo gelöste und ungelöste Stoffe voneinander getrennt werden. Die enzymhaltige Lösung wird über eine Chromatographiesäule 2 geleitet. Diese Säule arbeitet nach dem Prinzip der Affinitätschromatographie. Hier werden die Enzyme wiederaufbereitet und anschließend über die Leitung 5 dem Reaktionsprozeß wieder zugeführt. Die von den Enzymen abgetrennten Stoffe werden über die Leitung 6 abgeführt. Für die Affinitätschromatographie werden besondere enzymspezifische Liganden eingesetzt, insbesondere phenolische Verbindungen. Ebenso können proteinspezifische Liganden, insbesondere Tannin eingesetzt werden.In particular, mutants of Phanerochaete chrysosporium can be used. After completion of the lignin degradation, 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 dissolved 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, in particular phenolic compounds, are used for affinity chromatography. Protein-specific ligands, in particular tannin, can also be used.

Claims (11)

  1. A process for removing and/or converting lignin or the degradation products thereof from material containing lignocellulose with the help of obtained lignolytic enzymes
    characterized in that
    a) by adding oxidizing agents, reducing agents, salts and phenolic compounds to an aqueous solution of the raw materials containing lignin a redox potential is set in the range of 200 to 500 mV,
    b) then by adding the lignolytic enzymes a reaction degrading the lignin is initiated while simultaneously bleaching,
    c) the reaction is maintained at the value between 200 and 500 mV, constant temperature between 20 to 60°C, constant pH-value between 2 and 5 and while constantly stirring over 2 to 6 hours,
    d) the redox potential is determined continually by means of a redox electrode and is maintained by means of a control unit and controller during the entire reaction by adding oxidizing agents, reducing agents, salts, phenolic compounds and organic acids between 200 and 500 mV, and
    e) after terminating the reaction, the enzyme is led via a separation column, is purified there and again returned to the reaction process.
  2. The process according to claim 1,
    characterized in that the redox potential is adjusted in the range of 250 to 350 mV.
  3. The process according to claim 1 or 2,
    characterized in that H₂O₂, O₂ or ozone are used as oxidizing agents.
  4. The process according to any of claims 1 to 3,
    characterized in that ascorbinic acid, dithionite or sodium bisulphite are used as reducing agents.
  5. The process according to any of claims 1 to 4,
    characterized in that veratryl alcohol is used as phenolic compound.
  6. The process according to any of claims 1 to 5,
    characterized in that a pH-value of 3 is adjusted.
  7. The process according to any of claims 1 to 6,
    characterized in that a temperature of 40°C is adjusted.
  8. The process according to any of claims 1 to 7,
    characterized in that the enzyme purification is performed in the separation column by means of affinity chromatography.
  9. The process according to claim 8,
    characterized in that the affinity chromatography is performed with enzyme-specific ligands, particularly phenolic compounds.
  10. The process according to claim 9,
    characterized in that the affinity chromatography is performed with protein-specific ligands, particularly tannin.
  11. The process according to any of claims 1 to 10,
    characterized in that it is additionally bleached with common bleaching agents such as sodium hypochlorite, chlorine, ozone, O₂, chlorine dioxide.
EP87907315A 1986-10-24 1987-10-24 Process for producing cellulose from lignin-containing raw materials Expired - Lifetime EP0327576B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87907315T ATE86318T1 (en) 1986-10-24 1987-10-24 PROCESS FOR THE PRODUCTION OF PULP FROM RAW MATERIALS CONTAINING LIGNIN.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3636208 1986-10-24
DE19863636208 DE3636208A1 (en) 1986-10-24 1986-10-24 METHOD FOR DELIGNIFYING AND WHICH BLEACHING LIGNICELLULOSE-CONTAINING OR LIGNINAL MATERIAL OR LIGNIN BY ENZYMATIC TREATMENT

Publications (2)

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

Family

ID=6312392

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87907315A Expired - Lifetime EP0327576B1 (en) 1986-10-24 1987-10-24 Process for producing cellulose from lignin-containing raw materials

Country Status (11)

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

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 (en) * 1989-07-10 1993-04-26 Enso Gutzeit Oy Process for bleaching cellulose pulp
FI904456A0 (en) * 1989-09-12 1990-09-10 Sandoz Ag FOER FARING 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 (en) * 1989-11-17 1991-05-18 Enso Gutzeit Oy FOERFARANDE FOER TILLVERKNING AV MASSA.
FI92414B (en) * 1989-11-27 1994-07-29 Enso Gutzeit Oy Process for mass production
FI85389C (en) * 1989-12-12 1992-04-10 Enso Gutzeit Oy Process for mass production
FI900544A (en) * 1990-02-02 1991-08-03 Enso Gutzeit Oy Tutkimuskeskus FOERFARANDE FOER TILLVERKNING AV MASSA.
DE4008894A1 (en) * 1990-03-20 1991-09-26 Call Hans Peter METHOD FOR RECYCLING PAPER WITH ENZYMATIC PRINT INK REMOVAL
DE4008893A1 (en) * 1990-03-20 1991-09-26 Call Hans Peter METHOD FOR ENZYMATIC BLEACHING OF CELLULAS
DK249990D0 (en) * 1990-10-17 1990-10-17 Novo Nordisk As PROCEDURE FOR ENZYMATIC PULP TREATMENT
EP0486125A1 (en) * 1990-11-13 1992-05-20 JAPAN PULP & PAPER RESEARCH INSTITUTE, INC. Lignocellulolytic composition, process of producing the same and use of the same
FI905954A (en) * 1990-12-03 1992-06-04 Enso Gutzeit Oy FOERFARANDE FOER BLEKNING AV CELLULOSAMASSA.
JPH04240287A (en) * 1991-01-21 1992-08-27 Kobe Steel Ltd Bleaching of pulp
FI93230C (en) * 1991-03-22 1995-03-10 Genencor Int Europ Method for reducing resin difficulties in mechanical pulp
AT400153B (en) * 1991-05-02 1995-10-25 Voest Alpine Ind Anlagen METHOD FOR BLEACHING MATERIALS CONTAINING XYLAN AND LIGNOCELLULOSE
DE4137761A1 (en) * 1991-05-17 1992-11-19 Call Hans Peter METHOD FOR DELIGNIFYING LIGNOCELLULOSE-CONTAINING MATERIAL, BLEACHING AND TREATING WASTEWATER BY LACCASE WITH EXTENDED EFFECTIVENESS
FI914780A0 (en) * 1991-10-10 1991-10-10 Valtion Teknillinen FOERFARANDE FOER ENTSYMATISK BEHANDLING AV LIGNOCELLULOSAHALTIGA MATERIAL, I SYNNERHET CELLULOSAMASSOR.
CA2115881C (en) * 1993-02-25 2000-05-23 Michael G. Paice Non-chlorine bleaching of kraft pulp
JP3262646B2 (en) * 1993-07-09 2002-03-04 日本製紙株式会社 Pulp bleaching method
SE505980C2 (en) * 1993-12-23 1997-10-27 Bim Kemi Ab Ways to prevent peroxide-degrading enzymes by bleaching with hydrogen peroxide
PT879318E (en) * 1996-02-08 2002-07-31 Novozymes As A PROCESS FOR INCREASING THE NEGATIVE CHARGE OF A LIGNOCELLULOSIC MATERIAL AND A MODIFIED LIGNOCELLULOSIC MATERIAL WITH AN INCREASED LOAD DENSITY
DE19820947B4 (en) * 1997-05-12 2005-12-01 Call, Krimhild Enzymatic bleaching system with novel enzyme action enhancing compounds for altering, degrading or bleaching lignin, lignin containing materials, or altering or degrading coal, and methods using the bleaching system
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 (en) * 1964-05-05 1968-02-29 Aschaffenburger Zellstoffwerke Procedure for controlling bleaching with chlorine dioxide
FR1524581A (en) * 1966-05-25 1968-05-10 Solvay Process for adjusting the whiteness of cellulose pulp treated with hydrogen peroxide or a similar product
CA1232850A (en) * 1985-01-17 1988-02-16 Albert D. Friesen Purification of superoxide dismutase

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Abatract Bulletin of the Institute of Paper Chemistry, vol.57, No.7, January 1987, (Appleton, Wisconsin, US), M. Asther et al.: "Production of ligninolytic enzymes of Phanerochaete chrysosporium INA-12 in submerged agitated cultures", pages 956-957, abstract 8558 *
Abstract Bulletin of the Institute of Paper Chemistry, vol. 57, No. 7, January 1987, (Appleton, Wisconsin, US), P.J. Harvey et al.: "Lignin-degrading enzymes and the role of radical cations in lignin biodegradation", page 958, abstract 8575 *
Abstract Bulletin of the Institute of Paper Chemistry, vol. 57, No. 7, January 1987, (Appleton, Wisconsin, US), V.-B. Huynh et al.: "Oxidation of lignin model compounds by a manganese-dependent enzyme from phanerochaete chrysosporium as compared to chemically generated Mn(III)", page 959, abstract 8578 *
Tappi, vol. 61, No. 6, June 1978, B.I. Fleming et al.: "Soda pulping with anthraquinone. A mechanism", pages 43-46 *

Also Published As

Publication number Publication date
BR8707844A (en) 1989-10-03
HU202938B (en) 1991-04-29
FI95289B (en) 1995-09-29
DK170810B1 (en) 1996-01-22
DK344888D0 (en) 1988-06-23
DE3784515D1 (en) 1993-04-08
DE3636208A1 (en) 1988-05-05
WO1988003190A1 (en) 1988-05-05
ATE86318T1 (en) 1993-03-15
FI95289C (en) 1996-01-10
JPH02500990A (en) 1990-04-05
HUT50894A (en) 1990-03-28
FI891909A (en) 1989-04-21
AU605215B2 (en) 1991-01-10
DK344888A (en) 1988-06-23
NO175104C (en) 1994-08-31
JPH0718108B2 (en) 1995-03-01
AU8230387A (en) 1988-05-25
EP0327576A1 (en) 1989-08-16
NO175104B (en) 1994-05-24
FI891909A0 (en) 1989-04-21
NO882808L (en) 1988-06-24
NO882808D0 (en) 1988-06-24

Similar Documents

Publication Publication Date Title
EP0327576B1 (en) Process for producing cellulose from lignin-containing raw materials
EP0943032B1 (en) Multicomponent system for modifying, decomposing or bleaching lignin or lignin-containing materials, and process for using the same
EP0825294B2 (en) Multicomponent system for modifying, decomposing or bleaching lignin, or lignin-containing materials and method of using this system
WO1994029510A1 (en) Process for modifying, breaking down or bleaching lignin, materials containing lignin or like substances
WO1992020857A1 (en) Process, using enhanced-action laccase enzymes, for the delignification or bleaching of lignocellulose-containing material or for the treatment of waste water
EA005240B1 (en) Method for bleaching paper pulp
US5203964A (en) Process for producing cellulose from lignin containing raw materials using an enzyme or microorganism while monitoring and maintaining the redox potential
DE4129739A1 (en) Chlorine-free bleaching of paper pulp
EP0882814B1 (en) System and process for the electrochemical cleavage of compounds
WO1997036041A1 (en) Multicomponent system for changing, reducing or bleaching lignin, lignin-containing materials or similar substances as well as processes for its application
EP0447673B1 (en) Process of enzymatic bleaching of pulp
Shen et al. Effect of an electro-Fenton process on the biodegradation of lignin by Trametes versicolor
DE4008894C2 (en)
DE19723629B4 (en) Process for treating lignin, lignin-containing materials or similar substances
WO2020165007A1 (en) Method for cleaning process water circulated in a paper recycling system using enzymes
AT394865B (en) METHOD FOR PRODUCING A XYLANASE-RICH AND CELLULASE-LOW ENZYME SOLUTION
WO1998005818A1 (en) Multi-component system for modifying, decomposing, or bleaching lignin, lignin-containing materials or similar substances and process for its application
DE10215277A1 (en) Oxidation and bleaching systems (used e.g. in pulp delignification, waste water treatment, organic syntheses or coal liquefaction) work by hydrolase-catalyzed formation of hydroxamic acids
WO1998055489A1 (en) Multi-constituent system for modifying, degrading or bleaching lignin, materials containing lignin or similar substances, and method for using the same
Tachibana et al. Studies on Biological Treatment of Mechanical Pulps (I) Screening of Wood-Rot Fungi depressing Color Reversion of Mechanical Pulps
DE19804583A1 (en) Multi-component system for changing, breaking down or bleaching lignin, lignin-containing materials and processes for its use
EP2060541A1 (en) Process for recovering chemicals from wastewater including an oxidative pre-treatment
AT508330A1 (en) METHOD FOR PRODUCING SUGAR FROM A LIGNOCELLULOSIC MATERIAL
AT508867A1 (en) METHOD FOR PRODUCING SUGAR FROM A LIGNOCELLULOSIC MATERIAL
WO2009062580A2 (en) Method for producing fibrous material using renovated waste water

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