WO1996018770A2 - Systeme a plusieurs constituants pour modifier, degrader ou blanchir la lignine, les matieres contenant de la lignine ou analogues et procedes d'utilisation - Google Patents

Systeme a plusieurs constituants pour modifier, degrader ou blanchir la lignine, les matieres contenant de la lignine ou analogues et procedes d'utilisation Download PDF

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Publication number
WO1996018770A2
WO1996018770A2 PCT/EP1995/004965 EP9504965W WO9618770A2 WO 1996018770 A2 WO1996018770 A2 WO 1996018770A2 EP 9504965 W EP9504965 W EP 9504965W WO 9618770 A2 WO9618770 A2 WO 9618770A2
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WO
WIPO (PCT)
Prior art keywords
triazolo
alkyl
acid
esters
salts
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Application number
PCT/EP1995/004965
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German (de)
English (en)
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WO1996018770A3 (fr
Inventor
Hans-Peter Call
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Lignozym Gmbh
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Priority to JP08518274A priority Critical patent/JP3107828B2/ja
Priority to NZ300571A priority patent/NZ300571A/en
Priority to RU96118245A priority patent/RU2142479C1/ru
Priority to AU45350/96A priority patent/AU688660B2/en
Priority to EP95944012A priority patent/EP0745154B1/fr
Priority to SK1040-96A priority patent/SK104096A3/sk
Priority to BR9506801A priority patent/BR9506801A/pt
Priority to DE59503612T priority patent/DE59503612D1/de
Application filed by Lignozym Gmbh filed Critical Lignozym Gmbh
Priority to DK95944012T priority patent/DK0745154T3/da
Priority to KR1019960704448A priority patent/KR100197048B1/ko
Publication of WO1996018770A2 publication Critical patent/WO1996018770A2/fr
Priority to NO963410A priority patent/NO963410L/no
Priority to FI963210A priority patent/FI963210A0/fi
Publication of WO1996018770A3 publication Critical patent/WO1996018770A3/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. With both methods, cooking and under pressure Produces pulp.
  • the sulfate process works with the addition of NaOH and Na 2 S, while 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 cellulose and hemicellulose, must be removed, otherwise it will not be possible to produce non-yellowing and mechanically heavy-duty papers.
  • the wood-based production 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).
  • stone grinders wood sanding
  • TMP refiners
  • Phanerochaete chrysosporium is a very effective lignin degrader, attempts were made to isolate its enzymes and to use them in purified form for lignin degradation. However, this did not succeed because it turned out that the enzymes primarily lead to a repolymerization of the lignin and not to its degradation.
  • Biopulping is the treatment of wood chips with living fungal systems.
  • the goal here is to reduce cooking chemicals, improve cooking capacity and "extended cooking”.
  • 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 is the treatment of pulp wastewater, in particular bleaching wastewater, to decolorize it and reduce the AOX (reduction of chlo compounds in wastewater that cause chlorine or chlorine dioxide bleaching stages).
  • the possible structure of hard coal shows a three-dimensional network of polycyclic, aromatic ring systems with a "certain" similarity to lignin structures.
  • chelate substances siderophores such as ammonium oxalate
  • biosurfactants are believed to be cofactors.
  • 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.
  • Mimic substances that simulate the active center (prosthetic group) of lignolytic enzymes added. In this way, a significant improvement in performance could be achieved.
  • the enhancer substances are characterized in WO 94/12619 on the basis of their half-life.
  • enhancer substances are organic chemicals which contain at least two aromatic rings, at least one of which is substituted with defined radicals.
  • the object of the present invention is to provide a system for changing, breaking down or bleaching lignin containing lignin To provide materials or similar substances that are more effective than known systems.
  • the object is achieved by a multi-component system, which is characterized in that it a. optionally at least one oxidation catalyst and b. at least one suitable oxidizing agent and c. selects at least one mediator from the group of hydroxylamines, hydroxylamine derivatives, hydroxamic acids,
  • Hydroxamic acid derivatives the aliphatic, cycloaliphatic, heterocyclic or aromatic compounds, which contain at least one N-hydroxy, oxime, N-oxi or N, N'-dioxi function and d. optionally at least one comediator from the group of aryl-substituted alcohols, carbonyl compounds, aliphatic ethers, phenol ethers and / or olefins (alkenes) and e. comprises a small amount of at least one free amine of a mediator used in each case.
  • the multicomponent system according to the invention preferably comprises at least one oxidation catalyst.
  • the multicomponent system according to the invention preferably comprises at least one comediator.
  • 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.
  • Oxidoreductases of classes 1.1.1 to 1.97 according to the International Enzyme Nomenclature, Committee of the International Union of Biochemistry and Molecular Biology (Enzyme Nomenclature, Academic Press, Inc., 1992, pp. 24-154) can be used as the enzyme in the multicomponent system according to the invention .
  • 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 are accepted as acceptors NAD + or NADP + (subclass 1.1.1), cytochromes (1.1.2), oxygen (O 2 ) (1.1 .3), disulfides (1.1.4), quinones (1.1.5) or other acceptors (1.1.99).
  • the enzymes of class 1.1.5 with quinones as acceptors and the enzymes of class 1.1.3 with oxygen as acceptors are particularly preferred.
  • Cellobiose is particularly preferred in this class:
  • Enzymes of class 1.2 are also preferred.
  • This class of enzymes (1.1.5.1) includes those enzymes that oxidize aldehydes to the corresponding acids or oxo groups.
  • the acceptors can be NAD + , NADP + (1.2.1), cytochrome (1.2.2), oxygen (1.2.3), sulfides (1.2.4), iron-sulfur proteins (1.2.5) or other acceptors (1.2 .99).
  • the enzymes of group (1.2.3) with oxygen as the acceptor are particularly preferred here.
  • Enzymes of class 1.3 are also preferred
  • This class includes enzymes that target
  • acceptors are NAD + , NADP + (1.3.1), cytochromes (1.3.2), oxygen (1.3.3), quinones or related compounds (1.3.5), iron-sulfur proteins (1.3.7) or other acceptors (1.3.99).
  • 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. Also preferred are 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), disulfide (1.4.4), iron-sulfur proteins (1.4.7) or other acceptors
  • 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 (O 2 ) (1.5.3) and with quinones (1.5.5) are particularly preferred as acceptors.
  • Enzymes of class 1.6 which act on NADH or NADPH are also preferred.
  • acceptors here are NADP + (1.6.1), heme proteins (1.6.2), disulfides (1.6.4), quinones (1.6.5), NO 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. Also preferred are class 1.7 enzymes which act as donors on other NO 2 compounds and as acceptors cytochromes (1.7.2), oxygen (O 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 NAD + , NADP + (1.8.1), cytochromes (1.8.2), oxygen (O 2 ) (1.8.3), disulfides (1.8. 4), quinones (1.8.5), iron-sulfur proteins (1.8.7) or others (1.8.99).
  • class 1.9 enzymes which act as donors on heme groups and have oxygen (O 2 ) (1.9.3), NO 2 compounds (1.9.6) and others (1.9.99) as acceptors.
  • class 1.12 enzymes which act on hydrogen as a donor.
  • 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.
  • Enzymes of class 1.16 are also preferred.
  • Enzymes of class 1.16.3.1 (ferroxidase, e.g. ceruloplasmin) 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 (1.11.1) 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.
  • the chloride peroxidase (1.11.1.10), the L-ascorbate peroxidase (1.11.1.11), the phospholipid hydroperoxide-glutathione peroxidase (1.11.1.12), the manganese peroxidase (1.12.1.13), the diarylpropane Peroxidase (ligninase, lignin peroxidase) (1.11.1.14).
  • 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 act as acceptors
  • class 1.10.3 enzymes with oxygen (O 2 ) as the acceptor are particularly preferred.
  • the enzymes in this class are catechol oxidase (tyrosinase) (1.10.3.1), L-ascorbate oxidase
  • laccase (benzenediol: oxigen oxidoreductase)
  • enzymes are commercially available or can be obtained using 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 as well as genetically modified organisms are enzyme producers. Parts of unicellular or multicellular organisms are also conceivable as enzyme producers, especially cell cultures.
  • White rot fungi such as pleurotus, phlebia and trametes are used, for example, for the particularly preferred enzymes, such as those from group 1.11.1, but especially 1.10.3, and in particular for the production of laccases.
  • the multi-component system according to the invention comprises at least one oxidizing agent.
  • the oxidizing agents that can be used are, for example, air, oxygen, ozone, H 2 O 2 , organic peroxides, peracids such as peracetic acid, performic acid, persulfuric acid, persitric acid, metachloroperoxibenzoic acid, perchloric acid, perborates, peracetates, persulfates, peroxides or oxygen species and their radicals such as OH, OOH, Singlet oxygen, superoxide (O 2 -), ozonide, dioxygenyl cation
  • 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 (e.g. Caro's acid + benzotriazole gives hydroxybenztriazole) or can directly convert it.
  • oxidoreductases e.g. Dioxiranes from laccases plus carbonyls or which can chemically regenerate the mediator (e.g. Caro's acid + benzotriazole gives hydroxybenztriazole) or can directly convert it.
  • the multicomponent system according to the invention preferably comprises at least one compound as mediator (component c), which contains at least one N-hydroxyl, oxime, N-oxi or N-dioxi function and / or one of the compounds of the formula I, II, III, IV or V mentioned below, where the compounds of the formulas II, III, IV and V are preferred, the compounds of the formula III, IV and V are particularly preferred and compounds of the formula IV and V are particularly preferred.
  • component c which contains at least one N-hydroxyl, oxime, N-oxi or N-dioxi function and / or one of the compounds of the formula I, II, III, IV or V mentioned below, where the compounds of the formulas II, III, IV and V are preferred, the compounds of the formula III, IV and V are particularly preferred and compounds of the formula IV and V are particularly preferred.
  • Hydroxylamines (open-chain or cyclic, aliphatic or aromatic, heterocyclic) of the general formula I
  • the substituents R 1 and R 2 which may be the same or different, independently of one another represent one of the following groups: hydrogen, C 1 -C 12 -alkyl-, carbonyl-C 1 -C 6 -alkyl- , phenyl, aryl, the C 1 -C 12 alkyl, carbonyl-C 1 -C 6 alkyl, phenyl, aryl unsubstituted or further substituted one or more times with the radical R 3 and wherein the radical R 3 can represent one of the following groups: hydrogen, halogen, hydroxyl, formyl, carboxy and salts and esters thereof, amino, nitro, C 1 -C 12 alkyl, C 1 -C 6 alkyloxy , carbonyl-C 1 -C 6 -alkyl-, phenyl-, sulfono-, their esters and salts, sulfamoyl-, carbamoyl-, phospho-,
  • radicals R 9 to R 12 , R 15 and R 16 can be identical or different and can independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C 1 -C 12 alkyl, C 1 -C 6 alkyloxy, carbonyl-C 1 -C 5 alkyl, phenyl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and where the amino, carbamoyl and sulfamoyl groups of the radicals R 9 to R 12 , R 15 and R 16 can furthermore be unsubstituted or mono- or disubstituted by hydroxy, C 1 -C 3 alkyl, C 1 -C 3 alkoxy , and wherein the radicals R 15 and R 16 can form a common group -G- and -G-
  • the radicals R 5 to R 8 can be identical or different and, independently of one another, represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C 1 -C 12 alkyl, C 1 -C 6 -alkyloxy, carbonyl-C 1 -C 6 -alkyl, phenyl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and wherein the amino-, carbamoyl- and sulfamoyl- Groups of the radicals R 5 to R 8 further may be unsubstituted or mono- or disubstituted with hydroxy, C 1 -C 3 alkyl, C 1 -C 3 alkoxy and where the C 1 -C 12 alkyl, C 1 -C 6 alkyloxy, carbonyl -C
  • Groups can be: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C 1 -C 12 alkyl, C 1 -C 6 alkyloxy, carbonyl-C 1 -C 6 alkyl, phenyl, aryl .
  • the radicals R 5 to R 12 can be identical or different and, independently of one another, represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C 1 -C 12 alkyl, C 1 -C 6 -alkyloxy, carbonyl-C 1 -C 6 -alkyl, phenyl, aryl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and where the amino, carbamoyl and sulfamoyl groups of the radicals R 5 to R 12 may furthermore be unsubstituted or mono- or disubstituted by hydroxy, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy and where the C 1 -C 12 -alkyl-, C 1 -C 6 -alky
  • Hydrogen, halogen, hydroxy, formyl, carboxy and their Salts and esters amino, nitro, C 1 -C 12 alkyl, C 1 -C 6 alkyloxy, carbonyl-C 1 -C 6 alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and their esters and salts and where the carbamoyl, sulfamoyl, amino groups of the radical R 13 can be unsubstituted or can furthermore be mono- or disubstituted by the radical R 14 and the radical R 14 can be one of the following groups: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C 1 -C 12 alkyl, C 1 -C 6 alkyloxy, carbonyl-C 1 -C 6 alkyl, phenyl, aryl.
  • R 17 can be: hydrogen, C 1 -C 10 alkyl, C 1 -C 10 alkylcarbonyl, their C 1 -C 10 alkyl and C 1 -C 10 alkylcarbonyl unsubstituted or with a radical R 18 which , like R 3 is defined, can be substituted one or more times.
  • the radicals R 5 to R 8 can be identical or different and, independently of one another, represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C 1 -C 12 alkyl, C 1 -C 6 -alkyloxy, carbonyl-C 1 -C 6 -alkyl, phenyl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and wherein the amino-, carbamoyl- and sulfamoyl- Groups of the radicals R 5 to R 8 can furthermore be unsubstituted or mono- or disubstituted by hydroxy, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy and where the C 1 -C 12 -alkyl-, C 1 -C 6 -al
  • heterocycles which contain at least one N-hydroxy, oxime, N-oxy, N, N-dioxy function or a further heteroatom, such as O, S, Se, Te, such as:
  • condensed N-heterocycles such as triazolo and tetrazolo compounds which have at least one N-hydroxy, oxime, N-oxi, N, N-dioxi function and in addition to N a further heteroatom such as O, S, Se, Te can contain.
  • the multi-component system (d) comprises, for example, aliphatic ethers, aryl-substituted alcohols such as e.g.
  • the reaction is mediated in cascade form or the actual mediator compounds are recycled in situ, i.e. during the reaction and surprisingly leads to a substantial improvement in kappa reduction or a reduction in mediator dosage.
  • the additives mentioned under d) in claim 1 are preferably used in amounts of 0.01 to 0.5 mg per g of lignin-containing material. 0.01 to 0.1 mg per g of lignin-containing material are particularly preferably used.
  • the free amine of the respective mediator is preferably used in a mediator / amine ratio of 100: 1 to 1: 1, particularly preferably 20: 1 to 1: 1, particularly preferably 10: 1 to 2: 1.
  • Mg 2+ ions can be used, for example, as a salt, such as MgSO 4 .
  • concentration is in the range of 0.1-2 mg / g of lignin-containing material, preferably 0.2-0.6 mg / g.
  • a further increase in the effectiveness of the multicomponent system according to the invention can be achieved in that the multicomponent system, in addition to the Mg 2+ ions, also complexing agents such as, for example, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediamine triacetic acid (HEDTA), diethylenetriaminepentamethylene (phosphinetriaminepentamethylene 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 merh component system according to the invention is used in a process for treating lignin, for example, by mixing the respectively selected components a) to e) according to claim 1 simultaneously or in any order with an aqueous suspension of the lignin-containing material.
  • a method using the multicomponent system according to the invention in the presence of acid is preferred fabric or air at normal pressure up to 10 bar and in a pH range of 2 to 11, at a temperature of 20 to 95 ° C, preferably 40 - 95 ° C, and a consistency of 0.5 to 40%.
  • a finding that is unusual and surprising for the use of enzymes in pulp bleaching is that when the multicomponent system according to the invention is used, a
  • a process according to the invention is preferably carried out at consistencies of 12 to 15%, particularly preferably 14 to 15%.
  • preferably 100 to 100,000 IU enzyme per g lignin-containing material are used. 1,000 to 40,000 IU enzyme per g lignin-containing material are particularly preferably used.
  • 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 oxidizing agents present, 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, for example, in the case of laccase with the addition of oxygen or oxygen pressure, in the case of the peroxidases (for example lignin peroxidases, manganese peroxidases) with hydrogen peroxide.
  • the peroxidases for example 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.
  • the salts form cations in the reaction solution.
  • Such ions include Fe 2+ , Fe 3+ , Mn 2+ , Mn 3+ , Mn 4+ , Cu 2+ , Ca 2+ , Ti 3+ , Cer 4+ , Al 3+ .
  • the chelates present in the solution can also serve as mimic substances for the enzymes, for example for the laccases (copper complexes) or for the lignin or manganese peroxidases (heme complexes).
  • Mimic substances are substances that simulate the prosthetic groups of (here) oxidoreductases and can catalyze oxidation reactions, for example. 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.
  • polysaccharides are glucans, mannans, dextrans, levans,
  • Pectins alginates or plant gums and / or own polysaccharides formed by the fungi or produced in the mixed culture with yeasts and to name gelatin and albumin as proteins.
  • proteases such as pepsin, bromelin, papain, etc. These can include serve to achieve better access to lignin by breaking down the extensin C present in the wood, a protein rich in hydroxyproline.
  • protective colloids are amino acids, simple sugar, oligomer sugar, PEG types of various moles molecular weights, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes in question.
  • the process 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.
  • an O 2 stage can be used before the enzyme / mediator treatment or, as already mentioned, an acid wash or a Q stage (chelate stage) can be carried out.
  • Example 1/2 Enzymatic bleach and sulfate pulp.
  • the substance is then placed in a reaction bomb preheated to 45 ° C and incubated under 1-10 bar pressure for 1-4 hours.
  • the fabric is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C, 8% fabric density and 2% NaOH per g fabric.
  • the kappa number is determined.
  • the substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar overpressure for 1-4 hours.
  • the fabric is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C., 8% fabric density and 2% NaOH per g fabric.
  • Q stage 120 ml of tap water are mixed with 90 mg of DTPA and the pH is adjusted with 0.5 m of H2SO 4 so that pH 4.5 results after the addition of the cellulose.
  • the solution is made up to 200 ml and mixed for 2 min with a dough kneader.
  • the fabric is then left in a sealed beaker at 90 ° C.
  • Laccase / extraction stage 120 ml of tap water are included
  • the substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar pressure for 1-4 hours.
  • the fabric is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C, 8% fabric density and 2% NaOH per g fabric.
  • the kappa number is determined.
  • the kappa number is determined according to the Q level. The results are shown in Table 4.
  • the substance is then placed in a reaction bomb preheated to 45 ° C and incubated under 1-10 bar pressure for 1-4 hours.
  • the fabric is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C, 8% fabric density and 2% NaOH per g fabric.
  • the kappa number is determined.
  • the fabric is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C., 8% fabric density and 2% NaOH per g fabric.
  • the substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar pressure for 1-4 hours.
  • the fabric is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C, 8% fabric density and 2% NaOH per g fabric.
  • the kappa number is determined.
  • the fabric is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C., 8% fabric density and 2% NaOH per g fabric.
  • the kappa number is determined.
  • the substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar pressure for 1-4 hours.
  • the fabric is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C, 8% fabric density and 2% NaOH per g fabric.
  • the kappa number is determined.
  • the substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar pressure for 1-4 hours.
  • the fabric is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C, 8% fabric density and 2% NaOH per g fabric.
  • enzyme + mediator is added without washing, mixed (2 min) and the reaction is carried out again (same metering as in the first treatment).
  • the reaction is carried out again by adding all components.
  • the substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar pressure for 1-4 hours.
  • the fabric is then washed over a nylon sieve (30 ⁇ m).

Abstract

La présente invention concerne un système à plusieurs constituants pour modifier, dégrader ou blanchir la lignine, les matières contenant de la lignine ou analogues et des procédés d'utilisation de ce système. Ce système à plusieurs constituants se caractérise en ce qu'il contient: a) le cas échéant, au moins un catalyseur d'oxydation et b) au moins un oxydant approprié et c) au moins un médiateur sélectionné dans le groupe des hydroxylamines, dérivés d'hydroxylamines, acides hydroxamiques, dérivés d'acides hydroxamiques, des composés aliphatiques, cycloaliphatiques, hétérocycliques ou aromatiques qui comportent au moins une fonction N-hydroxy, oxime, N-oxy ou N, N'-dioxy et d) le cas échéant, au moins un comédiateur appartenant au groupe des alcools aromatiques, des composés carbonyles, des éthers aliphatiques, des phénoléthers et/ou des oléfines (alkènes) et e) une faible quantité d'au moins une amine libre d'un médiateur mis en ÷uvre dans chaque cas considéré.
PCT/EP1995/004965 1994-12-16 1995-12-15 Systeme a plusieurs constituants pour modifier, degrader ou blanchir la lignine, les matieres contenant de la lignine ou analogues et procedes d'utilisation WO1996018770A2 (fr)

Priority Applications (12)

Application Number Priority Date Filing Date Title
BR9506801A BR9506801A (pt) 1994-12-16 1995-12-15 Sistema de vários componentes para alterar degradar ou alvejar lignina materiais contendo lignina ou substâncias similares bem como processo para a sua aplicação
RU96118245A RU2142479C1 (ru) 1994-12-16 1995-12-15 Многокомпонентная система для изменения, разложения или отбеливания лигнина, содержащих лигнин материалов или угля и способ ее применения
AU45350/96A AU688660B2 (en) 1994-12-16 1995-12-15 Multicomponent system for modifying, decomposing or bleaching lignin, lignin-containing materials or similar substances and method of using this system
EP95944012A EP0745154B1 (fr) 1994-12-16 1995-12-15 Systeme a plusieurs constituants pour modifier, degrader ou blanchir la lignine, les matieres contenant de la lignine ou analogues et procedes d'utilisation
SK1040-96A SK104096A3 (en) 1994-12-16 1995-12-15 Multicomponent system for modifying, decomposing or bleaching lignin, lignin-containing materials or similar substances and method of using this system
JP08518274A JP3107828B2 (ja) 1994-12-16 1995-12-15 リグニンまたはリグニン含有物質を変化させるか、分解するか、または漂白するための組成物
DE59503612T DE59503612D1 (de) 1994-12-16 1995-12-15 Mehrkomponentensystem zum verändern, abbau oder bleichen von lignin, ligninhaltigen materialien oder ähnlichen stoffen sowie verfahren zu seiner anwendung
NZ300571A NZ300571A (en) 1994-12-16 1995-12-15 Multicomponent system for treating lignocellulose material
DK95944012T DK0745154T3 (da) 1994-12-16 1995-12-15 Flerkomponentsystem til ændring, nedbrydning eller blegning af lignin, ligninholdige materialer eller lignende stoffer samt
KR1019960704448A KR100197048B1 (ko) 1994-12-16 1995-12-15 리그닌, 리그닌함유재 또는 그 동일물질을 개질, 분해 또는 표백하는 조성물
NO963410A NO963410L (no) 1994-12-16 1996-08-15 Flerkomponentsystem for å modifisere, nedbryte eller bleke lignin, ligninholdige materialer eller tilsvarende stoffer, samt fremgangsmåte for anvendelse av dette
FI963210A FI963210A0 (fi) 1994-12-16 1996-08-16 Monikomponenttinen systeemi ligniinin, ligniinipitoisten aineiden tai samankaltaisten aineiden muuttamiseksi tai valkaisemiseksi sekä systeemin käyttömenetelmä

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP94119981A EP0717143A1 (fr) 1994-12-16 1994-12-16 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
EP94119981.2 1994-12-16

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WO1996018770A2 true WO1996018770A2 (fr) 1996-06-20
WO1996018770A3 WO1996018770A3 (fr) 1996-08-22

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PCT/EP1995/004965 WO1996018770A2 (fr) 1994-12-16 1995-12-15 Systeme a plusieurs constituants pour modifier, degrader ou blanchir la lignine, les matieres contenant de la lignine ou analogues et procedes d'utilisation

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EP (2) EP0717143A1 (fr)
JP (1) JP3107828B2 (fr)
KR (1) KR100197048B1 (fr)
CN (1) CN1142255A (fr)
AT (1) ATE171228T1 (fr)
AU (1) AU688660B2 (fr)
BR (1) BR9506801A (fr)
CA (1) CA2164394A1 (fr)
CZ (1) CZ243896A3 (fr)
DE (1) DE59503612D1 (fr)
DK (1) DK0745154T3 (fr)
ES (1) ES2122722T3 (fr)
FI (1) FI963210A0 (fr)
HU (1) HU215542B (fr)
NO (1) NO963410L (fr)
NZ (1) NZ300571A (fr)
PL (1) PL315913A1 (fr)
RU (1) RU2142479C1 (fr)
SK (1) SK104096A3 (fr)
TW (1) TW360729B (fr)
WO (1) WO1996018770A2 (fr)

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WO1998044189A1 (fr) * 1997-03-31 1998-10-08 Whitmire David R Decoloration enzymatique de pates de bois
KR19990023911A (ko) * 1997-08-28 1999-03-25 에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러 제조 도중에 리그닌 함유 펄프를 증백시키는 방법
DE19842662A1 (de) * 1998-09-17 2000-03-30 Consortium Elektrochem Ind Zusammensetzung und Verfahren zum Verändern, Abbau oder Bleichen von ligninhaltigen Materialien
US6087135A (en) * 1997-12-19 2000-07-11 Novo Nordisk A/S Modification of polysaccharides by means of a phenol oxidizing enzyme
WO2001031066A1 (fr) * 1999-10-28 2001-05-03 Kabushiki Kaisha Toyota Chuo Kenkyusho Procede, appareil et enzyme de reaction chimique
WO2003061550A2 (fr) * 2002-01-26 2003-07-31 Call, Krimhild Nouvelles activites catalytiques d'oxydo-reductases pour l'oxydation et/ou le blanchiment
EP0825294B2 (fr) † 1996-08-13 2005-02-09 Consortium für elektrochemische Industrie GmbH Système à plusieurs constituants pour modifier, dégrader ou blanchir la lignine, ou les matières contenant de la lignine ainsi que procédés l'utilisant
US7037909B2 (en) 2003-07-02 2006-05-02 Sugen, Inc. Tetracyclic compounds as c-Met inhibitors
US8343977B2 (en) 2009-12-30 2013-01-01 Arqule, Inc. Substituted triazolo-pyrimidine compounds
US9221756B2 (en) 2011-12-05 2015-12-29 University Of Leicester Pyrrole derivatives
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994012621A1 (fr) * 1992-12-01 1994-06-09 Novo Nordisk Amelioration de reactions enzymatiques
WO1994029510A1 (fr) * 1993-06-16 1994-12-22 Lignozym Gmbh Procede de modification, de degradation ou de blanchiment de la lignine, de materiaux contenant de la lignine ou de produits similaires

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994012621A1 (fr) * 1992-12-01 1994-06-09 Novo Nordisk Amelioration de reactions enzymatiques
WO1994029510A1 (fr) * 1993-06-16 1994-12-22 Lignozym Gmbh Procede de modification, de degradation ou de blanchiment de la lignine, de materiaux contenant de la lignine ou de produits similaires

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0825294B2 (fr) † 1996-08-13 2005-02-09 Consortium für elektrochemische Industrie GmbH Système à plusieurs constituants pour modifier, dégrader ou blanchir la lignine, ou les matières contenant de la lignine ainsi que procédés l'utilisant
DE19704054A1 (de) * 1997-02-04 1998-08-06 Stockhausen Chem Fab Gmbh Verfahren zur Herstellung von Faserstoffen mit verbesserten Eigenschaften
DE19704054C2 (de) * 1997-02-04 2000-08-10 Stockhausen Chem Fab Gmbh Verfahren zur Herstellung von Faserstoffen mit verbesserten Eigenschaften
US6344108B1 (en) 1997-02-04 2002-02-05 Stockhausen Gmbh & Co. Kg Using a dicarboxylic acid dialkyl ester brightening
WO1998044189A1 (fr) * 1997-03-31 1998-10-08 Whitmire David R Decoloration enzymatique de pates de bois
KR19990023911A (ko) * 1997-08-28 1999-03-25 에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러 제조 도중에 리그닌 함유 펄프를 증백시키는 방법
US6087135A (en) * 1997-12-19 2000-07-11 Novo Nordisk A/S Modification of polysaccharides by means of a phenol oxidizing enzyme
US6346401B1 (en) 1997-12-19 2002-02-12 Novozymes A/S Modification of polysaccharides by means of a phenol oxidizing enzyme
DE19842662A1 (de) * 1998-09-17 2000-03-30 Consortium Elektrochem Ind Zusammensetzung und Verfahren zum Verändern, Abbau oder Bleichen von ligninhaltigen Materialien
WO2001031066A1 (fr) * 1999-10-28 2001-05-03 Kabushiki Kaisha Toyota Chuo Kenkyusho Procede, appareil et enzyme de reaction chimique
WO2003061550A2 (fr) * 2002-01-26 2003-07-31 Call, Krimhild Nouvelles activites catalytiques d'oxydo-reductases pour l'oxydation et/ou le blanchiment
WO2003061550A3 (fr) * 2002-01-26 2004-09-10 Call Krimhild Nouvelles activites catalytiques d'oxydo-reductases pour l'oxydation et/ou le blanchiment
US7037909B2 (en) 2003-07-02 2006-05-02 Sugen, Inc. Tetracyclic compounds as c-Met inhibitors
US10010536B2 (en) 2005-05-10 2018-07-03 Intermune, Inc. Method of modulating stress-activated protein kinase system
USRE47142E1 (en) 2008-06-03 2018-11-27 Intermune, Inc. Compounds and methods for treating inflammatory and fibrotic disorders
US8343977B2 (en) 2009-12-30 2013-01-01 Arqule, Inc. Substituted triazolo-pyrimidine compounds
US9221756B2 (en) 2011-12-05 2015-12-29 University Of Leicester Pyrrole derivatives
US9675593B2 (en) 2012-10-02 2017-06-13 Intermune, Inc. Anti-fibrotic pyridinones
US10898474B2 (en) 2012-10-02 2021-01-26 Intermune, Inc. Anti-fibrotic pyridinones
US10376497B2 (en) 2012-10-02 2019-08-13 Intermune, Inc. Anti-fibrotic pyridinones
US10544161B2 (en) 2014-04-02 2020-01-28 Intermune, Inc. Anti-fibrotic pyridinones
US10233195B2 (en) 2014-04-02 2019-03-19 Intermune, Inc. Anti-fibrotic pyridinones
US9745253B2 (en) 2015-03-13 2017-08-29 Forma Therapeutics, Inc. Alpha-cinnamide compounds and compositions as HDAC8 inhibitors
US10508077B2 (en) 2015-03-13 2019-12-17 Forma Therapeutics, Inc. Alpha-cinnamide compounds and compositions as HDAC8 inhibitors
US10266487B2 (en) 2015-03-13 2019-04-23 Forma Therapeutics, Inc. Alpha-cinnamide compounds and compositions as HDAC8 inhibitors
US10988441B2 (en) 2015-03-13 2021-04-27 Valo Early Discovery, Inc. Alpha-cinnamide compounds and compositions as HDAC8 inhibitors
US11919839B2 (en) 2015-03-13 2024-03-05 Valo Health, Inc. Alpha-cinnamide compounds and compositions as HDAC8 inhibitors

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Publication number Publication date
CN1142255A (zh) 1997-02-05
WO1996018770A3 (fr) 1996-08-22
HU9602270D0 (en) 1996-10-28
FI963210A (fi) 1996-08-16
CZ243896A3 (en) 1997-01-15
FI963210A0 (fi) 1996-08-16
SK104096A3 (en) 1997-02-05
PL315913A1 (en) 1996-12-09
EP0745154B1 (fr) 1998-09-16
NO963410L (no) 1996-10-15
BR9506801A (pt) 1998-06-30
KR100197048B1 (ko) 1999-06-15
CA2164394A1 (fr) 1996-06-17
KR970701286A (ko) 1997-03-17
EP0745154A1 (fr) 1996-12-04
ATE171228T1 (de) 1998-10-15
NZ300571A (en) 1998-01-26
HUT76126A (en) 1997-06-30
JP3107828B2 (ja) 2000-11-13
DK0745154T3 (da) 1999-06-14
EP0717143A1 (fr) 1996-06-19
RU2142479C1 (ru) 1999-12-10
DE59503612D1 (de) 1998-10-22
ES2122722T3 (es) 1998-12-16
JPH09503257A (ja) 1997-03-31
NO963410D0 (no) 1996-08-15
AU4535096A (en) 1996-07-03
HU215542B (hu) 1999-01-28
AU688660B2 (en) 1998-03-12
TW360729B (en) 1999-06-11

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