EP0447673A1 - Process of enzymatic bleaching of pulp - Google Patents
Process of enzymatic bleaching of pulp Download PDFInfo
- Publication number
- EP0447673A1 EP0447673A1 EP90125380A EP90125380A EP0447673A1 EP 0447673 A1 EP0447673 A1 EP 0447673A1 EP 90125380 A EP90125380 A EP 90125380A EP 90125380 A EP90125380 A EP 90125380A EP 0447673 A1 EP0447673 A1 EP 0447673A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bleaching
- added
- aqueous
- containing solution
- pulp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000004061 bleaching Methods 0.000 title claims abstract description 21
- 230000002255 enzymatic effect Effects 0.000 title claims abstract description 6
- 229920002678 cellulose Polymers 0.000 claims abstract description 18
- 239000001913 cellulose Substances 0.000 claims abstract description 17
- 108090000790 Enzymes Proteins 0.000 claims abstract description 15
- 102000004190 Enzymes Human genes 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 230000002479 lignolytic effect Effects 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 12
- OEGPRYNGFWGMMV-UHFFFAOYSA-N (3,4-dimethoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC OEGPRYNGFWGMMV-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000007844 bleaching agent Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- -1 heme compounds Chemical class 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 229960001922 sodium perborate Drugs 0.000 claims description 3
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000004155 Chlorine dioxide Substances 0.000 claims description 2
- 229920001503 Glucan Polymers 0.000 claims description 2
- 108010029541 Laccase Proteins 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 108010059820 Polygalacturonase Proteins 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 claims description 2
- 108010093305 exopolygalacturonase Proteins 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 108010002430 hemicellulase Proteins 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims 2
- 229960001484 edetic acid Drugs 0.000 claims 2
- 229960003330 pentetic acid Drugs 0.000 claims 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims 1
- 108010054320 Lignin peroxidase Proteins 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 235000010980 cellulose Nutrition 0.000 abstract 2
- 238000013019 agitation Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 229920005610 lignin Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 241000222393 Phanerochaete chrysosporium Species 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 241000233866 Fungi Species 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 210000004671 cell-free system Anatomy 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000294754 Macroptilium atropurpureum Species 0.000 description 1
- 108700020962 Peroxidase Proteins 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 108060008724 Tyrosinase Proteins 0.000 description 1
- 102000003425 Tyrosinase Human genes 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1084—Bleaching ; Apparatus therefor with reducing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1084—Bleaching ; Apparatus therefor with reducing compounds
- D21C9/1089—Bleaching ; Apparatus therefor with reducing compounds with dithionites
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
- D21C9/153—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications with ozone
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Definitions
- the present invention relates to a process for the enzymatic bleaching of cellulose.
- Chlorine bleach is associated with major environmental problems.
- the kappa number ie the lignin content
- the pulp is thus brightened.
- the object of the present invention is to provide a process for the enzymatic bleaching of cellulose which no longer has the disadvantages of the biological and chemical bleaching processes.
- This object is achieved in that a) with the simultaneous addition of oxidizing and reducing agents and addition of salts and complexing agents to an aqueous cellulose-containing solution, a redox potential in the range between 200 and 500 mV is set, b) a bleaching reaction is started by adding lignolytic enzymes and c) the reaction is maintained with constant stirring for 15 minutes to 12 hours. This procedure prevents repolymerization of the lignin and makes depolymerization possible.
- the redox potential is preferably between 250 and 450 mV.
- it can be determined by means of a redox electrode and kept constant by means of a regulator and an actuator during the entire reaction time by adding oxidizing and reducing agents, salts and phenolic compounds.
- Hydrogen peroxide, oxygen and ozone are preferably used as the oxidizing agent.
- Ascorbic acid, dithionite and sodium bisulfite are suitable as reducing agents.
- Copper (II) sulfate is added to the cellulose-containing aqueous solution as the salt.
- salts Mn (II) sulfate, Mn (III) acetate, Fe (II) sulfate, Ti (III) chloride, Ce (III) nitrate and Ce (IV) ammonium nitrate can be used. Salts with the elements zinc, antimony and lead are also suitable. Possibly. phenolic compounds can be added to the aqueous pulp-containing solution. Veratryl alcohols have proven particularly useful as such.
- fatty acids e.g. Oleic acids
- heme compounds e.g. Hemoglobin
- bleaching reagents e.g. Sodium perborate
- post-bleaching can be carried out using conventional bleaching agents such as sodium hypochlorite, O2, chlorine dioxide, ozone, H2O2 and sodium ionite.
- EDTA ethylenediaminetetraacetic acid
- DTPA diethylenetriaminepentraacetic acid
- aqueous cellulose-containing solution Sodium hypochlorite, sodium perborate, detergents, surfactants and polysaccharides, such as glucans and xanthans, are suitable as such.
- Lignolytic enzymes are preferably used as enzymes in the method according to the invention. These include phenol oxidases, laccases and peroxidases. The effectiveness of the method can be increased by using pectinase and / or hemicellulases. Particularly suitable lignolytic enzymes are those which are obtained from the white rot fungus Phanerochaete chrysosporium. The use of such enzymes is already known from US Pat. Nos. 4,692,413, 4,690,895 and 4,687,741. However, according to these patents, enzymes obtained from special mutants from Phanerochaete chrysosporium are used for bleaching. According to the invention, however, this is not necessary.
- the pH is usually between 2 and 5. A pH of 3 is particularly preferred.
- the temperature is 20 to 60 ° C., preferably 40 ° C. If the conditions are observed, the substances mentioned are added Redox potential set from 200 to 500 mV. This is determined by the ratio of the various substances added in the reaction vessel. By appropriate measurement and control of the addition of the oxidizing and reducing agents, the salts and possibly the phenolic compounds, it can be maintained throughout the reaction time.
- the bleaching process is started by simultaneous dosing of H2O2 and sodium bisulfite solution.
- the redox potential of approx. 400 mV is maintained. After the process is initiated, it continues for 2 hours.
- the process is controlled and regulated by means of a redox electrode and a pump control.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Paper (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Breeding Of Plants And Reproduction By Means Of Culturing (AREA)
- Detergent Compositions (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
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)
dadurch gekennzeichnet, daß
characterized in that
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
dadurch gekennzeichnet, daß der pH-Wert 3 beträgt.Method according to one of claims 1 to 11,
characterized in that the pH is 3.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
dadurch gekennzeichnet, daß als Bleichreagenz Natriumperborat eingesetzt wird.The method of claim 23
characterized in that sodium perborate is used as the bleaching reagent.
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.
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.
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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4008893 | 1990-03-20 | ||
| DE4008893A DE4008893A1 (en) | 1990-03-20 | 1990-03-20 | METHOD FOR ENZYMATIC BLEACHING OF CELLULAS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0447673A1 true EP0447673A1 (en) | 1991-09-25 |
| EP0447673B1 EP0447673B1 (en) | 1995-03-08 |
Family
ID=6402620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90125380A Expired - Lifetime EP0447673B1 (en) | 1990-03-20 | 1990-12-22 | Process of enzymatic bleaching of pulp |
Country Status (13)
| Country | Link |
|---|---|
| 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)
| 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)
| 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. |
| CN1127523A (en) * | 1993-06-16 | 1996-07-24 | 汉斯-彼得·考尔 | Multicomponent bleaching system |
| EP0652321B1 (en) * | 1993-11-04 | 1998-01-21 | Morton International, Inc. | Chemical pulp bleaching |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3110117C2 (en) * | 1981-03-16 | 1983-09-29 | Adolf 5340 St. Gilgen Basler | Production of cellulose from wood or other lignocellulose-containing plants through microbial degradation of the lignocellulose |
| 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 |
| 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 |
-
1990
- 1990-03-20 DE DE4008893A patent/DE4008893A1/en active Granted
- 1990-12-22 DK DK90125380.7T patent/DK0447673T3/en active
- 1990-12-22 AT AT90125380T patent/ATE119593T1/en active
- 1990-12-22 EP EP90125380A patent/EP0447673B1/en not_active Expired - Lifetime
- 1990-12-22 ES ES90125380T patent/ES2072965T3/en not_active Expired - Lifetime
- 1990-12-22 DE DE59008655T patent/DE59008655D1/en not_active Expired - Fee Related
-
1991
- 1991-03-19 BR BR919106411A patent/BR9106411A/en not_active Application Discontinuation
- 1991-03-19 WO PCT/EP1991/000540 patent/WO1991014823A1/en active Application Filing
- 1991-03-19 HU HU922982A patent/HUT64119A/en unknown
- 1991-03-19 CA CA002078345A patent/CA2078345A1/en not_active Abandoned
- 1991-03-19 JP JP91506306A patent/JPH05505857A/en active Pending
- 1991-03-19 AU AU75432/91A patent/AU641494B2/en not_active Ceased
-
1992
- 1992-09-16 NO NO923601A patent/NO180388C/en unknown
- 1992-09-17 FI FI924169A patent/FI924169A0/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| 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)
| 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 |
|---|---|
| FI924169A (en) | 1992-09-17 |
| HUT64119A (en) | 1993-11-29 |
| BR9106411A (en) | 1993-05-04 |
| NO180388B (en) | 1996-12-30 |
| FI924169A0 (en) | 1992-09-17 |
| DE4008893C2 (en) | 1992-09-03 |
| JPH05505857A (en) | 1993-08-26 |
| DE4008893A1 (en) | 1991-09-26 |
| AU7543291A (en) | 1991-10-21 |
| DK0447673T3 (en) | 1995-07-24 |
| CA2078345A1 (en) | 1991-09-21 |
| AU641494B2 (en) | 1993-09-23 |
| EP0447673B1 (en) | 1995-03-08 |
| DE59008655D1 (en) | 1995-04-13 |
| NO923601L (en) | 1992-09-16 |
| NO923601D0 (en) | 1992-09-16 |
| ATE119593T1 (en) | 1995-03-15 |
| NO180388C (en) | 1997-04-09 |
| ES2072965T3 (en) | 1995-08-01 |
| HU9202982D0 (en) | 1993-01-28 |
| WO1991014823A1 (en) | 1991-10-03 |
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