EP0717143A1 - Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen sowie Verfahren zu seiner Anwendung - Google Patents

Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen sowie Verfahren zu seiner Anwendung Download PDF

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EP0717143A1
EP0717143A1 EP94119981A EP94119981A EP0717143A1 EP 0717143 A1 EP0717143 A1 EP 0717143A1 EP 94119981 A EP94119981 A EP 94119981A EP 94119981 A EP94119981 A EP 94119981A EP 0717143 A1 EP0717143 A1 EP 0717143A1
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EP
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Prior art keywords
triazolo
alkyl
acid
esters
salts
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EP94119981A
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German (de)
English (en)
French (fr)
Inventor
Hans-Peter Dr. Call
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Lignozym GmbH
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Lignozym GmbH
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Application filed by Lignozym GmbH filed Critical Lignozym GmbH
Priority to EP94119981A priority Critical patent/EP0717143A1/de
Priority to TW084112809A priority patent/TW360729B/zh
Priority to CA002164394A priority patent/CA2164394A1/en
Priority to ES95944012T priority patent/ES2122722T3/es
Priority to RU96118245A priority patent/RU2142479C1/ru
Priority to AU45350/96A priority patent/AU688660B2/en
Priority to EP95944012A priority patent/EP0745154B1/de
Priority to DK95944012T priority patent/DK0745154T3/da
Priority to PCT/EP1995/004965 priority patent/WO1996018770A2/de
Priority to DE59503612T priority patent/DE59503612D1/de
Priority to AT95944012T priority patent/ATE171228T1/de
Priority to CN95191657A priority patent/CN1142255A/zh
Priority to HU9602270A priority patent/HU215542B/hu
Priority to NZ300571A priority patent/NZ300571A/en
Priority to KR1019960704448A priority patent/KR100197048B1/ko
Priority to CZ962438A priority patent/CZ243896A3/cs
Priority to SK1040-96A priority patent/SK104096A3/sk
Priority to JP08518274A priority patent/JP3107828B2/ja
Priority to BR9506801A priority patent/BR9506801A/pt
Priority to PL95315913A priority patent/PL315913A1/xx
Publication of EP0717143A1 publication Critical patent/EP0717143A1/de
Priority to NO963410A priority patent/NO963410L/no
Priority to FI963210A priority patent/FI963210A0/fi
Withdrawn legal-status Critical Current

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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

  • 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 Na2S, while Ca (HSO3) 2 + SO2 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 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 after grinding (chemical, thermal or chemical-thermal).
  • Biopulping is the treatment of wood chips with living fungal systems.
  • 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 mill wastewater, especially bleaching mill wastewater to decolorize it and reduce the AOX (reduction of chlorinated compounds in the 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.
  • 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, lignin-containing materials or similar substances, which is more effective than known systems.
  • 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).
  • 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 (O2) (1.1.3), Disulfide (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 are particularly preferred. with oxygen as the acceptor.
  • Cellobiose quione-1-oxidoreductase (1.1.5.1) 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 aldehydes to the corresponding acids or oxo groups oxidize.
  • 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 ) his.
  • 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 act on CH-CH groups of the donor.
  • acceptors are NAD +, NADP + (1.3.1) cytochrome (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.
  • class 1.4 enzymes which act on CH-NH2 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 other 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.
  • 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 (O2) 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), NO2 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 NO2 compounds and acceptors as cytochromes (1.7.2), oxygen (O2) (1.7.3), iron-sulfur proteins (1.7.7) or others ( 1.7.99).
  • Class 1.7.3 with oxygen as the acceptor is particularly preferred here.
  • class 1.8 enzymes which act as donors on sulfur groups and acceptors NAD +, NADP + (1.8.1), cytochromes (1.8.2), oxygen (O2) (1.8.3), disulfides (1.8.4), Have 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 (O2) (1.9.3), NO2 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 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. ceruloplasmin) are particularly preferred here.
  • Further preferred enzymes are those of group 1.17 (action on CH2 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 (other oxidoreductases ) belong to.
  • 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), the glutathione peroxidase (1.11.1.9) are particularly preferred here, chloride peroxidase (1.11.1.10), L-ascorbate peroxidase (1.11.1.11), phospholipid hydroperoxide glutathione peroxidase (1.11.1.12), manganese peroxidase (1.12.1.13), 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 (1.10.2), oxygen (1.10.3) or others (1.10.99) act as acceptors.
  • enzymes of class 1.10.3 with oxygen (O2) 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 (benzenediol: oxigen oxidoreductase) (1.10.3.2.) being particularly preferred.
  • 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 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 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, H2O2 , organic peroxides, peracids such as peracetic acid, performic acid, persulfuric acid, persitric acid, metachloroperoxidbenzoic acid, perchloric acid, perborates, peracetates, persulfates, peroxides or oxygen species and their radicals such as OH, OOH, superoxide (singlet oxygen) O2 ⁇ ), ozonide, dioxygenyl cation (O2+), Dioxrane, Dioxitane or Fremy radicals are 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 (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 preferably comprises at least one compound which contains at least one N-hydroxyl, oxime, N-oxi or N-dioxi function and / or one of the compounds of the formula I mentioned below , II, III, IV or V, the compounds of the formulas II, III, IV and V being preferred, the compounds of the formulas III, IV and V being particularly preferred and compounds of the formulas IV and V being particularly preferred.
  • Hydroxylamines (open-chain or cyclic, aliphatic or aromatic, heterocyclic) of the general formula I
  • the substituents R1 and R2 which may be the same or different, independently represent one of the following groups: hydrogen, C1-C12-alkyl, carbonyl-C1-C6-alkyl, phenyl, aryl- whose C1-C12-alkyl-, carbonyl-C1-C6-alkyl-, phenyl-, aryl- unsubstituted or further substituted one or more times with the radical R3 and where the radical R3 can be one of the following groups: hydrogen, Halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C1-C12-alkyl, C1-C6-alkyloxy, carbonyl-C1-C6-alkyl, phenyl, sulfono-, whose Esters and salts, sul
  • the radicals R5 to R8 can be the same or different and independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C1-C12-alkyl, C1-C6-alkyloxy, carbonyl -C1-C6-alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and where the amino, carbamoyl and sufamoyl groups of the radicals R5 to R8 continue to be unsubstituted or a - Or be substituted twice with hydroxy, C1-C3-alkyl, C1-C3-alkoxy and where the C1-C12-alkyl, C1-C6-alkyloxy, carbonyl-C1-C6-alkyl, phenyl, ary
  • the radicals R5 to R12 can be the same or different and independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C1-C12-alkyl, C1-C6-alkyloxy, carbonyl-C1-C6-alkyl, phenyl, aryl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and wherein the amino, carbamoyl and sufamoyl groups of the radicals R5 to R12 further unsubstituted or substituted one or two times with hydroxy, C1-C3-alkyl, C1-C3-alkoxy and wherein the C1-C12-alkyl, C1-C6-alkyloxy, carbonyl-C1-C6-alkyl, phenyl,
  • R17 can be: hydrogen, C1-C10-alkyl, C1-C10-carbonyl whose C1-C10-alkyl and C1-C10-carbonyl are unsubstituted or can be substituted one or more times with a radical R18 which is defined as R3.
  • radicals R5 to R8 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, C1-C12-alkyl, C1-C6-alkyloxy, carbonyl-C1-C6-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 R5 to R8 continue to be unsubstituted or may be substituted once or twice with hydroxy, C1-C3-alkyl
  • 1-hydroxybenzotriazole 1-hydroxybenzotriazole, sodium salt.
  • 1-hydroxybenzotriazole potassium salt 1-hydroxybenzotriazole, lithium salt 1-hydroxybenzotriazole, ammonium salt 1-hydroxybenzotriazole, calcium salt 1-hydroxybenzotriazole, magnesium salt 1-hydroxybenzotriazole-6-sulfonic acid 1-hydroxybenzotriazole-6-sulfonic acid, monosodium salt 1-hydroxybenzotriazole-6-carboxylic acid 1-hydroxybenzotriazole-6-N-phenylcarboxamide 5-ethoxy-6-nitro-1-hydroxybenzotriazole 4-ethyl-7-methyl-6-nitro-1-hydroxybenzotriazole 2,3-bis (4-ethoxyphenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole 2,3-bis (2-bromo-4-methylphenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole 2,3-bis (4-bro
  • 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, for example 2,3-dimethoxybenzyl alcohol 3,4-dimethoxybenzyl alcohol 2,4-dimethoxybenzyl alcohol 2,6-dimethoxybenzyl alcohol Homovanillyl alcohol Ethylene glycol monophenyl ether 2-hydroxybenzyl alcohol 4-hydroxybenzyl alcohol 4-hydroxy-3-methoxybenzyl alcohol 2-methoxybenzyl alcohol 2,5-dimethoxybenzyl alcohol 3,4-dimethoxybenzylamine 2,4-dimethoxybenzylamine hydroch
  • 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.
  • Mg2+ ions can be used, for example, as a salt, e.g. MgSO4 can be used.
  • 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 Mg2+ ions also complexing agents such as e.g. Contains ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentametylenophosphonic 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 merh component system according to the invention is used in a process for treating lignin, for example, by selected components a) to e) 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 from 20 to 95 ° C., preferably 40-95 ° C., and one Fabric density from 0.5 to 40% carried out.
  • a finding that is unusual and surprising for the use of enzymes in cellulose bleaching is that when the multicomponent system according to the invention is used, increasing the consistency enables a significant increase in the kappa reduction.
  • 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 of lignin-containing material are particularly preferably used.
  • 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 oxide ionizing 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 glutation etc. can be used as reducing agents.
  • the reaction takes place with the addition of oxygen or oxygen 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.
  • the salts form cations in the reaction solution.
  • Such ions include Fe2 +, Fe3 +, Mn2 +, Mn3 +, Mn4 +, Cu 2+, Ca2 +, Ti3 +, Cer4 +, Al3 +.
  • 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 e.g. Can catalyze oxidation reactions.
  • NaOCl can also be added to the reaction mixture.
  • this compound can form Sindulett 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 chydroxypholine-rich protein present in the wood.
  • Amino acids simple sugars, oligomer sugars, amino acids, PEG types of the most varied molecular weights, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes can be considered as further protective colloids.
  • the process according to the invention can be used not only in the delignification (bleaching) of sulfate, sulfite, organolsolv or the like. 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 O2 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.
  • 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 substance is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C., 8% density and 2% NaOH per g substance.
  • 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 substance is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C., 8% density and 2% NaOH per g substance.
  • the kappa number is determined.
  • Example Enzymatic bleaching of sulfate pulps with an upstream Q stage.
  • 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 substance is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C., 8% density and 2% NaOH per g substance
  • the kappa number is determined.
  • the kappa number is determined according to the Q level. The results are shown in Table 3.
  • 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 substance is then washed over a nylon sieve (30 ⁇ m) and extracted for 1 hour at 60 ° C., 8% density and 2% NaOH per g substance.
  • 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 pulp is then washed over a nylon screen (30 .mu.m) and 1- Std. Extracted per g of fabric at 60 ° C, 8% consistency, and 2% NaOH.
  • 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 pulp is then washed over a nylon screen (30 .mu.m) and extracted per g of pulp 1 h. At 60 ° C, 8% consistency, and 2% NaOH.
  • 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 pulp is then washed over a nylon screen (30 .mu.m) and extracted per g of pulp 1 h. At 60 ° C, 8% consistency, and 2% NaOH.
  • the kappa number is determined.
  • the substance is then placed in a reaction bomb preheated to 45 ° C. and our 1-10 bar overpressure is incubated for 1-4 hours.
  • the pulp is then washed over a nylon screen (30 .mu.m) and extracted per g of pulp 1 h. At 60 ° C, 8% consistency, and 2% NaOH.
  • 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 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).

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EP94119981A 1994-12-16 1994-12-16 Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen sowie Verfahren zu seiner Anwendung Withdrawn EP0717143A1 (de)

Priority Applications (22)

Application Number Priority Date Filing Date Title
EP94119981A EP0717143A1 (de) 1994-12-16 1994-12-16 Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen sowie Verfahren zu seiner Anwendung
TW084112809A TW360729B (en) 1994-12-16 1995-12-01 Multi-components system for modifying decomposing or bleaching of lignin or materials containing it or similar components and the way to use it
CA002164394A CA2164394A1 (en) 1994-12-16 1995-12-04 Multi-component system for modifying, degrading or bleaching lignin, lignin-containing materials or similar substances and processes for its use
CN95191657A CN1142255A (zh) 1994-12-16 1995-12-15 改性、降解或漂白木素、含木素的材料或类似物质的多组分体系及其使用方法
KR1019960704448A KR100197048B1 (ko) 1994-12-16 1995-12-15 리그닌, 리그닌함유재 또는 그 동일물질을 개질, 분해 또는 표백하는 조성물
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 (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
DK95944012T DK0745154T3 (da) 1994-12-16 1995-12-15 Flerkomponentsystem til ændring, nedbrydning eller blegning af lignin, ligninholdige materialer eller lignende stoffer samt
PCT/EP1995/004965 WO1996018770A2 (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
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
AT95944012T ATE171228T1 (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
ES95944012T ES2122722T3 (es) 1994-12-16 1995-12-15 Sistema de componentes multiples para la modificacion, degradacion o blanqueo de lignina, materiales que contienen lignina o materiales analogos, y proceso para su empleo.
HU9602270A HU215542B (hu) 1994-12-16 1995-12-15 Többkomponensű rendszer lignin, lignintartalmú anyagok és hasonlók módosítására, lebontására vagy fehérítésére, valamint eljárás ilyen rendszer alkalmazására
NZ300571A NZ300571A (en) 1994-12-16 1995-12-15 Multicomponent system for treating lignocellulose material
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
CZ962438A CZ243896A3 (en) 1994-12-16 1995-12-15 Multicomponent system for conversion, degradation or bleaching of lignin, lignin-containing materials or the like matters and the way of use thereof
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
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
PL95315913A PL315913A1 (en) 1994-12-16 1995-12-15 Multicomponent system for modifying, decomposing or bleaching cellucotton, materials containing ir or similar materials and method of implementing this system
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 (1)

Application Number Priority Date Filing Date Title
EP94119981A EP0717143A1 (de) 1994-12-16 1994-12-16 Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen sowie Verfahren zu seiner Anwendung

Publications (1)

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EP0717143A1 true EP0717143A1 (de) 1996-06-19

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EP94119981A Withdrawn EP0717143A1 (de) 1994-12-16 1994-12-16 Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen sowie Verfahren zu seiner Anwendung
EP95944012A Expired - Lifetime EP0745154B1 (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

Family Applications After (1)

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EP95944012A Expired - Lifetime EP0745154B1 (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

Country Status (21)

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

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WO1997036041A1 (de) * 1996-03-27 1997-10-02 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum verändern, abbau oder bleichen von lignin, ligninhaltigen materialien oder ähnlichen stoffen sowie verfahren zu seiner anwendung
WO1998005818A1 (de) * 1996-08-01 1998-02-12 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum verändern, abbau oder bleichen von lignin, ligninhaltigen materialien oder ähnlichen stoffen sowie verfahren zu seiner anwendung
EP0825294A1 (de) * 1996-08-13 1998-02-25 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum Verändern, Abbau oder Blechen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen sowie Verfahren zu seiner Anwendung
WO1998026127A1 (de) * 1996-12-09 1998-06-18 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum verändern, abbau oder bleichen von lignin, ligninhaltigen materialien oder ähnlichen stoffen sowie verfahren zu seiner anwendung
DE19704054A1 (de) * 1997-02-04 1998-08-06 Stockhausen Chem Fab Gmbh Verfahren zur Herstellung von Faserstoffen mit verbesserten Eigenschaften
EP0882814A1 (de) * 1997-06-06 1998-12-09 Consortium für elektrochemische Industrie GmbH System und Verfahren zur elektrochemischen Spaltung von Verbindungen
WO1998055684A1 (de) * 1997-06-05 1998-12-10 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum verändern, abbau oder bleichen von lignin, ligninhaltigen materialien oder ähnlichen stoffen sowie verfahren zu seiner anwendung
WO1998056899A1 (en) * 1997-06-10 1998-12-17 Unilever N.V. Method for enhancing the activity of an enzyme, bleach composition, detergent composition and process for inhibiting dye transfer
WO1998059108A2 (de) * 1997-06-20 1998-12-30 Blume, Hildegard Oxidations- und bleichsystem mit enzymatisch hergestellten oxidationsmitteln
WO1999001607A2 (de) * 1997-06-20 1999-01-14 Call, Krimhild Enzymatisches oxidationssystem mit neuen enzymwirkungsverstärkenden verbindungen
WO1999016962A1 (de) * 1997-09-27 1999-04-08 Degussa-Hüls Aktiengesellschaft Verfahren zum delignifizieren und bleichen von zellstoffen unter verwendung elektrochemisch oxidierter organischer verbindungen
WO2000024963A1 (en) * 1998-10-22 2000-05-04 Ciba Specialty Chemicals Holding Inc. Inhibition of pulp and paper yellowing using hydroxylamines and other coadditives
WO2002049969A2 (de) * 2000-12-21 2002-06-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur beschleunigung biokatalytischer und/oder hormoneller prozesse und dessen verwendung
WO2002099023A2 (de) * 2001-06-05 2002-12-12 Call, Krimhild Enzymatische systeme zur generierung aktiver sauerstoffspezies zur reaktion mit anderen precursern zur oxidation und/oder bleiche
DE19820947B4 (de) * 1997-05-12 2005-12-01 Call, Krimhild Enzymatisches Bleichsystem mit neuen enzymwirkungsverstärkenden Verbindungen zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder Verändern oder Abbau von Kohle sowie Verfahren unter Verwendung des Bleichsystems
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WO2013045782A1 (fr) * 2011-09-30 2013-04-04 Arkema France Pretraitement enzymatique de bois dans un procede de fabrication de pate a papier mecanique
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WO1997036041A1 (de) * 1996-03-27 1997-10-02 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum verändern, abbau oder bleichen von lignin, ligninhaltigen materialien oder ähnlichen stoffen sowie verfahren zu seiner anwendung
WO1997036039A1 (de) * 1996-03-27 1997-10-02 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum verändern, abbau oder bleichen von lignin, ligninhaltigen materialien oder ähnlichen stoffen sowie verfahren zu seiner anwendung
WO1998005818A1 (de) * 1996-08-01 1998-02-12 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum verändern, abbau oder bleichen von lignin, ligninhaltigen materialien oder ähnlichen stoffen sowie verfahren zu seiner anwendung
EP0825294A1 (de) * 1996-08-13 1998-02-25 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum Verändern, Abbau oder Blechen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen sowie Verfahren zu seiner Anwendung
CN1102974C (zh) * 1996-08-13 2003-03-12 电化学工业有限公司（国际） 用于改性、降解或漂白木质素及含木质素材料的多组分系统及其使用方法
AU719140B2 (en) * 1996-12-09 2000-05-04 Consortium Fur Elektrochemische Industrie Gmbh Multi-component system for modifying, degrading or bleaching lignin, lignin-containing materials or similar substances and processes for its use
WO1998026127A1 (de) * 1996-12-09 1998-06-18 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum verändern, abbau oder bleichen von lignin, ligninhaltigen materialien oder ähnlichen stoffen sowie verfahren zu seiner anwendung
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
DE19704054A1 (de) * 1997-02-04 1998-08-06 Stockhausen Chem Fab Gmbh Verfahren zur Herstellung von Faserstoffen mit verbesserten Eigenschaften
DE19820947B4 (de) * 1997-05-12 2005-12-01 Call, Krimhild Enzymatisches Bleichsystem mit neuen enzymwirkungsverstärkenden Verbindungen zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder Verändern oder Abbau von Kohle sowie Verfahren unter Verwendung des Bleichsystems
WO1998055684A1 (de) * 1997-06-05 1998-12-10 Consortium für elektrochemische Industrie GmbH Mehrkomponentensystem zum verändern, abbau oder bleichen von lignin, ligninhaltigen materialien oder ähnlichen stoffen sowie verfahren zu seiner anwendung
EP0882814A1 (de) * 1997-06-06 1998-12-09 Consortium für elektrochemische Industrie GmbH System und Verfahren zur elektrochemischen Spaltung von Verbindungen
US6187170B1 (en) 1997-06-06 2001-02-13 Consortium für elektrochemische Industrie GmbH System for the electrochemical delignification of lignin-containing materials and a process for its application
WO1998056899A1 (en) * 1997-06-10 1998-12-17 Unilever N.V. Method for enhancing the activity of an enzyme, bleach composition, detergent composition and process for inhibiting dye transfer
US6225275B1 (en) 1997-06-10 2001-05-01 Lever Brothers Company, Division Of Conopco, Inc. Method for enhancing the activity of an enzyme
WO1999001607A3 (de) * 1997-06-20 1999-06-24 Call Krimhild Enzymatisches oxidationssystem mit neuen enzymwirkungsverstärkenden verbindungen
WO1998059108A2 (de) * 1997-06-20 1998-12-30 Blume, Hildegard Oxidations- und bleichsystem mit enzymatisch hergestellten oxidationsmitteln
WO1998059108A3 (de) * 1997-06-20 1999-03-18 Blume Hildegard Oxidations- und bleichsystem mit enzymatisch hergestellten oxidationsmitteln
WO1999001607A2 (de) * 1997-06-20 1999-01-14 Call, Krimhild Enzymatisches oxidationssystem mit neuen enzymwirkungsverstärkenden verbindungen
WO1999016962A1 (de) * 1997-09-27 1999-04-08 Degussa-Hüls Aktiengesellschaft Verfahren zum delignifizieren und bleichen von zellstoffen unter verwendung elektrochemisch oxidierter organischer verbindungen
WO2000024963A1 (en) * 1998-10-22 2000-05-04 Ciba Specialty Chemicals Holding Inc. Inhibition of pulp and paper yellowing using hydroxylamines and other coadditives
AU754737B2 (en) * 1998-10-22 2002-11-21 Ciba Specialty Chemicals Holding Inc. Inhibition of pulp and paper yellowing using hydroxylamines and other coadditives
WO2002049969A3 (de) * 2000-12-21 2003-01-30 Fraunhofer Ges Forschung Verfahren zur beschleunigung biokatalytischer und/oder hormoneller prozesse und dessen verwendung
WO2002049969A2 (de) * 2000-12-21 2002-06-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur beschleunigung biokatalytischer und/oder hormoneller prozesse und dessen verwendung
WO2002099023A2 (de) * 2001-06-05 2002-12-12 Call, Krimhild Enzymatische systeme zur generierung aktiver sauerstoffspezies zur reaktion mit anderen precursern zur oxidation und/oder bleiche
WO2002099023A3 (de) * 2001-06-05 2003-05-30 Call Krimhild Enzymatische systeme zur generierung aktiver sauerstoffspezies zur reaktion mit anderen precursern zur oxidation und/oder bleiche
EP1905418A2 (de) * 2006-09-01 2008-04-02 Henkel Kommanditgesellschaft auf Aktien Wasserstoffperoxid-Aktivierung mit N-Heterocyclen
EP1905418A3 (de) * 2006-09-01 2008-07-02 Henkel AG & Co. KGaA Wasserstoffperoxid-Aktivierung mit N-Heterocyclen
WO2013045782A1 (fr) * 2011-09-30 2013-04-04 Arkema France Pretraitement enzymatique de bois dans un procede de fabrication de pate a papier mecanique
FR2980805A1 (fr) * 2011-09-30 2013-04-05 Arkema France Pretraitement enzymatique de bois dans un procede de fabrication de pate a papier mecanique
US9834886B2 (en) 2011-09-30 2017-12-05 Arkema France Enzymatic pretreatment of wood in a method for producing mechanical paper pulp
CN103174047A (zh) * 2013-04-16 2013-06-26 枣庄鸿润纸业有限公司 一种过氧化氢酶法精制麦草浆的工艺

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JP3107828B2 (ja) 2000-11-13
HU215542B (hu) 1999-01-28
TW360729B (en) 1999-06-11
WO1996018770A2 (de) 1996-06-20
NO963410D0 (no) 1996-08-15
KR100197048B1 (ko) 1999-06-15
WO1996018770A3 (de) 1996-08-22
CN1142255A (zh) 1997-02-05
AU4535096A (en) 1996-07-03
BR9506801A (pt) 1998-06-30
PL315913A1 (en) 1996-12-09
FI963210A (fi) 1996-08-16
HUT76126A (en) 1997-06-30
CZ243896A3 (en) 1997-01-15
DE59503612D1 (de) 1998-10-22
DK0745154T3 (da) 1999-06-14
RU2142479C1 (ru) 1999-12-10
NZ300571A (en) 1998-01-26
SK104096A3 (en) 1997-02-05
JPH09503257A (ja) 1997-03-31
ES2122722T3 (es) 1998-12-16
ATE171228T1 (de) 1998-10-15
CA2164394A1 (en) 1996-06-17
HU9602270D0 (en) 1996-10-28
NO963410L (no) 1996-10-15
EP0745154A1 (de) 1996-12-04
KR970701286A (ko) 1997-03-17
AU688660B2 (en) 1998-03-12
FI963210A0 (fi) 1996-08-16

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