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WO1997036039A1 - Systeme a plusieurs constituants pour la modification, la degradation ou le blanchiment de la lignine, de materiaux contenant de la lignine ou de substances analogues, et procedes d'utilisation d'un tel systeme - Google Patents

Systeme a plusieurs constituants pour la modification, la degradation ou le blanchiment de la lignine, de materiaux contenant de la lignine ou de substances analogues, et procedes d'utilisation d'un tel systeme Download PDF

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Publication number
WO1997036039A1
WO1997036039A1 PCT/EP1997/001545 EP9701545W WO9736039A1 WO 1997036039 A1 WO1997036039 A1 WO 1997036039A1 EP 9701545 W EP9701545 W EP 9701545W WO 9736039 A1 WO9736039 A1 WO 9736039A1
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Prior art keywords
radical
lignin
alkyl
salt
ester
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PCT/EP1997/001545
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German (de)
English (en)
Inventor
Hans-Peter Call
Original Assignee
Consortium für elektrochemische Industrie GmbH
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Publication date
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Priority to AU21603/97A priority Critical patent/AU2160397A/en
Publication of WO1997036039A1 publication Critical patent/WO1997036039A1/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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/003—Catalysts comprising hydrides, coordination complexes or organic compounds containing enzymes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/0004—Oxidoreductases (1.)
    • C12N9/0055—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10)
    • C12N9/0057—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10) with oxygen as acceptor (1.10.3)
    • C12N9/0061—Laccase (1.10.3.2)
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/22—Preparation of oxygen-containing organic compounds containing a hydroxy group aromatic
    • 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

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, pulp is produced 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 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
  • 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 which is usually carried out with immobilized fungal systems, is the treatment of pulp wastewater, in particular bleaching wastewater, for decolorization and reduction of the AOX (reduction of chlorinated compounds in the wastewater which 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 under 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 respectively 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 oximes of the general formula I or II
  • X is the same or different and is 0, S, or NR- 1 - where
  • R 1 hydrogen, hydroxy, formyl, carbamoyl, Sulfonorest, ester or salt of Sulfonorests, sulfamoyl, nitro, amino, phenyl, aryl-C 1 - C 5 ⁇ alkyl, C 1 -C 12 -Alkyl-, C 1 -C 5 -alkoxy-, Means phospho, phosphono, phosphonooxy, ester or salt of the phosphonooxy, where carbamoyl, sulfamoyl, amino and phenyl unsubsti- r y tuiert or may be mono- or polysubstituted by a radical R, and aryl-C - ⁇ - Cg-alkyl, C-
  • R 2 is the same or different and is hydroxyl, formyl, carboxy, ester or salt of carboxy, carbamoyl, sulfono ester or salt of sulfono, sulfamoyl, nitro, amino, phenyl, CL-Cg- Alkyl, C j -C ⁇ alkoxy radical means and
  • radicals R 3 and R 4 are identical or different and are halogen, carboxy, ester or salt of the carboxy radical, or have the meanings mentioned for R, or are linked to form a ring t-CR 7RRl n with n equal to 2, 3 or 4 are and
  • R 5 and R6 have the meanings given for R1 and
  • R 7 and R8 are identical or different and represent halogen, carboxy radical, ester or salt of the carboxy radical, or have the meanings mentioned for R.
  • mediators in the multicomponent system according to the invention are compounds of the general formula I in which X is 0 or S and the other radicals have the meanings given above.
  • An example of such a compound is dimethyl 2-hydroxyiminomalonate.
  • mediators are isonitroso derivatives of cyclic ureides of the general formula II.
  • examples of such compounds are 1-methylvioluric acid, 1, 3-dimethylvioluric acid, thiovioluric acid, alloxane-4, 5-dioxime,
  • mediator is alloxan-5-oxime hydrate (violuric acid) and / or its esters, ethers or salts.
  • the multicomponent system according to the invention contains mediators which are less expensive than HBT.
  • 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.
  • 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. be used.
  • 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 class 1.1.5 with quinones as acceptors and the enzymes of class 1.1.3 with oxygen as acceptors are particularly preferred.
  • Cellobiose quinone-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 which oxidize aldehydes to the corresponding acids or oxo groups.
  • the acceptors can be NAD + , NADP + (1.2.1), cytochromes (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 act on CH-CH groups of the donor.
  • acceptors are NAD + , NADP + (1.3.1), Cyto ⁇ chrome (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).
  • Bilirubin oxidase (1.3.3.5) is particularly preferred.
  • the enzymes of class (1.3.3) with oxygen as the acceptor and (1.3.5) with quinones etc. as the 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.
  • acceptors are NAD + , NADP + (1.5.1), oxygen (1.5.3), disulfide (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.
  • 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 NAD + , NADP + (1.8.1), cytochromes (1.8.2), oxygen (0 2 ) (1.8.3), disulphides as acceptors de (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 have oxygen (0 2 ) (1.9.3), NO 2 compounds (1.9.6) and others (1.9.99) as acceptors.
  • Group 1.9.3 with oxygen (0 2 ) as acceptor (cytochrome oxidases) is particularly preferred here.
  • 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 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.
  • 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), 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 (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, the laccases (benzol 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. In principle, both naturally occurring and genetically modified organisms can be enzyme producers. Parts of single-cell or multicellular organisms are also conceivable as enzyme producers, especially cell cultures.
  • the multi-component system according to the invention comprises at least one oxidizing agent.
  • Suitable oxidizing agents are air, oxygen, ozone, H 2 O 2 , organic peroxides, peracids such as peracetic acid, performic acid, persulfuric acid, persalpic acid, metachloroperoxibenzoic acid, perchloric acid, perborates, peracetates, persulfates, peroxides or acids ⁇ substance species and their radicals such as OH ', OOH', singlet oxygen, superoxide (0 2 ' ⁇ ), ozonide, dioxygenyl cation (0 2 + ), di ⁇ oxirane, dioxetane or fremy radicals are used.
  • organic peroxides such as peracetic acid, performic acid, persulfuric acid, persalpic acid, metachloroperoxibenzoic acid, perchloric acid, perborates, peracetates, persulfates, peroxides or acids ⁇ substance species and their radicals such as OH ', OOH
  • 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 directly implement it.
  • oxidoreductases e.g. Dioxiranes from laccases plus carbonyls or which can chemically regenerate the mediator or directly implement it.
  • 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.
  • the Mg ions can be used, for example, as a salt, such as MgSO * .
  • the concentration is in the range of 0.1-2 mg / g of lignin-containing material, preferably 0.2-0.6 mg / g.
  • the multicomponent system in addition to the Mg + ions also complexing agents such as, for example, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentamethylene - contains phosphonic acid (DTMPA), nitrilotriacetic acid (NTA), polyphosphoric acid (PPA) etc.
  • the concentration is in Range of 0.2-5 mg / g of lignin-containing material, preferably 1-3 mg.
  • the multi-component system according to the invention is used in a process for treating lignin, for example, by mixing the respectively selected components a) to c) 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%.
  • an acid wash (pH 2 to 6, preferably 4 to 5) or Q stage (pH 2 to 6, preferably 4 to 5) before the enzyme mediator stage led to a considerable degree in some pulps Kappa reduction compared to treatment without this special pretreatment leads.
  • the substances customary for this purpose (such as EDTA, DTPA) are used as chelating agents. They are preferably used in concentrations of 0.1% / t to 1% / t, particularly preferably 0.1% / t to 0.5% / t. In the process according to the invention, preferably 0.01 to 10,000 IU enzyme per g lignin-containing material are used.
  • lignin-containing material 1 U corresponds to the conversion of 1 ⁇ mol of 2,2'-azino-bis (3-ethyl-benzothiazoline) -6-sulfonic acid diammonium salt) (ABTS) / min / ml enzyme).
  • oxidizing agent per g of lignin-containing material preferably 0.01 mg to 100 mg of oxidizing agent per g of lignin-containing material is used. 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 are 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 proceeds with air or oxygen supply or oxygen or air pressure, in the case of 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 + glucose oxidase 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.
  • Other metal salts can also be added to the reaction solution.
  • the salts form cations in the reaction solution.
  • Such ions include Fe, 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 (haem grain 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. 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 own polysaccharides formed by the fungi or produced in the mixed culture with yeasts and in particular gelatin and albumin as proteins are to be mentioned here in particular as polysaccharides.
  • These substances mainly serve as protective colloids for the enzymes.
  • 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.
  • Amino acids simple sugars, oligomer sugars, PEG types of the most varied molecular weights, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes can be used as further protective colloids.
  • the method according to the invention can be used not only in the delignification (bleaching) of sulfate, sulfite, organosol, etc.
  • Cellulose and wood pulp are used, but also in the production of cellulose or wood pulp (refiner / wood pulp) in general, for example from wood or annual plants.
  • defibrillation should be ensured by the usual cooking processes and / or mechanical processes or pressure (i.e. very gentle treatment up to kappa numbers in the range of> 50 kappa or> 10% lignin content).
  • 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 significantly lower kappa values and considerable 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.
  • Example 1 Enzymatic bleaching with violuric acid and Softwood sulfate pulp
  • reaction bomb preheated to 45 ° C and incubated under 1 - 10 bar oxygen pressure for 10 to 40 minutes.
  • 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 cellulose. After washing the fabric again, the kappa number is determined.
  • 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 cellulose. After washing the fabric again, the kappa number is determined.
  • Solutions A and B are combined and made up to 33 ml.
  • 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.
  • the kappa number is determined.
  • Solutions A and B are combined and made up to 33 ml.
  • 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 cellulose. After washing the fabric again, the kappa number is determined. Depending on the incubation period, the following delignification rates are achieved:

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Abstract

Système à plusieurs constituants pour la modification, la dégradation ou le blanchiment de la lignine, de matériaux contenant de la lignine ou de substances analogues, renfermant a) éventuellement au moins un catalyseur d'oxydation, et b) au moins un agent d'oxydation approprié, et c) au moins un médiateur, caractérisé en ce que le médiateur est choisi dans le groupe des oximes de formule générale (I) et (II), ainsi que leurs sels, éthers ou esters, ou les restes X sont identiques ou différents et désignent O, S ou NR1, R1 désigne un hydrogène, un reste hydroxy, formyle, carbamoyle, sulfono, un ester ou un sel d'un reste sulfono, un reste sulfamoyle, nitro, amino, phényle, arylalkyle C¿1?-C5, alkyle C1-C12, alcoxy, C1-C5, carbonyle C1-C10, carbonylalkyle C1-C6, un reste phospho, phosphono, phosphono-oxy, un ester ou un sel du reste phosphono-oxy, les restes carbamoyle, sulfamoyle, amino et phényle pouvant être non substitués ou substitués une ou plusieurs fois par un reste R?2¿, et les restes arylalkyle C¿1?-C5, alkyle C1-C12, alcoxy C1-C5, carbonyle C1-C10-, carbonylalkyle C1-C6 pouvant être saturés ou insaturés, ramifiés ou non ramifiés et pouvant être substituées, une ou plusieurs fois par un reste R?2¿, les restes R2 sont identiques ou différents et désignent un hydroxy, formyle, carboxy, un ester ou un sel du reste carboxy, un reste carbamoyle ou sulfono, un ester ou un sel du reste sulfono, un sulfamoyle, nitro, amino, phényle, alkyle C¿1?-C5, alcoxy C1-C5, et les restes R?3-R4¿ sont identiques ou différents et désignent un halogène, un reste carboxy, un ester ou un sel du reste carboxy ou ont les significations indiquées pour R1, et où R3 et R4 peuvent être liés éventuellement à un cycle [-CR7R8]n, avec n égal à 1, 2, 3 ou 4, et R5 et R6 ont les significations indiquées pour R?1, et R7 et R8¿ ont les significations indiquées pour R3 et R4.
PCT/EP1997/001545 1996-03-27 1997-03-26 Systeme a plusieurs constituants pour la modification, la degradation ou le blanchiment de la lignine, de materiaux contenant de la lignine ou de substances analogues, et procedes d'utilisation d'un tel systeme WO1997036039A1 (fr)

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Application Number Priority Date Filing Date Title
AU21603/97A AU2160397A (en) 1996-03-27 1997-03-26 A multicomponent system for changing, degrading or bleaching lignin, lignin-containing materials or similar substances and processes for its use

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DE19612194.9 1996-03-27
DE19612194A DE19612194A1 (de) 1996-03-27 1996-03-27 Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen sowie Verfahren zu seiner Anwendung

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WO1997036039A1 true WO1997036039A1 (fr) 1997-10-02

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Cited By (7)

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EP0885868A1 (fr) * 1997-06-06 1998-12-23 Consortium für elektrochemische Industrie GmbH Procédé d'oxydation pour préparer d'aldéhydes et de cétones en présence des composés contenant de l'azote
WO2003052201A1 (fr) * 2001-12-17 2003-06-26 Consejo Superior De Investigaciones Científicas Nouveau procede de blanchiment enzymatique sans chlorure de pates de haute qualite obtenues de plantes herbacees ou arbustives
US6660128B1 (en) 1998-04-16 2003-12-09 Pulp And Paper Research Institute Of Canada Oxidase process for pulp
GB2391011A (en) * 2002-07-19 2004-01-28 Crosmill Ltd Bleaching cellulose suspensions
CN103080415A (zh) * 2010-07-01 2013-05-01 诺维信公司 纸浆的漂白
US12168011B2 (en) 2022-02-21 2024-12-17 Verona Pharma Plc Formulation production process
US12251384B1 (en) 2023-06-26 2025-03-18 Verona Pharma Plc Particulate composition

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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
DE19726241A1 (de) * 1997-06-20 1998-12-24 Call Krimhild Erweitertes enzymatisches Multikomponentensystem zur Behandlung von Abwässern, zur Herstellung von Holzverbundstoffen, zum Deinken von Altpapier, Colour stripping von Altpapier, zum Einsatz als Oxidationssystem bei der organischen Synthese und zum Einsatz bei der Kohleverflüssigung
CN100404753C (zh) * 2002-10-18 2008-07-23 梅秀泉 氧化法全棉秆造新闻纸浆及其制备方法
CN100404754C (zh) * 2002-10-18 2008-07-23 梅秀泉 生物/氧化法造芦苇浆的制备方法
US20070272377A1 (en) * 2003-12-25 2007-11-29 Xiuquan Mei Fully Closed, Zero Discharge, Clean Oxidizing Pulping Technology and Process
CN100420788C (zh) * 2003-12-25 2008-09-24 梅秀泉 全封闭零排放生物/氧化法清洁造纸浆方法和由此获得的纸浆

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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

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US3728461A (en) * 1970-08-31 1973-04-17 Gates Rubber Co Use of violuric acid as a fungicide or bactericide
DE3216639A1 (de) * 1981-05-07 1982-11-25 CIBA-GEIGY AG, 4002 Basel Verfahren zum delignifizieren von lignocellulosematerial
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
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

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US6023000A (en) * 1997-06-06 2000-02-08 Consortium fur elektrochemisch Industrie GmbH Process for the preparation of aldehydes and ketones
US6297403B1 (en) 1997-06-06 2001-10-02 Consortium für elektrochemische Industrie GmbH Process for the preparation of aldehydes and ketones
EP0885868A1 (fr) * 1997-06-06 1998-12-23 Consortium für elektrochemische Industrie GmbH Procédé d'oxydation pour préparer d'aldéhydes et de cétones en présence des composés contenant de l'azote
US6660128B1 (en) 1998-04-16 2003-12-09 Pulp And Paper Research Institute Of Canada Oxidase process for pulp
ES2189683B1 (es) * 2001-12-17 2005-02-01 Consejo Superior De Investigaciones Cientificas Nuevo procedimiento para el blanqueo enzimatico libre de cloro de pastas de alta calidad obtenidas de plantas herbaceas o arbustivas.
WO2003052201A1 (fr) * 2001-12-17 2003-06-26 Consejo Superior De Investigaciones Científicas Nouveau procede de blanchiment enzymatique sans chlorure de pates de haute qualite obtenues de plantes herbacees ou arbustives
ES2189683A1 (es) * 2001-12-17 2003-07-01 Consejo Superior Investigacion Nuevo procedimiento para el blanqueo enzimatico libre de cloro de pastas de alta calidad obtenidas de plantas herbaceas o arbustivas
GB2391011A (en) * 2002-07-19 2004-01-28 Crosmill Ltd Bleaching cellulose suspensions
CN103080415A (zh) * 2010-07-01 2013-05-01 诺维信公司 纸浆的漂白
US9222078B2 (en) 2010-07-01 2015-12-29 Novozymes A/S Bleaching of pulp
CN106120422A (zh) * 2010-07-01 2016-11-16 诺维信公司 纸浆的漂白
CN106120422B (zh) * 2010-07-01 2018-11-20 诺维信公司 纸浆的漂白
US12168011B2 (en) 2022-02-21 2024-12-17 Verona Pharma Plc Formulation production process
US12251384B1 (en) 2023-06-26 2025-03-18 Verona Pharma Plc Particulate composition

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DE19612194A1 (de) 1997-10-02

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