EP0447673A1 - Process of enzymatic bleaching of pulp - Google Patents

Process of enzymatic bleaching of pulp Download PDF

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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
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Prior art keywords
bleaching
added
aqueous
containing solution
pulp
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German (de)
French (fr)
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EP0447673B1 (en
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Hans-Peter Dr. Call
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LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG UND ZUM VERT
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LIGNOZYM GESELLSCHAFT ZUR HERSTELLUNG und ZUM VERTRIEB VON ENZYMEN mbH
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1084—Bleaching ; Apparatus therefor with reducing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1084—Bleaching ; Apparatus therefor with reducing compounds
    • D21C9/1089—Bleaching ; Apparatus therefor with reducing compounds with dithionites
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
    • D21C9/153—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications with ozone
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides

Definitions

  • the present invention relates to a 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.

Abstract

The present invention concerns a process for the enzymatic bleaching of celluloses in which a) a redox potential in the range between 200 and 500 mV is set with the simultaneous dosed addition of oxidation and reducing agents and the addition of salts and complex formers to provide an aqueous cellulose-containing solution; b) a bleaching reaction is initiated by the addition of lignolytic enzymes; and c) the reaction is maintained for 15 minutes to 12 hours under continuous agitation.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum enzymatischen Bleichen von Zellstoffen.The present invention relates to a process for the enzymatic bleaching of cellulose.

Die bisher bekannten biologischen Verfahren zur Zellstoffherstellung arbeiten mit Mikroorganismen, insbesondere mit Pilzen. So ist aus der DE-PS 31 10 117 ein Verfahren zur Gewinnung von Zellulose aus Holz oder anderen Pflanzenfasernmaterialien bekannt, bei dem die Lignozellulose mit Hilfe von Weißfäulepilzen abgebaut wird. Die mit Mikroorganismen arbeitenden Verfahren haben jedoch erhebliche Nachteile. So ist es bislang nicht möglich, ohne gleichzeitiges Wachstum der Mikroorganismen und ohne Verlust an Cellulose 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. From DE-PS 31 10 117 a method for the production of cellulose from wood or other plant fiber materials is known, in which the lignocellulose is broken down with the help of white rot fungi. However, the processes using microorganisms have considerable disadvantages. So far it has not been possible to achieve degradation and detachment of the lignin from its companion polymers (cellulose) without simultaneous growth of the microorganisms and without loss of cellulose. The simultaneous growth of the fungus leads to very long breakdown times, which can take up to several weeks.

In den letzten Jahren sind wegen der dargestellten Schwierigkeiten des Einsatzes von Mikroorganismen die Verwendungsmöglichkeiten für isolierte Enzymsysteme untersucht worden. Insbesondere wurden die Enzyme des Weißfäulepilzes Phanerochaete chrysosporium erforscht 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 das Gleichgewicht der Reaktion auf der Polymerisationsseite liegt, d.h. zellfreie Systeme bauen kein Lignin ab bzw. polymerisieren es.In recent years, the possible uses for isolated enzyme systems have been investigated because of the difficulties presented with the use of microorganisms. In particular, the enzymes of the white rot fungus Phanerochaete chrysosporium were researched 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, the equilibrium of the reaction lies on the polymerization side, i.e. cell-free systems do not break down or polymerize lignin.

In der Literatur ist auch seit der Entdeckung der lignolytischen Enzyme beim Weißfäulepilz Phanerochaete chrysosporium eine Reihe von enzymatischen Verfahren zum Bleichen von Zellstoff mit lebenden Pilzsystemen und auch von zellfreien Systemen bekannt geworden. Ebenso wurde eine Reihe von Versuchen unternommen, mit Hämsystemen zu bleichen. Alle diese Systeme benötigen Reaktionszeiten von mehr als 12 Stunden. D.h. allen diesen Systemen sind ein großer Zeitaufwand und hohe Kosten zu eigen. Letzteres trifft insbesondere für die reinen Hämsysteme zu.Since the discovery of the lignolytic enzymes in the white rot fungus Phanerochaete chrysosporium, a number of enzymatic processes for bleaching pulp with living fungal systems and also cell-free systems have become known in the literature. A number of attempts have also been made to bleach with heme systems. All of these systems require response times of more than 12 hours. I.e. all of these systems are time consuming and costly. The latter applies in particular to the pure hamming systems.

Heutzutage wird eine Bleiche noch rein chemisch in mehreren Stufen unter Zusatz von Chlor durchgeführt. Die Chlorbleiche ist aber mit großen Umweltproblemen verbunden. Bei den Bleichverfahren wird im allgemeinen durch Entfernung der beim Kochprozeß zur Ligninentfernung entstandenen chromophoren Restlignin-Kondensationsprodukte die Kappazahl, d.h. der Ligningehalt erniedrigt und so der Zellstoff aufgehellt.Nowadays, bleaching is still done chemically in several stages with the addition of chlorine. Chlorine bleach is associated with major environmental problems. In the bleaching process, the kappa number, ie the lignin content, is generally reduced by removing the chromophoric residual lignin condensation products formed during the lignin removal process, and the pulp is thus brightened.

Die vorliegende Erfindung hat sich nunmehr die Aufgabe gestellt, ein Verfahren zum enzymatischen Bleichen von Zellstoffen zur Verfügung zu stellen, welches die aufgezeigten Nachteile der biologischen und chemischen Bleichverfahren nicht mehr aufweist.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.

Diese Aufgabe wird dadurch gelöst, daß a) unter gleichzeitiger Zudosierung von Oxidations- und Reduktionsmitteln und Zusatz von Salzen und Komplexbildnern zu einer wässrigen zellstoffhaltigen Lösung ein Redoxpotential im Bereich zwischen 200 und 500 mV eingestellt, b) durch Zugabe von lignolytischen Enzymen eine Bleichreaktion gestartet und c) die Reaktion unter ständigem Rühren über 15 Minuten bis 12 Stunden aufrechterhalten wird. Durch diese Verfahrensführung wird eine Repolymerisierung des Lignins verhindert und eine Depolymerisierung erst möglich gemacht.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.

Das Redoxpotential liegt vorzugsweise zwischen 250 und 450 mV. Es kann bei dem erfindungsgemäßen Verfahren mittels einer Redoxelektrode ermittelt und mittels eines Reglers und eines Stellgliedes während der gesamten Reaktionszeit durch die Zugabe von Oxidations- und Reduktionsmitteln, Salzen und phenolischen Verbindungen konstant gehalten werden.The redox potential is preferably between 250 and 450 mV. In the method according to the invention, 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.

Als Oxidationsmittel werden vorzugsweise Wasserstoffperoxid, Sauerstoff und Ozon eingesetzt. Als Reduktionsmittel kommen Ascorbinsäure, Dithionit und Natrium-Bisulfit in Frage.Hydrogen peroxide, oxygen and ozone are preferably used as the oxidizing agent. Ascorbic acid, dithionite and sodium bisulfite are suitable as reducing agents.

Als Salz wird der zellstoffhaltigen wässrigen Lösung Kupfer(II) sulfat zugesetzt. Zusätzlich können als Salze Mn(II)sulfat, Mn (III)Acetat, Fe(II)sulfat, Ti(III)chlorid, Ce(III)nitrat und Ce(IV)amoniumnitrat eingesetzt werden. Ebenso kommen Salze mit den Elementen Zink, Antimon und Blei in Betracht. Ggf. können der wässrigen zellstoffhaltigen Lösung phenolische Verbindungen zugesetzt werden. Als solche haben sich inbesondere Veratrylalkohole bewährt.Copper (II) sulfate is added to the cellulose-containing aqueous solution as the salt. In addition, 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.

Ferner können der wässrigen zellstoffhaltigen Lösung Fettsäuren z.B. Ölsäuren, Hämverbindungen z.B. Hämoglobin und Bleichreagenzien z.B. Natriumperborat zugesetzt werden. Darüber hinaus kann eine Nachbleiche mit gängigen Bleichmitteln, wie Natriumhypochlorit, O₂, Chlordioxid, Ozon, H₂O₂ und Natriumtionit durchgeführt werden.Furthermore, fatty acids e.g. Oleic acids, heme compounds e.g. Hemoglobin and bleaching reagents e.g. Sodium perborate can be added. In addition, post-bleaching can be carried out using conventional bleaching agents such as sodium hypochlorite, O₂, chlorine dioxide, ozone, H₂O₂ and sodium ionite.

Außerdem sei darauf hingewiesen, daß der Zusatz von Komplexbildnern für den Erfolg des erfindungsgemäßen Verfahrens sehr wichtig ist. Als solche werden vorzugsweise Ethylendiamintetraessigsäure (EDTA) oder Diethylentriaminpentraessigsäure (DTPA) eingesetzt. Sobald das erforderliche Redoxpotential eingestellt ist, beginnt relativ schnell der Bleichprozeß, der innerhalb weniger Minuten schon beendet sein kann, allerdings mit kaum erniedrigter Kappazahl, welche in Abhängigkeit vom Zellstoffgehalt nach einigen Stunden bis zu 90 % vermindert werden kann.It should also be pointed out that the addition of complexing agents is very important for the success of the process according to the invention. As such, preference is given to using ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentraacetic acid (DTPA). As soon as the required redox potential has been set, the bleaching process begins relatively quickly, which can be completed within a few minutes, but with a hardly reduced kappa number, which can be reduced by up to 90% after a few hours, depending on the cellulose content.

Zusätzlich zu den genannten Stoffen können der wässrigen zellstoffhaltigen Lösung weitere Substanzen zugesetzt werden. Als solche kommen Natriumhypochlorit, Natriumperborat, Detergenzien, Tenside und Polysaccharide, wie Glukane und Xanthane in Betracht.In addition to the substances mentioned, further substances can be added to the aqueous cellulose-containing solution. Sodium hypochlorite, sodium perborate, detergents, surfactants and polysaccharides, such as glucans and xanthans, are suitable as such.

Als Enzyme werden bei dem erfindungsgemäßen Verfahren vorzugsweise lignolytische Enzyme eingesetzt. Hierzu zählen unter anderem Phenoloxidasen, Laccasen und Peroxidasen. Die Wirksamkeit des Verfahrens kann durch Einsatz von Pektinase und/oder Hemicellulasen noch erhöht werden. Besonders geeignete lignolytische Enzyme sind solche, die aus dem Weißfäulepilz Phanerochaete chrysosporium gewonnen werden. Der Einsatz solcher Enzyme ist bereits aus den US-PS 4 692 413, 4 690 895 und 4 687 741 bekannt. Allerdings werden nach diesen Patentschriften aus speziellen Mutanten aus Phanerochaete chrysosporium gewonnene Enzyme zum Bleichen eingesetzt. Erfindungsgemäß ist dies hingegen nicht erforderlich. Vielmehr können bei Einhaltung der dargestellten Bedingungen alle heute bekannten lignolytischen Enzyme eingesetzt werden. Der Hauptunterschied ist in der Funktion der zudosierten reduzierenden oder oxidierenden Stoffe und Mediatoren, welche als Radikalfänger fungieren, zu sehen. Diese Stoffe verhindern nämlich eine Repolymerisierung des Lignins und ermöglichen dadurch erst einen Ligninabbau in der beschriebenen Weise und Menge innerhalb der erwähnten kurzen Zeitspanne.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. Rather, all lignolytic enzymes known today can be used if the conditions shown are observed. The main difference is the function of the added reducing or oxidizing substances and mediators, which act as radical scavengers. This is because these substances prevent the lignin from repolymerizing and thus enable lignin degradation in the manner and quantity described within the short period of time mentioned.

Bei dem erfindungsgemäßen Verfahren liegt der pH-Wert gewöhnlich zwischen 2 und 5. Besonders bevorzugt wird ein pH-Wert von 3. Die Temperatur beträgt 20 bis 60° C, vorzugsweise 40° C. Bei Einhaltung der Bedingungen wird unter Zusatz der genannten Stoffe ein Redoxpotential von 200 bis 500 mV eingestellt. Dabei wird dies durch das Verhältnis der verschiedenen zugesetzten Stoffe im Reaktionsgefäß bestimmt. Durch die entsprechende Messung und Regelung der Zugabe der Oxidations- und Reduktionsmittel, der Salze und ggf. der phenolischen Verbindungen kann es während der gesamten Reaktionszeit aufrechterhalten werden.In the process according to the invention, 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.

Mit dem geschilderten Bleichverfahren ist es erstmals gelungen, innerhalb sehr kurzer Zeit (15 Minuten - 2 Stunden) bei physiologischen Temperaturen (40° C) ohne Druck und mit geringsten Zugaben an chemischen Stoffen kostengünstig und vor allem umweltschonend Zellstoffe zu bleichen. Ein weiterer Vorteil des erfindungsgemäßen Verfahrens ist die Möglichkeit der kontinuierlichen Verfahrensführung.With the bleaching process described, it has been possible for the first time to bleach cellulose inexpensively and above all in an environmentally friendly manner within a very short time (15 minutes - 2 hours) at physiological temperatures (40 ° C) without pressure and with the smallest addition of chemical substances. Another advantage of the process according to the invention is the possibility of continuous process control.

Das erfindungsgemäße Verfahren wird anhand der folgenden Beispiele näher erläutert:
50 g atro Zellstoff (Sulfatzellstoff) werden in einem Rührgefäß bei 1 % Stoffdichte bei ca. 500 rpm und 40 °C gerührt. Der pH-Wert wird mit 1 n HCL auf pH 3 eingestellt. Es werden 0,1 - 1,5 % H₂O₂ auf atro Stoff bezogen, ca. 2 x 10⁻⁵ % - 2 x 10⁻³ % Veratrylalkohol (VA) und 0,1 % EDTA oder DTPA, 0,001 - 0,01 % Kupfer(II)sulfat bezogen auf atro Stoff zugesetzt. Nach Zugabe von 500 - 5000 IU lignolytischer Enzyme (1 IU = Umsatz von 1 nmol VA/min. in Veratrylaldehyd) wird der Bleichprozeß durch gleichzeitige Dosierung von H₂O₂ und Natrium-Bisulfit-Lösung in Gang gesetzt. Hierbei wird das Redoxpotential von ca. 400 mV aufrechterhalten. Nachdem der Prozeß eingeleitet ist, wird dieser für 2 Stunden fortgesetzt. Die Steuerung und Regelung des Prozesses wird mittels einer Redoxelektrode und einer Pumpensteuerung durchgeführt.The process according to the invention is explained in more detail using the following examples:
50 g of dry cellulose (sulfate pulp) are stirred in a stirred vessel at 1% consistency at approx. 500 rpm and 40 ° C. The pH is adjusted to pH 3 with 1N HCL. There are 0.1 - 1.5% H₂O₂ related to atro material, approx. 2 x 10⁻⁵% - 2 x 10⁻³% veratryl alcohol (VA) and 0.1% EDTA or DTPA, 0.001 - 0.01% Copper (II) sulfate based on dry substance added. After adding 500 - 5000 IU of lignolytic enzymes (1 IU = conversion of 1 nmol VA / min. In veratrylaldehyde) 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.

Claims (27)

Verfahren zum enzymatischen Bleichen von Zellstoffen,
dadurch gekennzeichnet, daß a) unter gleichzeitiger Zudosierung von Oxidations- und Reduktionsmitteln und Zusatz von Salzen und Komplexbildnern zu einer wässrigen zellstoffhaltigen Lösung ein Redoxpotential im Bereich zwischen 200 und 500 mV eingestellt, b) durch Zugabe von lignolytischen Enzymen eine Bleichreaktion gestartet und c) die Reaktion unter ständigem Rühren über 15 Minuten bis 12 Stunden aufrechterhalten wird. Process for the enzymatic bleaching of cellulose,
characterized 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. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, daß das Redoxpotential zwischen 250 und 450 mV liegt.Method according to claim 1,
characterized in that the redox potential is between 250 and 450 mV. Verfahren nach Anspruch 1 oder 2,
dadurch gekennzeichnet, daß als Oxidationsmittel H₂O₂, O₂ oder Ozon eingesetzt werden.Method according to claim 1 or 2,
characterized in that H₂O₂, O₂ or ozone are used as the oxidizing agent. Verfahren nach einem der Ansprüche 1 bis 3,
dadurch gekennzeichnet, daß als Reduktionsmittel Ascorbinsäure, Dithionit oder Natrium-Bisulfit eingesetzt werden.Method according to one of claims 1 to 3,
characterized in that ascorbic acid, dithionite or sodium bisulfite are used as reducing agents. Verfahren nach einem der Ansprüche 1 bis 4,
dadurch gekennzeichnet, daß als lignolytische Enzyme Ligninperoxidasen und Laccasen eingesetzt werden.Method according to one of claims 1 to 4,
characterized in that lignin peroxidases and laccases are used as lignolytic enzymes. Verfahren nach einem der Ansprüche 1 bis 5,
dadurch gekennzeichnet, daß als Salz Kupfer(II)sulfat eingesetzt wird.Method according to one of claims 1 to 5,
characterized in that copper (II) sulfate is used as salt. Verfahren nach einem der Ansprüche 1 bis 6,
dadurch gekennzeichnet, daß zusätzlich zu Kupfer(II)sulfat als Salz Mn(II)sulfat, Mn(III)acetat, Fe(II)sulfat, Ti(III)chlorid, Ce(III)nitrat und/oder Ce(IV) amoniumnitrat eingesetzt werden.Method according to one of claims 1 to 6,
characterized in that in addition to copper (II) sulfate as salt Mn (II) sulfate, Mn (III) acetate, Fe (II) sulfate, Ti (III) chloride, Ce (III) nitrate and / or Ce (IV) ammonium nitrate be used. Verfahren nach einem der Ansprüche 1 bis 7 ,
dadurch gekennzeichnet, daß zur Einstellung des Redoxpotentials zusätzlich phenolische Verbindungen der zellstoffhaltigen wässrigen Lösung zugesetzt werden.Method according to one of claims 1 to 7,
characterized in that in order to adjust the redox potential, additional phenolic compounds are added to the cellulose-containing aqueous solution. Verfahren nach Anspruch 8,
dadurch gekennzeichnet, daß als phenolische Verbindung Veratrylalkohol eingesetzt wird.A method according to claim 8,
characterized in that veratryl alcohol is used as the phenolic compound. Verfahren nach einem der Ansprüche 1 bis 9,
dadurch gekennzeichnet, daß zusätzlich zu den lignolytischen Enzymen Pektinasen und/oder Hemicellulasen eingesetzt werden.Method according to one of claims 1 to 9,
characterized in that pectinases and / or hemicellulases are used in addition to the lignolytic enzymes. Verfahren nach einem der Ansprüche 1 bis 10,
dadurch gekennzeichnet, daß der pH-Wert zwischen 2 und 5 liegt.Method according to one of claims 1 to 10,
characterized in that the pH is between 2 and 5. Verfahren nach einem der Ansprüche 1 bis 11,
dadurch gekennzeichnet, daß der pH-Wert 3 beträgt.Method according to one of claims 1 to 11,
characterized in that the pH is 3. Verfahren nach einem der Ansprüche 1 bis 12,
dadurch gekennzeichnet, daß die Temperatur zwischen 20 und 60° C liegt.Method according to one of claims 1 to 12,
characterized in that the temperature is between 20 and 60 ° C. Verfahren nach einem der Ansprüche 1 bis 13,
dadurch gekennzeichnet, daß die Temperatur bei 40° C liegt.Method according to one of claims 1 to 13,
characterized in that the temperature is 40 ° C. Verfahren nach einem der Ansprüche 1 bis 14,
dadurch gekennzeichnet, daß Natriumhypochlorit der Reaktionslösung zugesetzt wird.Method according to one of claims 1 to 14,
characterized in that sodium hypochlorite is added to the reaction solution. Verfahren nach einem der Ansprüche 1 bis 15,
dadurch gekennzeichnet, daß als Komplexbildner Ethylendiamin-tetraessigsäure (EDTA) oder Diethylentriamin-pentaessigsäure (DTPA) eingesetzt werden.Method according to one of claims 1 to 15,
characterized in that ethylenediamine-tetraacetic acid (EDTA) or diethylenetriamine-pentaacetic acid (DTPA) are used as complexing agents. Verfahren nach einem der Ansprüche 1 bis 16,
dadurch gekennzeichnet, daß zur wässrigen, zellstoffhaltigen Lösung Polysaccharide zugesetzt werden.Method according to one of claims 1 to 16,
characterized in that polysaccharides are added to the aqueous, pulp-containing solution. Verfahren nach Anspruch 17,
dadurch gekennzeichnet, daß die Polysaccharide Glukane und/oder Xanthan sind.The method of claim 17
characterized in that the polysaccharides are glucans and / or xanthan. Verfahren nach einem der Ansprüche 1 bis 18,
dadurch gekennzeichnet, daß der wässrigen, zellstoffhaltigen Lösung Detergenzien zugesetzt werden.Method according to one of claims 1 to 18,
characterized in that detergents are added to the aqueous, pulp-containing solution. Verfahren nach einem der Ansprüche 1 bis 19,
dadurch gekennzeichnet, daß der wässrigen, zellstoffhaltigen Lösung Tenside zugesetzt werden.Method according to one of claims 1 to 19,
characterized in that surfactants are added to the aqueous, cellulose-containing solution. Verfahren nach einem der Ansprüche 1 bis 20,
dadurch gekennzeichnet, daß der wässrigen, zellstoffhaltigen Lösung Fettsäuren zugesetzt werden.Method according to one of claims 1 to 20,
characterized in that fatty acids are added to the aqueous, pulp-containing solution. Verfahren nach einem der Ansprüche 1 bis 21,
dadurch gekennzeichnet, daß der wässrigen, zellstoffhaltigen Lösung Hämverbindungen zugesetzt werden.Method according to one of claims 1 to 21,
characterized in that heme compounds are added to the aqueous, pulp-containing solution. Verfahren nach einem der Ansprüche 1 bis 22,
dadurch gekennzeichnet, daß der wässrigen, zellstoffhaltigen Lösung zusätzlich Bleichreagenzien beigegeben werden.Method according to one of claims 1 to 22,
characterized in that bleaching agents are additionally added to the aqueous, pulp-containing solution. Verfahren nach Anspruch 23,
dadurch gekennzeichnet, daß als Bleichreagenz Natriumperborat eingesetzt wird.The method of claim 23
characterized in that sodium perborate is used as the bleaching reagent. Verfahren nach einem der Ansprüche 1 bis 24,
dadurch gekennzeichnet, daß nach Abschluß der Reaktion mit NaOH und/oder H₂SO₄ extrahiert wird.Method according to one of claims 1 to 24,
characterized in that after the reaction is extracted with NaOH and / or H₂SO₄. Verfahren nach einem der Ansprüche 1 bis 25,
dadurch gekennzeichnet, daß eine Nachbleichung mittels gängiger Bleichmittel vorgenommen wird.Method according to one of claims 1 to 25,
characterized in that post-bleaching is carried out using conventional bleaching agents. Verfahren nach Anspruch 26,
dadurch gekennzeichnet, daß zum Nachbleichen Natriumhypochlorit, Chlor, Chlordioxid, O₂, Ozon, H₂O₂ und Natriumdithionit verwendet werden.The method of claim 26
characterized in that sodium hypochlorite, chlorine, chlorine dioxide, O₂, ozone, H₂O₂ and sodium dithionite are used for bleaching.
EP90125380A 1990-03-20 1990-12-22 Process of enzymatic bleaching of pulp Expired - Lifetime EP0447673B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4008893A DE4008893A1 (en) 1990-03-20 1990-03-20 METHOD FOR ENZYMATIC BLEACHING OF CELLULAS
DE4008893 1990-03-20

Publications (2)

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

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EP90125380A Expired - Lifetime EP0447673B1 (en) 1990-03-20 1990-12-22 Process of enzymatic bleaching of pulp

Country Status (13)

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EP (1) EP0447673B1 (en)
JP (1) JPH05505857A (en)
AT (1) ATE119593T1 (en)
AU (1) AU641494B2 (en)
BR (1) BR9106411A (en)
CA (1) CA2078345A1 (en)
DE (2) DE4008893A1 (en)
DK (1) DK0447673T3 (en)
ES (1) ES2072965T3 (en)
FI (1) FI924169A0 (en)
HU (1) HUT64119A (en)
NO (1) NO180388C (en)
WO (1) WO1991014823A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992020857A1 (en) * 1991-05-17 1992-11-26 Call Hans Peter Process, using enhanced-action laccase enzymes, for the delignification or bleaching of lignocellulose-containing material or for the treatment of waste water
EP0634520A1 (en) * 1993-07-15 1995-01-18 SOLVAY (Société Anonyme) Process for bleaching paper pulp
US5691193A (en) * 1993-02-25 1997-11-25 Pulp And Paper Research Institute Of Canada Non-chlorine bleaching of kraft pulp
WO1999009244A1 (en) * 1997-08-14 1999-02-25 Takashi Watanabe Chemical method for lignin depolymerization
WO1999054545A1 (en) * 1998-04-16 1999-10-28 Pulp And Paper Research Institute Of Canada Oxidase process for pulp and dye oxidation
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

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI914780A0 (en) * 1991-10-10 1991-10-10 Valtion Teknillinen FOERFARANDE FOER ENTSYMATISK BEHANDLING AV LIGNOCELLULOSAHALTIGA MATERIAL, I SYNNERHET CELLULOSAMASSOR.
DE59409297D1 (en) * 1993-06-16 2000-05-25 Call Hans Peter MULTI-COMPONENT BLEACHING SYSTEM
EP0652321B1 (en) * 1993-11-04 1998-01-21 Morton International, Inc. Chemical pulp bleaching

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WO1988003190A1 (en) * 1986-10-24 1988-05-05 Call Hans Peter Process for producing cellulose from lignin-containing raw materials
EP0345715A1 (en) * 1988-06-08 1989-12-13 International Paper Company Enzymatic delignification of lignocellulosic material

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

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WO1988003190A1 (en) * 1986-10-24 1988-05-05 Call Hans Peter Process for producing cellulose from lignin-containing raw materials
EP0345715A1 (en) * 1988-06-08 1989-12-13 International Paper Company Enzymatic delignification of lignocellulosic material

Non-Patent Citations (1)

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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 (en) * 1991-05-17 1992-11-26 Call Hans Peter Process, using enhanced-action laccase enzymes, for the delignification or bleaching of lignocellulose-containing material or for the treatment of waste water
US5691193A (en) * 1993-02-25 1997-11-25 Pulp And Paper Research Institute Of Canada Non-chlorine bleaching of kraft pulp
EP0634520A1 (en) * 1993-07-15 1995-01-18 SOLVAY (Société Anonyme) Process for bleaching paper pulp
BE1007272A3 (en) * 1993-07-15 1995-05-09 Solvay Method of a pulp bleach.
AU682363B2 (en) * 1993-07-15 1997-10-02 Solvay (Societe Anonyme) Process for bleaching a paper pulp
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
WO1999009244A1 (en) * 1997-08-14 1999-02-25 Takashi Watanabe Chemical method for lignin depolymerization
US6214976B1 (en) 1997-08-14 2001-04-10 T. Watababe Chemical method for lignin depolymerization
WO1999054545A1 (en) * 1998-04-16 1999-10-28 Pulp And Paper Research Institute Of Canada Oxidase process for pulp and dye oxidation
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
DE4008893A1 (en) 1991-09-26
NO923601L (en) 1992-09-16
HU9202982D0 (en) 1993-01-28
EP0447673B1 (en) 1995-03-08
DE4008893C2 (en) 1992-09-03
CA2078345A1 (en) 1991-09-21
FI924169A (en) 1992-09-17
HUT64119A (en) 1993-11-29
BR9106411A (en) 1993-05-04
AU641494B2 (en) 1993-09-23
ATE119593T1 (en) 1995-03-15
WO1991014823A1 (en) 1991-10-03
NO180388B (en) 1996-12-30
FI924169A0 (en) 1992-09-17
DE59008655D1 (en) 1995-04-13
ES2072965T3 (en) 1995-08-01
NO923601D0 (en) 1992-09-16
NO180388C (en) 1997-04-09
DK0447673T3 (en) 1995-07-24
AU7543291A (en) 1991-10-21
JPH05505857A (en) 1993-08-26

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