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WO1998005818A1 - Systeme a plusieurs composants pour modifier, decomposer ou blanchir de la lignine, des materiaux contenant de la lignine ou des substances analogues et procede permettant de l'utiliser - Google Patents

Systeme a plusieurs composants pour modifier, decomposer ou blanchir de la lignine, des materiaux contenant de la lignine ou des substances analogues et procede permettant de l'utiliser Download PDF

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Publication number
WO1998005818A1
WO1998005818A1 PCT/EP1997/004173 EP9704173W WO9805818A1 WO 1998005818 A1 WO1998005818 A1 WO 1998005818A1 EP 9704173 W EP9704173 W EP 9704173W WO 9805818 A1 WO9805818 A1 WO 9805818A1
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WO
WIPO (PCT)
Prior art keywords
nitrosophenol
lignin
nitroso
acid
component system
Prior art date
Application number
PCT/EP1997/004173
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German (de)
English (en)
Inventor
Johannes Freudenreich
Jürgen STOHRER
Manfred Amann
Robert Müller
Original Assignee
Consortium für elektrochemische Industrie GmbH
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 Consortium für elektrochemische Industrie GmbH filed Critical Consortium für elektrochemische Industrie GmbH
Priority to AU38506/97A priority Critical patent/AU3850697A/en
Publication of WO1998005818A1 publication Critical patent/WO1998005818A1/fr

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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
    • 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
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes

Definitions

  • Multi-component system for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances as well as processes for its use
  • the present invention relates to a multi-component system for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances, and methods for its use.
  • the sulfate and sulfite processes are the main processes used today for pulp production. Both methods produce pulp under cooking and under pressure.
  • the sulfate process works with the addition of NaOH and Na 2 S, while Ca (HS0 3 ) 2 + S0 2 is used in the sulfite process.
  • the main aim of all processes is to remove the lignin from the plant material, wood or annual plants used.
  • the lignin which is the main constituent of the plant material (stem or stem) with the cellulose and He icellulose, must be removed, otherwise it is not possible to produce non-yellowing and mechanically heavy-duty papers.
  • the wood fabrication processes work with stone grinders (wood sanding) or with refiners (TMP), which defibrillate the wood by grinding after appropriate pretreatment (chemical, thermal or chemical-thermal).
  • Biopulping is the treatment of wood chips with living mushroom systems.
  • Another advantage is the mostly existing improvement in the mechanical properties of the fabric, a disadvantage the poorer final whiteness.
  • Biobleaching also works with in-vivo systems.
  • the boiled pulp (Softwood / Hardwood) is inoculated with fungus before bleaching and treated for days to weeks. Only after this long treatment time does a significant decrease in kappa number and increase in whiteness become apparent, which makes the process uneconomical for implementation in the usual bleaching sequences.
  • Another application that is usually carried out with immobilized fungal systems is the treatment of pulp wastewater, in particular bleaching wastewater, to decolorize it and reduce the AOX (reduction of chlorinated compounds in the wastewater that cause chlorine or chlorine dioxide bleaching stages).
  • chelating substances siderophores such as ammonium oxalate
  • biosurfactants are assumed to be the cofactor.
  • the application PCT / EP87 / 00635 describes a system for removing lignin from lignin-cellulose-containing material with simultaneous bleaching, which works with lignolytic enzymes from white rot fungi with the addition of reducing and oxidizing agents and phenolic compounds as mediators.
  • enhancer substances are organic chemicals which contain at least two aromatic rings, at least one of which is substituted with defined radicals.
  • WO 94/29510 describes a method for enzymatic delignification, in which enzymes are used together with mediators.
  • Compounds with the structure NO, NOH or HRNOH are generally disclosed as mediators.
  • HBT 1-Hydroxy-lH-benzotriazole
  • the present invention relates to a multi-component system for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances
  • mediator characterized in that the mediator is selected from the group of vicinally nitroso-substituted aromatic alcohols of the general formulas la or ib
  • R 1 , R 2 , R 3 and R 4 are the same or different and are hydrogen, halogen, hydroxy, formyl, carbamoyl, carboxy, ester or salt of carboxy, sulfono, ester or salt of sulfono, sulfamoyl, Nitro-, nitroso-, cyano, amino-, phenyl-, aryl-C 1 -C 5 -alkyl-, C 1 -C 12 -alkyl-, C- j ⁇ -Cg-alkoxy-, C l -C 10 - Carbonyl, arDon y 1 ⁇ c ⁇ " c 6 ⁇ al * : y 1 "'phospho-, phosphono-, Mean phosphonoxy residue, ester or salt of the phosphonoxy residue,
  • carbamoyl, sulfamoyl, amino and phenyl radicals can be unsubstituted or substituted one or more times with a radical R 5 and the aryl-C - ⁇ - Cg-alkyl, C- L -C 12 alkyl, C j ⁇ -CG alkoxy, C 1 -C 10 carboxylic ⁇ y 1 ⁇ 'carbonyl-C - ⁇ - Cg-alkyl radicals can be saturated or unsaturated, may be branched or unbranched, and with a radical R 5 or can be substituted several times, wherein
  • R 5 is the same or different and is hydroxyl, formyl, carboxy, ester or salt of carbox, carbamoyl, sulfono, sulfamoyl, nitro, nitroso, amino, phenyl, C - ⁇ - Cg-alkyl- , C- j ⁇ - C 5 -alkoxy radical means or
  • R 6 , R 7 , R 8 and R 9 are the same or different and have the meanings given for R 1 to R 4 .
  • Aromatic alcohols are preferably to be understood as meaning phenols or higher-condensed derivatives of phenol.
  • Preferred mediators in the multicomponent system according to the invention are compounds of the general formula Ia or Ib, the synthesis of which can be attributed to the nitrosation of substituted phenols.
  • Examples of such compounds are 2-nitrosophenol, 3-methyl-6-nitrosophenol, 2-methyl-6-nitrosophenol, 4-methyl-6-nitrosophenol, 3-ethyl-6-nitrosophenol, 2-ethyl-6-nitrosophenol, 4 -Ethyl-6-nitrosophenol, 4-isopropyl-6-nitrosophenol, 4-tert.butyl-6-nitrosophenol, 2-phenyl-6-nitrosophenol, 2-benzyl-6-nitrosophenol, 4-benzyl-6-nitrosophenol, 2 -Hydroxy-3-nitrosobenzyl alcohol, 2-hydroxy-3-nitrosobenzoic acid,
  • 4-hydroxy-3-nitrosobenzoic acid 2-methoxy-6-nitrosophenol, 3, 4-dimethyl-6-nitrosophenol, 2, 4-dimethyl-6-nitrosophenol, 3, 5-dimethyl-6-nitrosophenol, 2, 5- Dimethyl-6-nitrosophenol, 2-nitrosoresorcinol, 4-nitrosoresorcinol, 2-nitrosoorcinol, 2-nitrosophloroglucin and 4-nitrosopyrogallol, 4-nitroso-3-hydroxyaniline, 4-nitro-2-nitrosophenol.
  • mediators are o-nitroso derivatives of higher condensed aromatic alcohols.
  • examples of such compounds are 2-nitroso-1-naphthol, 1-methyl-3-nitroso-2-naphthol and 9-hydroxy-10-nitroso-phenanthrene.
  • mediators are 1-nitroso-2-naphthol, 1-nitroso-2-naphthol-3, 6-disulfonic acid, 2-nitroso-1-naphthol-4-sulfonic acid,
  • the multicomponent system according to the invention contains mediators which are less expensive than HBT.
  • the invention thus also relates to the use of mediators mentioned in claim 1 as component c) for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances.
  • the multicomponent system according to the invention preferably comprises at least one oxidation catalyst.
  • Enzymes are preferably used as oxidation catalysts in the multicomponent system according to the invention.
  • the term enzyme also encompasses enzymatically active proteins or peptides or prosthetic groups of enzymes.
  • the multicomponent system according to the invention can be used as the enzyme
  • Enzymes of the classes mentioned below are preferably used:
  • Class 1.1 enzymes which comprise all dehydrogenases which act on primary, secondary alcohols and semiacetals and which accept NAD + or NADP + (subclass 1.1.1), cytochrome (1.1.2), oxygen (0 2 ) (1.1.3), disulfides (1.1.4), quinones (1.1.5) or the other acceptors (1.1.99).
  • the enzymes of this class are particularly preferred.
  • Class 1.1.5 with quinones as acceptors and the enzymes of class 1.1.3 with oxygen as acceptors.
  • Cellobiose quinone-l-oxidoreductase (1.1.5.1) is particularly preferred in this class.
  • Enzymes of class 1.2 are also preferred.
  • This enzyme class includes those enzymes that oxidize aldehydes to the corresponding acids or oxo groups.
  • the acceptors can be NAD + , NADP + (1.2.1), Cytochro e (1.2.2), Oxygen
  • Enzymes of class 1.3 are also preferred.
  • This class includes enzymes that act on the CH-CH groups of the donor.
  • acceptors are NAD + , NADP + (1.3.1), cytochrome (1.3.2), oxygen (1.3.3), quinones or related
  • Bilirubin oxidase (1.3.3.5) is particularly preferred.
  • the enzymes of class (1.3.3) with oxygen as acceptor and (1.3.5) with quinones etc. as acceptor are also particularly preferred here.
  • class 1.4 enzymes which act on CH-NH 2 groups of the donor.
  • acceptors are NAD + , NADP + (1.4.1), cytochrome (1.4.2), oxygen (1.4.3), disulfides (1.4.4), iron-sulfur proteins (1.4.7) or others Acceptors (1.4.99).
  • Enzymes of class 1.4.3 with oxygen as the acceptor are also particularly preferred here.
  • class 1.5 enzymes which act on CH-NH groups of the donor.
  • the corresponding acceptors are NAD + , NADP + (1.5.1), oxygen (1.5.3), disulfides (1.5.4), quinones (1.5.5) or other acceptors (1.5.99).
  • Enzymes with oxygen (0 2 ) (1.5.3) and with quinones (1.5.5) as acceptors are also particularly preferred here.
  • Enzymes of class 1.6 which act on NADH or NADPH are also preferred.
  • the acceptors here are NADP (1.6.1), heme proteins (1.6.2), disulfides (1.6.4), quinones (1.6.5), N0 2 groups (1.6.6), and a flavin (1.6.8) or some other acceptors (1.6.99).
  • Enzymes of class 1.6.5 with quinones as acceptors are particularly preferred here.
  • class 1.7 enzymes which act as donors on other N0 2 compounds and acceptors cytochrome (1.7.2), oxygen (0 2 ) (1.7.3), iron-sulfur proteins (1.7.7 ) or others (1.7.99).
  • class 1.8 enzymes which act as donors on sulfur groups and acceptors NAD + , NADP (1.8.1), cytochromes (1.8.2), oxygen (0 2 ) (1.8.3), disulfides (1.8 .4), quinones (1.8.5), iron-sulfur proteins (1.8.7) or others (1.8.99).
  • Class 1.8.3 with oxygen is particularly preferred and (1.8.5) with quinones as acceptors.
  • class 1.9 enzymes which act as donors on heme groups and oxygen as acceptors
  • class 1.12 enzymes which act as a donor on hydrogen.
  • the acceptors are NAD or NADP + (1.12.1) or others (1.12.99). Enzymes of class 1.13 and 1.14 (oxigenases) are also preferred.
  • Preferred enzymes are also those of class 1.15 which act as acceptors on superoxide radicals.
  • Superoxide dismutase (1.15.1.1) is particularly preferred here.
  • Enzymes of class 1.16 are also preferred.
  • Enzymes of class 1.16.3.1 (ferroxidase, e.g. Ceruloplas in) are particularly preferred here.
  • Further preferred enzymes are those of group 1.17 (action on CH 2 groups which are oxidized to -CHOH-), 1.18 (action on reduced ferredoxin as donor), 1.19 (action on reduced flavodoxin as donor) and 1.97 (others Oxidoreductases).
  • the enzymes of group 1.11 are also particularly preferred. which act on a peroxide as an acceptor. This only subclass (l.ll.l) contains the peroxidases.
  • the cytochrome C peroxidases (1.11.1.5), catalase (1.11.1.6), the peroxidase (1.11.1.6), the iodide peroxidase (1.11.1.8) and the glutathione peroxidase (1.11.1.9) are particularly preferred here.
  • Enzymes of class 1.10 which act on biphenols and related compounds are very particularly preferred. They catalyze the oxidation of biphenols and ascorbates. NAD + , NADP + (1.10.1), cytochrome (1.10.2), oxygen (1.10.3) or others (1.10.99) act as acceptors.
  • class 1.10.3 enzymes with oxygen (0 2 ) as the acceptor are particularly preferred.
  • the enzymes in this class are catechol oxidase (tyrosinase) (1.10.3.1), L-ascorbate oxidase (1.10.3.3), o-aminophenol oxidase (1.10.3.4) and laccase (benzenediol: oxigen oxidoreductase) (1.10.3.2 ) is preferred, with the laccases (benzene diol: oxigen oxidoreductase) (1.10.3.2) being particularly preferred.
  • the enzymes mentioned are commercially available or can be obtained by standard methods. Plants, animal cells, bacteria and fungi, for example, come into consideration as organisms for the production of the enzymes. Basically, both naturally occurring and genetically modified organisms can be enzyme producers. Parts of unicellular or multicellular organisms are also conceivable as enzyme producers, especially cell cultures.
  • white rot fungi such as pleurus, phlebia and trametes are used, for example.
  • the multi-component system according to the invention comprises at least one oxidizing agent.
  • oxidizing agents are air, oxygen, ozone, H 2 0 2 , organic peroxides, peracids such as peracetic acid, performic acid, persulfuric acid, persitric acid, metachloroperoxybenzoic acid, perchloric acid, perborates, peracetates, persulfates, peroxides or oxygen species and their radicals such as OH, OOH, Singlet oxygen, superoxide (0 2 ⁇ ), ozonide, dioxygenyl cation (0 2 + ), dioxiranes, dioxetanes or fremy radicals can be used.
  • oxidizing agents are used which can either be generated by the corresponding oxidoreductases e.g. Dioxiranes from laccases plus carbonyls or which can chemically regenerate the mediator or implement it directly.
  • oxidoreductases e.g. Dioxiranes from laccases plus carbonyls or which can chemically regenerate the mediator or implement it directly.
  • the invention also relates to the use of substances which, according to the invention, are suitable as mediators for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances.
  • Mg 2+ ions can be used as a salt, such as MgS0 4 , at.spi.elswei.se.
  • concentration is in the range of 0.1-2 mg / g lignin-containing. Material, preferably at 0.2-0.6 mg / g.
  • the multicomponent system in addition to the Mg 24 ions also complexing agents such as e.g. Contains ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenedia diacetic acid (HEDTA), diethylenetriapentamethylenephosphonic acid (DTMPA), nitrilotriacetic acid (NTA), polyphosphoric acid (PPA) etc.
  • the concentration is in the range of 0.2-5 mg / g of lignin-containing material, preferably 1-3 mg.
  • the use of the multicomponent system according to the invention in a process for treating lignin takes place, for example, in that the components a) to c) mixes according to claim 1 simultaneously or in any order with an aqueous suspension of the lignin-containing material.
  • a process using the multicomponent system according to the invention is preferred in the presence of oxygen or air at atmospheric pressure up to 10 bar and in a pH range from 2 to 11, at a temperature of 20 to 95 ° C., preferably 40-95 ° C. , and a consistency of 0.5 to 40%.
  • a process according to the invention is preferably carried out at consistencies of 8 to 35%, particularly preferably 9 to 15%.
  • the substances used for this purpose are used as chelating agents in the Q stage. They are preferably used in concentrations of 0.1% to 1% (w / w based on dry cellulose), particularly preferably 0.1% to 0.5% (w / w based on dry cellulose).
  • preferably 0.01 to 100,000 IU enzyme per g lignin-containing material are used. It is particularly preferred to use 0.1 to 100, particularly preferably 1 to 40 IU enzyme per g lignin-containing material (1 U corresponds to the conversion of 1 ⁇ mol 2,2'-Azino-bis (3-ethyl-benzothiazoline-6-sulfonic acid diammonium salt) (ABTS) / min / ml enzyme).
  • ABTS 2,2'-Azino-bis (3-ethyl-benzothiazoline-6-sulfonic acid diammonium salt)
  • oxidizing agent preferably 0.01 mg to 100 mg of oxidizing agent are used per g of lignin-containing material. 0.01 to 50 mg of oxidizing agent per g of lignin-containing material are particularly preferably used.
  • 0.5 to 80 mg of mediator per g of lignin-containing material is preferably used.
  • 0.5 to 40 mg of mediator per g of lignin-containing material is particularly preferably used.
  • reducing agents can be added which, together with the existing oxidizing agents, serve to set a certain redox potential.
  • Sodium bisulfite, sodium dithionite, ascorbic acid, thio compounds, mercapto compounds or glutathione etc. can be used as reducing agents.
  • the reaction takes place with air or oxygen supply or oxygen or air overpressure, with the peroxidases (e.g. lignin peroxidases, manganese peroxidases) with hydrogen peroxide.
  • the peroxidases e.g. lignin peroxidases, manganese peroxidases
  • the oxygen can also be generated in situ by hydrogen peroxide + catalase and hydrogen peroxide by glucose + GOD or other systems.
  • radical formers or radical scavengers can be added to the system. These can improve the interaction within the Red / Ox and radical mediators.
  • metal salts can also be added to the reaction solution. These are important in conjunction with chelating agents as radical formers or red / ox centers.
  • the salts form cations in the reaction solution.
  • Such ions include Fe 24-, Fe3 + '
  • the chelates present in the solution can also act as mimic substances for the enzymes, for example for the
  • Laccases copper complexes
  • lignin or manganese peroxidases heme complexes
  • Mimic substances are to be understood as substances that the prosthetic groups of
  • NaOCl can also be added to the reaction mixture. In combination with hydrogen peroxide, this compound can form singlet oxygen.
  • Non-ionic, anionic, cationic and amphoteric surfactants are suitable as such.
  • the detergents can improve the penetration of the enzymes and mediators into the fiber.
  • Glucans, mannans, dextrans, levans, pectins, alginates or plant gums and / or proprietary polysaccharides formed by the fungi or produced in a mixed culture with yeasts are to be mentioned here in particular as polysaccharides and gelatin and albumin as proteins.
  • proteases such as pepsin, bromelin, papain, etc. These can serve, inter alia, to achieve better access to lignin by breaking down the extensin C present in the wood, hydroxyproline-rich protein.
  • Amino acids, simple sugars, oligomer sugars, PEG types of the most varied molecular weights, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes can be considered as further protective colloids.
  • the method according to the invention can be used not only in the delignification (bleaching) of sulfate, sulfite, organosol, etc. Pulp and wood pulp are used, but also in the production of pulp in general, whether from wood or annual plants, if defibrillation by the usual cooking methods (possibly connected with mechanical processes or pressure) i.e. a very gentle cooking up to kappa numbers, which can be in the range of approx. 50 - 120 kappa, is guaranteed.
  • the treatment can be repeated several times, either after washing and extraction of the treated material with NaOH or without these intermediate steps. This leads to kappa values which can be reduced still further and to substantial increases in whiteness.
  • a 0 2 stage can be used before the enzyme / mediator treatment or, as already mentioned, an acid wash or Q stage (chelate stage) can be carried out.
  • Solutions A and B are added together and made up to 33 ml. After adding the pulp, mix with a dough kneader for 2 min.
  • the substance is then placed in a reaction bomb preheated to 45 ° C and incubated under 1-10 bar oxygen pressure for 1-4 hours.
  • the material is then washed over a nylon sieve (30 ⁇ ) and extracted for 1 hour at 60 ° C., 2% consistency and 8% NaOH per g of pulp.
  • the fabric is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C., 2% fabric density and 8% NaOH per g of pulp.
  • Example 5 Enzymatic bleaching with l-nitroso-2-naphthol-3,6-disulfonic acid and Softwood sulfate pulp
  • Solutions A and B are added together and made up to 33 ml. After adding the pulp, mix with a dough kneader for 2 min.
  • the substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar oxygen pressure for 1-4 hours.
  • the material is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C., 2% consistency and 8% NaOH per g of pulp.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un système à plusieurs composants servant à modifier, décomposer ou blanchir de la lignine, des matériaux contenant de la lignine ou des substances analogues contenant a) éventuellement au moins un catalyseur d'oxydation et b) au moins un agent d'oxydation approprié et c) au moins un médiateur, qui se caractérise en ce que le médiateur est sélectionné dans le groupe des alcools aromatiques à substitution nitroso vicinale des formules générales (Ia) ou (Ib), ainsi que leurs sels, éthers ou esters.
PCT/EP1997/004173 1996-08-01 1997-07-31 Systeme a plusieurs composants pour modifier, decomposer ou blanchir de la lignine, des materiaux contenant de la lignine ou des substances analogues et procede permettant de l'utiliser WO1998005818A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU38506/97A AU3850697A (en) 1996-08-01 1997-07-31 Multi-component system for modifying, decomposing, or bleaching lignin, lignin-containing materials or similar substances and process for its application

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19631131.4 1996-08-01
DE1996131131 DE19631131A1 (de) 1996-08-01 1996-08-01 Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen sowie Verfahren zu seiner Anwendung

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Publication Number Publication Date
WO1998005818A1 true WO1998005818A1 (fr) 1998-02-12

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000014195A1 (fr) * 1998-09-04 2000-03-16 Unilever N.V. Compositions de blanchiment

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2569660T3 (es) 2007-06-08 2016-05-12 Mannkind Corporation Inhibidores de la IRE-1alfa

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992020857A1 (fr) * 1991-05-17 1992-11-26 Call Hans Peter Procede a rendement ameliore pour la delignification de produits lignocellulosiques, ainsi que pour le blanchiment et le traitement d'eaux residuaires au moyen de laccases
WO1995001426A1 (fr) * 1993-06-29 1995-01-12 Novo Nordisk A/S Renforcement de reactions aux laccases
EP0717143A1 (fr) * 1994-12-16 1996-06-19 Lignozym GmbH Système à plusieurs composants pour modifier, dégrader ou blanchir la lignine, des matériaux contenant de la lignine ou des produits similaires de même que leur procédé d'utilisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992020857A1 (fr) * 1991-05-17 1992-11-26 Call Hans Peter Procede a rendement ameliore pour la delignification de produits lignocellulosiques, ainsi que pour le blanchiment et le traitement d'eaux residuaires au moyen de laccases
WO1995001426A1 (fr) * 1993-06-29 1995-01-12 Novo Nordisk A/S Renforcement de reactions aux laccases
EP0717143A1 (fr) * 1994-12-16 1996-06-19 Lignozym GmbH Système à plusieurs composants pour modifier, dégrader ou blanchir la lignine, des matériaux contenant de la lignine ou des produits similaires de même que leur procédé d'utilisation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000014195A1 (fr) * 1998-09-04 2000-03-16 Unilever N.V. Compositions de blanchiment

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DE19631131A1 (de) 1998-02-05
AU3850697A (en) 1998-02-25

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