EP0943032B1 - Multicomponent system for modifying, decomposing or bleaching lignin or lignin-containing materials, and process for using the same - Google Patents
Multicomponent system for modifying, decomposing or bleaching lignin or lignin-containing materials, and process for using the same Download PDFInfo
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- EP0943032B1 EP0943032B1 EP97952038A EP97952038A EP0943032B1 EP 0943032 B1 EP0943032 B1 EP 0943032B1 EP 97952038 A EP97952038 A EP 97952038A EP 97952038 A EP97952038 A EP 97952038A EP 0943032 B1 EP0943032 B1 EP 0943032B1
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- Prior art keywords
- nitrosopyridine
- radical
- hydroxy
- dihydroxy
- lignin
- Prior art date
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Classifications
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- 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
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- 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 or containing lignin Materials and procedures for its Application.
- the sulfate and sulfite processes are the main processes used today for pulp production. Both methods produce pulp under cooking and under pressure.
- the sulfate process works with the addition of NaOH and Na 2 S, while the sulfite process uses Ca (HSO 3 ) 2 + SO 2 .
- the main goal of all procedures is the removal of the lignin from the used plant material, wood or Annual plants.
- the lignin that is associated with cellulose and hemicellulose Main component of the plant material must be removed, otherwise it is not possible non-yellowing and mechanically heavy-duty papers to manufacture.
- the wood production processes work with stone grinders (Wood sanding) or with refiners (TMP), which the wood after appropriate Pretreatment (chemical, thermal or chemical-thermal) defibrillate by grinding.
- Wood sanding Wood sanding
- TMP refiners
- Biopulping is the treatment of wood chips with living mushroom systems.
- the goal here is to reduce the amount of cooking chemicals that Improve cooking capacity and "extended cooking".
- Improved kappa reduction is also an advantage after cooking compared to cooking without pretreatment reached.
- Biobleaching also works with in-vivo systems.
- the cooked pulp (Softwood / Hardwood) is before bleaching inoculated with the fungus and treated for days to weeks. Just after this long treatment period, a significant one becomes apparent Kappa reduction and whiteness, what the process uneconomical for an implementation in the usual Bleaching sequences.
- Chelate substances are used as a cofactor in addition to the lignolytic enzymes (Siderophores such as ammonium oxalate) and biosurfactants on.
- the enhancer substances are described in WO 94/12619 on the basis of their Characterized half-life.
- enhancer substances are organic chemicals, containing at least two aromatic rings, of which at least one substituted with defined radicals is.
- WO 94/29510 describes a method for enzymatic delignification, where enzymes are used together with mediators become. Connections with are generally used as mediators of structure NO, NOH or HRNOH.
- HBT 1-Hydroxy-1H-benzotriazole
- Examples of compounds in the multicomponent system according to the invention can be used as mediators (component c) can be 2,6-dihydroxy-3-nitrosopyridine, 2,3-dihydroxy-4-nitrosopyridine, 2,6-dihydroxy-3-nitrosopyridine-4-carboxylic acid, 2,4-dihydroxy-3-nitrosopyridine, 3-hydroxy-2-mercaptopyridine, 2-hydroxy-3-mercaptopyridine, 2,6-diamino-3-nitrosopyridine, 2,6-diamino-3-nitrosopyridine-4-carboxylic acid, 2-hydroxy-3-nitrosopyridine, 3-hydroxy-2-nitrosopyridine, 2-mercapto-3-nitrosopyridine, 3-mercapto-2-nitrosopyridine, 2-amino-3-nitrosopyridine, 3-amino-2-nitrosopyridine, 2,4-dihydroxy-3-nitrosoquinoline, 8-hydroxy-5-nitrosoquinoline, 2,3-dihydroxy-4-nitrosoquino
- Preferred mediators are 2,6-dihydroxy-3-nitrosopyridine, 2, 6-diamino-3-nitrosopyridine, 2,6-dihydroxy-3-nitrosopyridine-4-carboxylic acid, 2,4-dihydroxy-3-nitrosopyridine, 2-hydroxy-3-mercaptopyridine, 2-mercapto-3-pyridinol, 2,4-dihydroxy-3-nitrosoquinoline, 8-hydroxy-5-nitrosoquinoline, 2,3-dihydroxy-4-nitrosoquinoline as well as tautomers of these compounds.
- the multicomponent system according to the invention contains mediators, which are cheaper than those known from the prior art Mediators, in particular, are less expensive than HBT.
- Oxidation catalysts in the multi-component system according to the invention Enzymes used.
- enzyme also includes enzymatically active Proteins or peptides or prosthetic groups of enzymes.
- the enzyme in the multicomponent system according to the invention Oxidoreductases of classes 1.1.1 to 1.97 according to international standards Enzyme Nomenclature, Committee of the International Union of Biochemistry and Molecular Biology (Enzyme Nomenclature, Academic Press, Inc., 1992, pp. 24-154) can be 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 this class are particularly preferred Class 1.1.5 with quinones as acceptors and the enzymes of the Class 1.1.3 with oxygen as the acceptor.
- Cellobiose is particularly preferred in this class: quinone-1-oxidoreductase (1.1.5.1).
- Enzymes of class 1.2 are also preferred. This class of enzymes 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) are particularly preferred here with oxygen as the acceptor.
- Enzymes of class 1.3 are also preferred.
- enzymes are summarized that are based on CH-CH groups of the donor.
- 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).
- Bilirubin oxidase (1.3.3.5) is particularly preferred.
- 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 other acceptors ( 1.4.99).
- Enzymes of class 1.4.3 are also particularly preferred here Oxygen as an acceptor.
- 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 are based on NADH are also preferred or NADPH work.
- 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 are particularly preferred here Quinones as acceptors.
- class 1.7 enzymes which act on donors of other NO 2 compounds and which accept cytochromes (1.7.2), oxygen (O 2 ) (1.7.3), iron-sulfur proteins (1.7.7) or others (1.7.99).
- Class 1.7.3 with oxygen is particularly preferred here as an acceptor.
- 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.
- Enzymes of class 1.12 which are based on hydrogen are also preferred act 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 (Oxigenases).
- preferred enzymes are those of class 1.15 which are based on Superoxide radicals act as acceptors.
- Enzymes of class 1.16 are also preferred.
- Enzymes of class 1.16.3.1 are particularly preferred here (Ferroxidase, e.g. ceruloplasmin).
- 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 are particularly preferred here (1.11.1.5), catalase (1.11.1.6), the peroxidase (1.11.1.6), iodide peroxidase (1.11.1.8), 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 (O 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-A-minophenol Oxidase (1.10.3.4) and laccase (benzene diol: oxigen Oxidoreductase) (1.10.3.2) is preferred, the laccases (benzenediol: Oxigen oxidoreductase) (1.10.3.2) is particularly preferred are.
- the enzymes mentioned are commercially available or can be win according to standard procedures.
- organisms for production the enzymes come from plants, animal cells, Bacteria and fungi into consideration. Basically, both naturally occurring as well as genetically modified organisms Be an enzyme producer. Parts of unicellular are also or multicellular organisms conceivable as enzyme producers, especially cell cultures.
- particularly preferred enzymes such as those from the group 1.11.1 but above all 1.10.3 and especially for production laccases, for example, are white rot fungi such as pleurotus, Phlebia and Trametes used.
- 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 (O 2 + ), dioxirane, dioxetane or fremy radicals can be used.
- Oxidizing agents are preferably used which either generated by the corresponding oxidoreductases can be e.g. Dioxiranes from laccases plus carbonyls or that can regenerate the mediator chemically or directly can implement.
- the invention also relates to the use of substances which according to the invention are suitable as mediators for changing, Degradation or bleaching of lignin or materials containing lignin.
- 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 (ED-TA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediamine triacetic acid (HEDTA), diethylenetriaminepentamethylenephosphonic acid ( , Nitrilotriacetic acid (NTA), polyphosphoric acid (PPA) etc. contains.
- the concentration is in the range of 0.2-5 mg / g of lignin-containing material, preferably 1-3 mg.
- a method using the method according to the invention is preferred Multi-component system in the presence of oxygen or air at normal pressure up to 10 bar and in a pH range from 2 to 11, preferably at a temperature of 20 to 95 ° C 40 - 95 ° C, and a consistency of 0.5 to 40% carried out.
- one according to the invention is preferred Process with material densities of 8 to 35%, particularly preferred 9 to 15% performed.
- the chelating agents become those Common substances (such as EDTA, DTPA) are used. They are preferably used in concentrations of 0.1% to 1% (w / w based on dry pulp), particularly preferably 0.1 % to 0.5% (w / w based on dry pulp) used.
- lignin-containing material 0.01 to 100,000 IU enzyme used per g of lignin-containing material. Especially 0.1 to 100 are particularly preferred 1 to 40 IU enzyme are used per g of lignin-containing material (1 U corresponds to the conversion of 1 ⁇ mol 2,2'-Azino-bis (3-ethyl-benzothiazoline-6-sulfonic acid diammonium salt) (ABTS) / min / ml enzyme
- oxidizing agent used per g of lignin-containing material.
- 0.01 to 50 mg of oxidizing agent are particularly preferred used per g of lignin-containing material.
- reducing agents can be added together with the existing oxidizing agents for adjustment serve a certain redox potential.
- Sodium bisulfite, sodium dithionite, Ascorbic acid, thio compounds, mercapto compounds or glutathione etc. can be used.
- the reaction takes place under air or Oxygen supply or oxygen or air pressure from, at the peroxidases (e.g. lignin peroxidases, manganese peroxidases) with hydrogen peroxide.
- peroxidases e.g. lignin peroxidases, manganese peroxidases
- oxygen also by hydrogen peroxide + catalase and hydrogen peroxide by glucose + GOD or other systems in situ to be generated.
- Radical formers or radical scavengers can also be added to the system (Trapping OH or OOH radicals, for example) added become. These can influence the interaction within the Red / Ox and improve 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 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 such to understand substances that the prosthetic groups of (here) simulate oxidoreductases and e.g. Oxidation reactions can catalyze.
- NaOCl can also be added to the reaction mixture. This compound can interact with hydrogen peroxide Form singlet oxygen.
- detergents it is also possible to use detergents to work. As such come non-ionic, anionic, cationic and amphoteric surfactants.
- the detergents can penetrate the enzymes and mediators into the fiber improve.
- Polysaccharides can also be beneficial for the reaction and / or add proteins.
- Polysaccharides glucans, mannans, dextrans, levans, pectins, Alginates or plant gums and / or your own mushrooms polysaccharides formed or produced in mixed culture with yeasts and to name gelatin and albumin as proteins.
- proteases such as pepsin, bromelin, papain etc. These can include serve by breaking down the extensin C present in the wood, Hydroxyproline-rich protein, better access to lignin to reach.
- protective colloids are amino acids, simple sugar, Oligomeric sugar, PEG types of the most varied Molecular weights, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes in question.
- the method according to the invention can be used not only for delignification (Bleaching) of sulfate, sulfite, organosol, etc.
- Pulp and wood pulp are used, but also in the manufacture of cellulose in general, be it from Wood or annual plants when defibrillated by the usual cooking methods (possibly connected with mechanical Process or printing) i.e. a very gentle cooking up to kappa numbers that range from about 50 to 120 kappa can lie, 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.
Abstract
Description
Die vorliegende Erfindung betrifft ein Mehrkomponentensystem zum Verändern, Abbau oder Bleichen von Lignin, oder ligninhaltigen Materialien sowie Verfahren zu seiner Anwendung.The present invention relates to a multi-component system for changing, breaking down or bleaching lignin or containing lignin Materials and procedures for its Application.
Als heute hauptsächlich zur Zellstoffherstellung verwendete Verfahren sind das Sulfat- und das Sulfitverfahren zu nennen. Mit beiden Verfahren wird unter Kochung und unter Druck Zellstoff erzeugt. Das Sulfat-Verfahren arbeitet unter Zusatz von NaOH und Na2S, während im Sulfit-Verfahren Ca(HSO3)2 + SO2 zur Anwendung kommt.The sulfate and sulfite processes are the main processes used today for pulp production. Both methods produce pulp under cooking and under pressure. The sulfate process works with the addition of NaOH and Na 2 S, while the sulfite process uses Ca (HSO 3 ) 2 + SO 2 .
Alle Verfahren haben als Hauptziel die Entfernung des Lignins aus dem verwendeten Pflanzenmaterial, Holz oder Einjahrespflanzen.The main goal of all procedures is the removal of the lignin from the used plant material, wood or Annual plants.
Das Lignin, das mit der Cellulose und der Hemicellulose den Hauptbestandteil des Pflanzenmaterials (Stengel oder Stamm) ausmacht, muß entfernt werden, da es sonst nicht möglich ist, nicht vergilbende und mechanisch hochbelastbare Papiere herzustellen.The lignin that is associated with cellulose and hemicellulose Main component of the plant material (stem or stem) must be removed, otherwise it is not possible non-yellowing and mechanically heavy-duty papers to manufacture.
Die Holzstofferzeugungsverfahren arbeiten mit Steinschleifern (Holzschliff) oder mit Refinern (TMP), die das Holz nach entsprechender Vorbehandlung (chemisch, thermisch oder chemisch-thermisch) durch Mahlen defibrillieren.The wood production processes work with stone grinders (Wood sanding) or with refiners (TMP), which the wood after appropriate Pretreatment (chemical, thermal or chemical-thermal) defibrillate by grinding.
Diese Holzstoffe besitzen noch einen Großteil des Lignins. Sie werden v. a. für die Herstellung von Zeitungen, Illustrierten, etc. verwendet.These wood materials still contain a large part of the lignin. she be v. a. for the production of newspapers, magazines, etc. used.
Seit einigen Jahren werden die Möglichkeiten des Einsatzes von Enzymen für den Ligninabbau erforscht. Der Wirkmechanismus derartiger lignolytischer Systeme ist erst vor wenigen Jahren aufgeklärt worden, als es gelang, durch geeignete Anzuchtbedingungen und Induktorzusätze bei dem Weißfäulepilz Phanerochaete chrysosporium zu ausreichenden Enzymmengen zu kommen. Hierbei wurden die bis dahin unbekannten Ligninperoxidasen und Manganperoxidasen entdeckt. Da Phanerochaete chrysosporium ein sehr effektiver Ligninabbauer ist, versuchte man dessen Enzyme zu isolieren und in gereinigter Form für den Ligninabbau zu verwenden. Dies gelang jedoch nicht, da sich herausstellte, daß die Enzyme vor allem zu einer Repolymerisation des Lignins und nicht zu dessen Abbau führen.For some years now, the possibilities of using Enzymes for lignin degradation researched. The mechanism of action Such lignolytic systems is only a few years ago been enlightened when it succeeded through appropriate growing conditions and inductor additives in the white rot fungus Phanerochaete chrysosporium to get sufficient amounts of enzyme. The previously unknown lignin peroxidases and Manganese peroxidases discovered. Since Phanerochaete chrysosporium is very effective lignin degrader, one tried its enzymes to isolate and in purified form for lignin degradation use. However, this did not work because it turned out that the enzymes mainly cause repolymerization of the lignin and do not lead to its degradation.
Ähnliches gilt auch für andere lignolytische Enzymspezies wie Laccasen, die das Lignin mit Hilfe von Sauerstoff anstelle von Wasserstoffperoxid oxidativ abbauen. Es konnte festgestellt werden, daß es in allen Fällen zu ähnlichen Prozessen kommt. Es werden nämlich Radikale gebildet, die wieder selbst miteinander reagieren und somit zur Polymerisation führen.The same applies to other lignolytic enzyme species such as Laccases that replace the lignin with the help of oxygen decompose oxidatively from hydrogen peroxide. It was found be that there are similar processes in all cases is coming. Radicals are formed, which are themselves react with each other and thus lead to polymerization.
So gibt es heute nur Verfahren, die mit in-vivo Systemen arbeiten (Pilzsysteme). Hauptschwerpunkte von Optimierungsversuchen sind das sogenannte Biopulping und das Biobleaching.Today there are only processes that work with in-vivo systems (Mushroom systems). Main focus of optimization attempts are so-called biopulping and biobleaching.
Unter Biopulping versteht man die Behandlung von Holzhackschnitzeln mit lebenden Pilzsystemen.Biopulping is the treatment of wood chips with living mushroom systems.
Es gibt 2 Arten von Applikationsformen:
Hier ist das Ziel, die Reduzierung von Kochchemikalien, die Verbesserung der Kochkapazität und "extended cooking".The goal here is to reduce the amount of cooking chemicals that Improve cooking capacity and "extended cooking".
Als Vorteile werden auch eine verbesserte Kappareduzierung nach dem Kochen im Vergleich zu einem Kochen ohne Vorbehandlung erreicht.Improved kappa reduction is also an advantage after cooking compared to cooking without pretreatment reached.
Nachteile dieser Verfahren sind eindeutig die langen Behandlungszeiten (mehrere Wochen) und v.a. die nicht gelöste Kontaminierungsgefahr während der Behandlung, wenn man auf die wohl unwirtschaftliche Sterilisation der Hackschnitzel verzichten will.The disadvantages of these procedures are clearly the long treatment times (several weeks) and especially the unresolved Risk of contamination during treatment if one is on the dispense with uneconomic sterilization of the wood chips want.
Das Biobleaching arbeitet ebenfalls mit in-vivo Systemen. Der gekochte Zellstoff (Softwood/Hardwood) wird vor der Bleiche mit dem Pilz beimpft und für Tage bis Wochen behandelt. Nur nach dieser langen Behandlungszeit zeigt sich eine signifikante Kappazahlerniedrigung und Weißesteigerung, was den Prozeß unwirtschaftlich für eine Implementierung in den gängigen Bleichsequenzen macht.Biobleaching also works with in-vivo systems. The cooked pulp (Softwood / Hardwood) is before bleaching inoculated with the fungus and treated for days to weeks. Just after this long treatment period, a significant one becomes apparent Kappa reduction and whiteness, what the process uneconomical for an implementation in the usual Bleaching sequences.
Eine weitere meist mit immobilisierten Pilzsystemen durchgeführte Applikation ist die Behandlung von Zellstoffabrikationsabwässern, insbesondere Bleichereiabwässern zu deren Entfärbung und Reduzierung des AOX (Reduzierung von chlorierten Verbindungen im Abwasser, die Chlor- oder Chlordioxid-Bleichstufen verursachen).Another mostly carried out with immobilized mushroom systems Application is the treatment of pulp wastewater, in particular bleaching waste water to decolorize them and reduction of AOX (reduction of chlorinated Compounds in wastewater, the chlorine or chlorine dioxide bleaching stages cause).
Darüber hinaus ist bekannt, Hemicellulasen u.a. Xylanasen, Mannanasen als "Bleichbooster" einzusetzen.It is also known that hemicellulases, etc. Xylanases, Use mannanases as "bleach boosters".
Diese Enzyme sollen hauptsächlich gegen das nach dem Kochprozeß das Restlignin zum Teil überdeckende reprecipitierte Xylan wirken und durch dessen Abbau die Zugänglichkeit des Lignins für die in den nachfolgenden Bleichsequenzen angewendeten Bleichchemikalien (v.a. Chlordioxid) erhöhen. Die im Labor nachgewiesenen Einsparungen von Bleichchemikalien wurden in großem Maßstab nur bedingt bestätigt, so daß man diesen Enzymtyp allenfalls als Bleichadditiv einstufen kann.These enzymes are primarily intended to counteract that after the cooking process Recycled xylan partially covering the residual lignin act and by its degradation the accessibility of the lignin for those used in the subsequent bleaching sequences Increase bleaching chemicals (especially chlorine dioxide). The one in the laboratory proven savings of bleaching chemicals have been made in Large scale confirmed only to a limited extent, so that this type of enzyme can at best be classified as a bleaching additive.
Als Cofaktor neben den lignolytischen Enzymen nimmt man Chelatsubstanzen (Siderophoren, wie Ammoniumoxalat) und Biotenside an.Chelate substances are used as a cofactor in addition to the lignolytic enzymes (Siderophores such as ammonium oxalate) and biosurfactants on.
In der Anmeldung PCT/EP87/00635 wird ein System zur Entfernung von Lignin aus lignincellulosehaltigem Material unter gleichzeitiger Bleiche beschrieben, welches mit lignolytischen Enzymen aus Weißfäulepilzen unter Zusatz von Reduktions- und Oxidationsmitteln und phenolischen Verbindungen als Mediatoren arbeitet.In the application PCT / EP87 / 00635 there is a removal system of lignin from lignin cellulosic material with simultaneous Bleach described, which with lignolytic enzymes from white rot fungi with the addition of reducing and oxidizing agents and phenolic compounds as mediators is working.
In der DE 4008893C2 werden zusätzlich zu Red/Ox-System "Mimic Substanzen", die das aktive Zentrum (prosthetische Gruppe) von lignolytischen Enzymen simulieren, zugesetzt. So konnte eine erhebliche Performanceverbesserung erzielt werden.In DE 4008893C2, in addition to the Red / Ox system, "Mimic Substances "that the active center (prosthetic group) of Simulate lignolytic enzymes, added. So one could significant performance improvement can be achieved.
In der Anmeldung PCT/EP92/01086 wird als zusätzliche Verbesserung eine Redoxkaskade mit Hilfe von im Oxidationspotential "abgestimmten" phenolischen oder nichtphenolischen Aromaten eingesetzt.In the application PCT / EP92 / 01086 there is an additional improvement a redox cascade with the help of oxidation potential "Matched" phenolic or non-phenolic aromatics used.
Bei allen drei Verfahren ist die Limitierung für einen groß-technischen Einsatz die Anwendbarkeit bei geringen Stoffdichten (bis maximal 4%) und bei den beiden letzten Anmeldungen die Gefahr des "Ausleachens" von Metallen beim Einsatz der Chelatverbindungen, die v.a. bei nachgeschalteten Peroxidbleichstufen zur Zerstörung des Peroxids führen können.In all three processes, the limitation is for a large-scale one Use the applicability with low consistency (up to a maximum of 4%) and for the last two registrations the danger of "leaching" of metals when using the Chelate compounds, which with downstream peroxide bleaching stages can lead to the destruction of the peroxide.
Aus WO/12619, WO 94/12620 und WO 94/12621 sind Verfahren bekannt, bei welchen die Aktivität von Peroxidase mittels sogenannter Enhancer-Substanzen gefördert werden.Methods are known from WO / 12619, WO 94/12620 and WO 94/12621, in which the activity of peroxidase by means of so-called Enhancer substances are promoted.
Die Enhancer-Substanzen werden in WO 94/12619 anhand ihrer Halbwertslebensdauer charakterisiert. The enhancer substances are described in WO 94/12619 on the basis of their Characterized half-life.
Gemäß WO 94/12620 sind Enhancer-Substanzen durch die Formel A=N-N=B charakterisiert, wobei A und B jeweils definierte cyclische Reste sind.According to WO 94/12620, enhancer substances are represented by the formula A = N-N = B characterized, where A and B each defined cyclic Leftovers are.
Gemäß WO 94/12620 sind Enhancer-Substanzen organische Chemikalien, die mindestens zwei aromatische Ringe enthalten, von denen zumindest einer mit jeweils definierten Resten substituiert ist.According to WO 94/12620, enhancer substances are organic chemicals, containing at least two aromatic rings, of which at least one substituted with defined radicals is.
Alle drei Anmeldungen betreffen "dye transfer Inhibition" und den Einsatz der jeweiligen Enhancer-Substanzen zusammen mit Peroxidasen als Detergent-Additiv oder Detergent-Zusammensetzung im Waschmittelbereich. Zwar wird in der Beschreibung der Anmeldung auf eine Verwendbarkeit zum Behandeln von Lignin verwiesen, aber eigene Versuche mit den in den Anmeldungen konkret offenbarten Substanzen zeigten, daß sie als Mediatoren zur Steigerung der Bleichwirkung der Peroxidasen beim Behandeln von ligninhaltigen Materialien keine Wirkung zeigten!All three applications concern "dye transfer inhibition" and the use of the respective enhancer substances together with Peroxidases as a detergent additive or detergent composition in the detergent area. Although in the description of the Registration for usability to treat lignin referenced, but own experiments with those in the registrations Substances specifically disclosed showed that they act as mediators to increase the bleaching effect of the peroxidases during treatment of materials containing lignin showed no effect!
WO 94/29510 beschreibt ein Verfahren zur enzymatischen Delignifizierung, bei dem Enzyme zusammen mit Mediatoren eingesetzt werden. Als Mediatoren werden allgemein Verbindungen mit der Struktur NO-, NOH- oder HRNOH offenbart.WO 94/29510 describes a method for enzymatic delignification, where enzymes are used together with mediators become. Connections with are generally used as mediators of structure NO, NOH or HRNOH.
Von den in WO 94/29510 aufgeführten Mediatoren liefert 1-Hydroxy-1H-benzotriazol (HBT) die besten Ergebnisse in der Delignifizierung. HBT hat jedoch verschiedene Nachteile:Of the mediators listed in WO 94/29510 1-Hydroxy-1H-benzotriazole (HBT) the best results in the Delignification. However, HBT has several disadvantages:
Es ist nur zu hohen Preisen und nicht in hinreichenden Mengen verfügbar.It is only at high prices and not in sufficient quantities available.
Es reagiert unter Delignifizierungsbedingungen zu 1H-Benzotriazol. Diese Verbindung ist relativ schlecht abbaubar und kann in größeren Mengen eine beträchtliche Umweltbelastung darstellen. Es führt in gewissem Umfang zu einer Schädigung von Enzymen. Seine Delignifizierungsgeschwindigkeit ist nicht allzu hoch. It reacts under delignification conditions 1H-benzotriazole. This connection is relatively poorly degradable and in large quantities can cause significant environmental pollution represent. To some extent, it leads to damage of enzymes. Its delignification rate is not too high.
Es ist daher wünschenswert, Systeme zum Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen zur Verfügung zu stellen, die die genannten Nachteile nicht oder in geringerem Maße aufweisen.It is therefore desirable to change, dismantle or Bleaching lignin, materials containing lignin or the like To provide substances that have the disadvantages mentioned not or have to a lesser extent.
Die vorliegende Erfindung betrifft daher ein Mehrkomponentensystem
zum Verändern, Abbau oder Bleichen von Lignin oder ligninhaltigen
Materialien enthaltend
Überraschend wurde gefunden, daß das erfindungsgemäße Mehrkomponentensystem mit den genannten Mediatoren nicht die Nachteile der aus dem Stand der Technik bekannten Mehrkomponentensysteme aufweist.It has surprisingly been found that the multicomponent system according to the invention with the mediators mentioned not the disadvantages the multi-component systems known from the prior art having.
Bevorzugt sind als Mediatoren im erfindungsgemäßen Mehrkomponentensystem
Verbindungen der allgemeinen Formel (I), (II)
oder (III)
Als Mediatoren im erfindungsgemäßen Mehrkomponentensystem besonders
bevorzugt sind Verbindungen der allgemeinen Formel (I)
oder (II) sowie deren Tautomere, Salze, Ether oder Ester, wobei
in den Formeln (I) und (II) besonders bevorzugt zwei zueinander
ortho- ständige Reste R1 Hydroxy- und Nitrosorest
oder Hydroxy- und Mercaptorest oder Nitrosorest- und Aminorest
bedeuten und
wobei
in which
Beispiele für Verbindungen, die im erfindungsgemäßen Mehrkomponentensystem als Mediatoren (Komponente c) eingesetzt werden können, sind 2,6-Dihydroxy-3-nitrosopyridin, 2,3-Dihydroxy-4-nitrosopyridin, 2,6-Dihydroxy-3-nitrosopyridin-4-carbonsäure, 2,4-Dihydroxy-3-nitrosopyridin, 3-Hydroxy-2-mercaptopyridin, 2-Hydroxy-3-mercaptopyridin, 2,6-Diamino-3-nitrosopyridin, 2,6-Diamino-3-nitroso-pyridin-4-carbonsäure, 2-Hydroxy-3-nitrosopyridin, 3-Hydroxy-2-nitrosopyridin, 2-Mercapto-3-nitrosopyridin, 3-Mercapto-2-nitrosopyridin, 2-Amino-3-nitrosopyridin, 3-Amino-2-nitrosopyridin, 2,4-Dihydroxy-3-nitrosochinolin, 8-Hydroxy-5-nitrosochinolin, 2,3-Dihydroxy-4-nitrosochinolin, 3-Hydroxy-4-nitrosoisochinolin, 4-Hydroxy-3-nitrosoisochinolin, 8-Hydroxy-5-nitrosoisochinolin sowie Tautomere dieser Verbindungen.Examples of compounds in the multicomponent system according to the invention can be used as mediators (component c) can be 2,6-dihydroxy-3-nitrosopyridine, 2,3-dihydroxy-4-nitrosopyridine, 2,6-dihydroxy-3-nitrosopyridine-4-carboxylic acid, 2,4-dihydroxy-3-nitrosopyridine, 3-hydroxy-2-mercaptopyridine, 2-hydroxy-3-mercaptopyridine, 2,6-diamino-3-nitrosopyridine, 2,6-diamino-3-nitrosopyridine-4-carboxylic acid, 2-hydroxy-3-nitrosopyridine, 3-hydroxy-2-nitrosopyridine, 2-mercapto-3-nitrosopyridine, 3-mercapto-2-nitrosopyridine, 2-amino-3-nitrosopyridine, 3-amino-2-nitrosopyridine, 2,4-dihydroxy-3-nitrosoquinoline, 8-hydroxy-5-nitrosoquinoline, 2,3-dihydroxy-4-nitrosoquinoline, 3-hydroxy-4-nitrosoisoquinoline, 4-hydroxy-3-nitrosoisoquinoline, 8-hydroxy-5-nitrosoisoquinoline as well as tautomers of these compounds.
Als Mediatoren sind bevorzugt 2,6-Dihydroxy-3-nitrosopyridin, 2, 6-Diamino-3-nitrosopyridin, 2,6-Dihydroxy-3-nitrosopyridin-4-carbonsäure, 2,4-Dihydroxy-3-nitrosopyridin, 2-Hydroxy-3-mercaptopyridin, 2-Mercapto-3-pyridinol, 2,4-Dihydroxy-3-nitrosochinolin, 8-Hydroxy-5-nitrosochinolin, 2,3-Dihydroxy-4-nitrosochinolin sowie Tautomere dieser Verbindungen.Preferred mediators are 2,6-dihydroxy-3-nitrosopyridine, 2, 6-diamino-3-nitrosopyridine, 2,6-dihydroxy-3-nitrosopyridine-4-carboxylic acid, 2,4-dihydroxy-3-nitrosopyridine, 2-hydroxy-3-mercaptopyridine, 2-mercapto-3-pyridinol, 2,4-dihydroxy-3-nitrosoquinoline, 8-hydroxy-5-nitrosoquinoline, 2,3-dihydroxy-4-nitrosoquinoline as well as tautomers of these compounds.
Das erfindungsgemäße Mehrkomponentensystem enthält Mediatoren, die kostengünstiger als die aus dem Stand der Technik bekannten Mediatoren, insbesondere kostengünstiger als HBT sind.The multicomponent system according to the invention contains mediators, which are cheaper than those known from the prior art Mediators, in particular, are less expensive than HBT.
Darüber hinaus wird bei Einsatz der erfindungsgemäßen Mediatoren eine Steigerung der Delignifizierungsgeschwindigkeit erzielt. In addition, when using the mediators according to the invention an increase in the rate of delignification achieved.
Als Oxidationskatalysatoren werden im erfindungsgemäßen Mehrkomponentensystem Enzyme eingesetzt. Im Sinne der Erfindung umfaßt der Begriff Enzym auch enzymatisch aktive Proteine oder Peptide oder prosthetische Gruppen von Enzymen.Oxidation catalysts in the multi-component system according to the invention Enzymes used. In the sense of the Invention, the term enzyme also includes enzymatically active Proteins or peptides or prosthetic groups of enzymes.
Als Enzym können im erfindungsgemäßen Mehrkomponentensystem Oxidoreduktasen der Klassen 1.1.1 bis 1.97 gemäß Internationaler Enzym-Nomenklature, Committee of the International Union of Biochemistry and Molecular Biology (Enzyme Nomenclature, Academic Press, Inc., 1992, S. 24-154) eingesetzt werden.The enzyme in the multicomponent system according to the invention Oxidoreductases of classes 1.1.1 to 1.97 according to international standards Enzyme Nomenclature, Committee of the International Union of Biochemistry and Molecular Biology (Enzyme Nomenclature, Academic Press, Inc., 1992, pp. 24-154) can be used.
Vorzugsweise werden Enzyme der im folgenden genannten Klassen eingesetzt:Enzymes of the classes mentioned below are preferred used:
Enzyme der Klasse 1.1, die alle Dehydrogenasen, die auf primäre, sekundäre Alkohole und Semiacetale wirken, umfassen und die als Akzeptoren NAD+ oder NADP+ (Subklasse 1.1.1), Cytochrome (1.1.2), Sauerstoff (O2) (1.1.3), Disulfide (1.1.4), Chinone (1.1.5) oder die andere Akzeptoren haben (1.1.99).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).
Aus dieser Klasse sind besonders bevorzugt die Enzyme der Klasse 1.1.5 mit Chinonen als Akzeptoren und die Enzyme der Klasse 1.1.3 mit Sauerstoff als Akzeptor.The enzymes of this class are particularly preferred Class 1.1.5 with quinones as acceptors and the enzymes of the Class 1.1.3 with oxygen as the acceptor.
Insbesondere bevorzugt in dieser Klasse ist Cellobiose: quinone-1-oxidoreduktase (1.1.5.1).Cellobiose is particularly preferred in this class: quinone-1-oxidoreductase (1.1.5.1).
Weiterhin bevorzugt sind Enzyme der Klasse 1.2. Diese Enzymklasse umfaßt solche Enzyme, die Aldehyde zu den korrespondierenden Säuren oder Oxo-Gruppen oxidieren. Die Akzeptoren können NAD+, NADP+ (1.2.1), Cytochrome (1.2.2), Sauerstoff (1.2.3), Sulfide (1.2.4), Eisen-Schwefel-Proteine (1.2.5) oder andere Akzeptoren (1.2.99) sein.Enzymes of class 1.2 are also preferred. This class of enzymes 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).
Besonders bevorzugt sind hier die Enzyme der Gruppe (1.2.3) mit Sauerstoff als Akzeptor.The enzymes of group (1.2.3) are particularly preferred here with oxygen as the acceptor.
Weiterhin bevorzugt sind Enzyme der Klasse 1.3. Enzymes of class 1.3 are also preferred.
In dieser Klasse sind Enzyme zusammengefaßt, die auf CH-CH-Gruppen des Donors wirken.In this class, enzymes are summarized that are based on CH-CH groups of the donor.
Die entsprechenden Akzeptoren sind NAD+, NADP+ (1.3.1), Cytochrome (1.3.2), Sauerstoff (1.3.3), Chinone oder verwandte Verbindungen (1.3.5), Eisen-Schwefel-Proteine (1.3.7) oder andere Akzeptoren (1.3.99).The corresponding 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).
Besonders bevorzugt ist die Bilirubinoxidase (1.3.3.5).Bilirubin oxidase (1.3.3.5) is particularly preferred.
Hier sind ebenfalls die Enzyme der Klasse (1.3.3) mit Sauerstoff als Akzeptor und (1.3.5) mit Chinonen etc. als Akzeptor besonders bevorzugt.Here are also the enzymes of class (1.3.3) with oxygen as acceptor and (1.3.5) with quinones etc. as acceptor particularly preferred.
Weiterhin bevorzugt sind Enzyme der Klasse 1.4, die auf CH-NH2-Gruppen des Donors wirken.Also preferred are class 1.4 enzymes which act on CH-NH 2 groups of the donor.
Die entsprechenden Akzeptoren sind NAD+, NADP+ (1.4.1), Cytochrome (1.4.2), Sauerstoff (1.4.3), Disulfide (1.4.4), Eisen-Schwefel-Proteine (1.4.7) oder andere Akzeptoren (1.4.99).The corresponding 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).
Besonders bevorzugt sind auch hier Enzyme der Klasse 1.4.3 mit Sauerstoff als Akzeptor.Enzymes of class 1.4.3 are also particularly preferred here Oxygen as an acceptor.
Weiterhin bevorzugt sind Enzyme der Klasse 1.5, die auf CH-NH-Gruppen des Donors wirken. Die entsprechenden Akzeptoren sind NAD+, NADP+ (1.5.1), Sauerstoff (1.5.3), Disulfide (1.5.4), Chinone (1.5.5) oder andere Akzeptoren (1.5.99).Also preferred are 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).
Auch hier sind besonders bevorzugt Enzyme mit Sauerstoff (O2) (1.5.3) und mit Chinonen (1.5.5) als Akzeptoren.Here too, enzymes with oxygen (O 2 ) (1.5.3) and with quinones (1.5.5) are particularly preferred as acceptors.
Weiterhin bevorzugt sind Enzyme der Klasse 1.6, die auf NADH oder NADPH wirken. Enzymes of class 1.6 which are based on NADH are also preferred or NADPH work.
Die Akzeptoren sind hier NADP+ (1.6.1), Hämproteine (1.6.2), Disulfide (1.6.4), Chinone (1.6.5), NO2-Gruppen (1.6.6), und ein Flavin (1.6.8) oder einige andere Akzeptoren (1.6.99).The 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).
Besonders bevorzugt sind hier Enzyme der Klasse 1.6.5 mit Chinonen als Akzeptoren.Enzymes of class 1.6.5 are particularly preferred here Quinones as acceptors.
Weiterhin bevorzugt sind Enzyme der Klasse 1.7, die auf andere NO2-Verbindungen als Donatoren wirken und als Akzeptoren Cytochrome (1.7.2), Sauerstoff (O2) (1.7.3), Eisen-Schwefel-Proteine (1.7.7) oder andere (1.7.99) haben.Also preferred are class 1.7 enzymes which act on donors of other NO 2 compounds and which accept cytochromes (1.7.2), oxygen (O 2 ) (1.7.3), iron-sulfur proteins (1.7.7) or others (1.7.99).
Hier sind besonders bevorzugt die Klasse 1.7.3 mit Sauerstoff als Akzeptor.Class 1.7.3 with oxygen is particularly preferred here as an acceptor.
Weiterhin bevorzugt sind Enzyme der Klasse 1.8, die auf Schwefelgruppen als Donatoren wirken und als Akzeptoren NAD+, NADP+ (1.8.1), Cytochrome (1.8.2), Sauerstoff (O2) (1.8.3), Disulfide (1.8.4), Chinone (1.8.5), Eisen-Schwefel-Proteine (1.8.7) oder andere (1.8.99) haben.Also preferred are 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).
Besonders bevorzugt ist die Klasse 1.8.3 mit Sauerstoff (O2) und (1.8.5) mit Chinonen als Akzeptoren.Class 1.8.3 with oxygen (O 2 ) and (1.8.5) with quinones as acceptors is particularly preferred.
Weiterhin bevorzugt sind Enzyme der Klasse 1.9, die auf Hämgruppen als Donatoren wirken und als Akzeptoren Sauerstoff (O2) (1.9.3), NO2-Verbindungen (1.9.6) und andere (1.9.99) haben.Also preferred are 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.
Besonders bevorzugt ist hier die Gruppe 1.9.3 mit Sauerstoff (O2) als Akzeptor (Cytochromoxidasen).Group 1.9.3 with oxygen (O 2 ) as acceptor (cytochrome oxidases) is particularly preferred here.
Weiterhin bevorzugt sind Enzyme der Klasse 1.12, die auf Wasserstoff als Donor wirken.Enzymes of class 1.12 which are based on hydrogen are also preferred act as a donor.
Die Akzeptoren sind NAD+ oder NADP+ (1.12.1) oder andere (1.12.99). The acceptors are NAD + or NADP + (1.12.1) or others (1.12.99).
Desweiteren bevorzugt sind Enzyme der Klasse 1.13 und 1.14 (Oxigenasen).Enzymes of class 1.13 and 1.14 are also preferred (Oxigenases).
Weiterhin sind bevorzugte Enzyme die der Klasse 1.15 , die auf Superoxid-Radikale als Akzeptoren wirken.Furthermore, preferred enzymes are those of class 1.15 which are based on Superoxide radicals act as acceptors.
Besonders bevorzugt ist hier die Superoxid-Dismutase (1.15.1.1).Superoxide dismutase is particularly preferred here (1.15.1.1).
Weiterhin sind bevorzugt Enzyme der Klasse 1.16.Enzymes of class 1.16 are also preferred.
Als Akzeptoren wirken NAD+ oder NADP+ (1.16.1) oder Sauerstoff (O2) (1.16.3).NAD + or NADP + (1.16.1) or oxygen (O 2 ) (1.16.3) act as acceptors.
Besonders bevorzugt sind hier Enzyme der Klasse 1.16.3.1 (Ferroxidase, z.B. Ceruloplasmin).Enzymes of class 1.16.3.1 are particularly preferred here (Ferroxidase, e.g. ceruloplasmin).
Weiterhin bevorzugte Enzyme sind diejenigen, die der Gruppe 1.17 (Wirkung auf CH2-Gruppen, die zu -CHOH- oxidiert werden), 1.18 (Wirkung auf reduziertes Ferredoxin als Donor), 1.19 (Wirkung auf reduziertes Flavodoxin als Donor) und 1.97(andere Oxidoreduktasen) angehören.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).
Weiterhin besonders bevorzugt sind die Enzyme der Gruppe 1.11. die auf ein Peroxid als Akzeptor wirken. Diese einzige Subklasse (1.11.1) enthält die Peroxidasen.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.
Besonders bevorzugt sind hier die Cytochrom-C-Peroxidasen (1.11.1.5), Catalase (1.11.1.6), die Peroxydase (1.11.1.6), die Iodid-Peroxidase (1.11.1.8), die Glutathione-Peroxidase (1.11.1.9), die Chlorid-Peroxidase (1.11.1.10), die L-Ascorbat-Peroxidase (1.11.1.11), die Phospholipid-Hydroperoxid-Glutathione-Peroxidase (1.11.1.12), die Mangan-Peroxidase (1.12.1.13), die Diarylpropan-Peroxidase (Ligninase, Lignin-Peroxidase) (1.11.1.14).The cytochrome C peroxidases are particularly preferred here (1.11.1.5), catalase (1.11.1.6), the peroxidase (1.11.1.6), iodide peroxidase (1.11.1.8), 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).
Ganz besonders bevorzugt sind Enzyme der Klasse 1.10, die auf Biphenole und verwandten Verbindungen wirken. Sie katalysieren die Oxidation von Biphenolen und Ascorbaten. Als Akzeptoren fungieren NAD+, NADP+ (1.10.1), Cytochrome (1.10.2), Sauerstoff (1.10.3) oder andere (1.10.99).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.
Von diesen wiederum sind Enzyme der Klasse 1.10.3 mit Sauerstoff (O2) als Akzeptor besonders bevorzugt.Of these in turn, class 1.10.3 enzymes with oxygen (O 2 ) as the acceptor are particularly preferred.
Von den Enzymen dieser Klasse sind die Enzyme Catechol Oxidase (Tyrosinase) (1.10.3.1), L-Ascorbate Oxidase (1.10.3.3), o-A-minophenol Oxidase (1.10.3.4) und Laccase (Benzoldiol: Oxigen Oxidoreduktase) (1.10.3.2) bevorzugt, wobei die Laccasen (Benzoldiol: Oxigen Oxidoreduktase) (1.10.3.2) insbesondere bevorzugt sind.Of the enzymes in this class, the enzymes are catechol oxidase (Tyrosinase) (1.10.3.1), L-ascorbate oxidase (1.10.3.3), o-A-minophenol Oxidase (1.10.3.4) and laccase (benzene diol: oxigen Oxidoreductase) (1.10.3.2) is preferred, the laccases (benzenediol: Oxigen oxidoreductase) (1.10.3.2) is particularly preferred are.
Die genannten Enzyme sind käuflich erhältlich oder lassen sich nach Standardverfahren gewinnen. Als Organismen zur Produktion der Enzyme kommen beispielsweise Pflanzen, tierische Zellen, Bakterien und Pilze in Betracht. Grundsätzlich können sowohl natürlich vorkommende als auch gentechnisch veränderte Organismen Enzymproduzenten sein. Ebenso sind Teile von einzelligen oder mehrzelligen Organismen als Enzymproduzenten denkbar, vor allem Zellkulturen.The enzymes mentioned are commercially available or can be win according to standard procedures. As organisms for production the enzymes come from plants, animal cells, Bacteria and fungi into consideration. Basically, both naturally occurring as well as genetically modified organisms Be an enzyme producer. Parts of unicellular are also or multicellular organisms conceivable as enzyme producers, especially cell cultures.
Für die insbesondere bevorzugten Enzyme, wie die aus der Gruppe 1.11.1 vor allem aber 1.10.3 und insbesondere zur Produktion von Laccasen werden beispielsweise Weißfäulepilze wie Pleurotus, Phlebia und Trametes verwendet.For the particularly preferred enzymes, such as those from the group 1.11.1 but above all 1.10.3 and especially for production laccases, for example, are white rot fungi such as pleurotus, Phlebia and Trametes used.
Das erfindungsgemäße Mehrkomponentensystem umfaßt mindestens ein Oxidationsmittel. Als Oxidationsmittel können beispielsweise Luft, Sauerstoff, Ozon, H2O2, organische Peroxide, Persäuren wie die Peressigsäure, Perameisensäure, Perschwefelsäure, Persalpetersäure, Metachlorperoxibenzosäure, Perchlorsäure, Perborate, Peracetate, Persulfate, Peroxide oder Sauerstoffspezies und deren Radikale wie OH, OOH, Singulettsauerstoff, Superoxid (O2 -), Ozonid, Dioxygenyl-Kation (O2 +), Dioxirane, Dioxetane oder Fremy Radikale eingesetzt werden. 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 (O 2 + ), dioxirane, dioxetane or fremy radicals can be used.
Vorzugsweise werden solche Oxidationsmittel eingesetzt, die entweder durch die entsprechenden Oxidoreduktasen generiert werden können z.B. Dioxirane aus Laccasen plus Carbonylen oder die chemisch den Mediator regenerieren können oder diesen direkt umsetzen können.Oxidizing agents are preferably used which either generated by the corresponding oxidoreductases can be e.g. Dioxiranes from laccases plus carbonyls or that can regenerate the mediator chemically or directly can implement.
Die Erfindung betrifft auch die Verwendung von Substanzen, welche erfindungsgemäß als Mediatoren geeignet sind zum Verändern, Abbau oder Bleichen von Lignin oder ligninhaltigen Materialien.The invention also relates to the use of substances which according to the invention are suitable as mediators for changing, Degradation or bleaching of lignin or materials containing lignin.
Die Wirksamkeit des Mehrkomponentensystems beim Verändern, Abbau oder Bleichen von Lignin, ligninhaltigen Materialien oder ähnlichen Stoffen ist häufig nochmals gesteigert, wenn neben den genannten Bestandteilen noch Mg2+ Ionen vorhanden sind. Die Mg2+ Ionen können beispielsweise als Salz, wie z.B. MgSO4, eingesetzt werden. Die Konzentration liegt im Bereich von 0,1 - 2 mg/g ligninhaltigem Material, vorzugsweise bei 0,2 - 0,6 mg/g.The effectiveness of the multi-component system when changing, breaking down or bleaching lignin, lignin-containing materials or similar substances is often further increased if Mg 2+ ions are present in addition to the components mentioned. The Mg 2+ ions can be used, for example, as a salt, such as MgSO 4 . The concentration is in the range of 0.1-2 mg / g of lignin-containing material, preferably 0.2-0.6 mg / g.
In manchen Fällen läßt sich eine weitere Steigerung der Wirksamkeit des erfindungsgemäßen Mehrkomponentensystems dadurch erreichen, daß das Mehrkomponentensystem neben den Mg2+ Ionen auch Komplexbildner wie z.B. Ethylendiamintetraessigsäure (ED-TA), Diethylentriaminpentaessigsäure (DTPA), Hydroxyethylendiamintriessigsäure (HEDTA), Diethylentriaminpentamethylenphosphonsäure (DTMPA), Nitrilotriessigsäure (NTA), Polyphosphorsäure (PPA) etc. enthält. Die Konzentration liegt im Bereich von 0,2 - 5 mg/g ligninhaltigem Material, vorzugsweise bei 1 - 3 mg.In some cases 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 (ED-TA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediamine triacetic acid (HEDTA), diethylenetriaminepentamethylenephosphonic acid ( , Nitrilotriacetic acid (NTA), polyphosphoric acid (PPA) etc. contains. The concentration is in the range of 0.2-5 mg / g of lignin-containing material, preferably 1-3 mg.
Der Einsatz des erfindungsgemäßen Mehrkomponentensystems in einem Verfahren zu Behandeln von Lignin erfolgt beispielsweise dadurch, daß man die jeweils ausgewählten Komponenten a) bis c) gemäß Anspruch 1 gleichzeitig oder in beliebiger Reihenfolge mit einer wässrigen Suspension des ligninhaltigen Materials mischt. The use of the multicomponent system according to the invention in for example, a method for treating lignin in that the selected components a) to c) according to claim 1 simultaneously or in any order with an aqueous suspension of the lignin-containing material mixes.
Vorzugsweise wird ein Verfahren unter Einsatz des erfindungsgemäßen Mehrkomponentensystems in Gegenwart von Sauerstoff oder Luft bei Normaldruck bis 10 bar und in einem pH-Bereich von 2 bis 11, bei einer Temperatur von 20 bis 95°C, vorzugsweise 40 - 95°C, und einer Stoffdichte von 0,5 bis 40 % durchgeführt.A method using the method according to the invention is preferred Multi-component system in the presence of oxygen or air at normal pressure up to 10 bar and in a pH range from 2 to 11, preferably at a temperature of 20 to 95 ° C 40 - 95 ° C, and a consistency of 0.5 to 40% carried out.
Ein für den Einsatz von Enzymen bei der Zellstoffbleiche ungewöhnlicher und überraschender Befund ist, daß beim Einsatz des erfindungsgemäßen Mehrkomponentensystems eine Steigerung der Stoffdichte eine erhebliche Steigerung der Kappaerniedrigung ermöglicht.One more unusual for the use of enzymes in pulp bleaching and surprising finding is that when using the multicomponent system according to the invention an increase in Material density a significant increase in kappa reduction enables.
Aus ökonomischen Gründen bevorzugt wird ein erfindungsgemäßes Verfahren bei Stoffdichten von 8 bis 35 %, besonders bevorzugt 9 bis 15 % durchgeführt.For reasons of economy, one according to the invention is preferred Process with material densities of 8 to 35%, particularly preferred 9 to 15% performed.
Überraschenderweise zeigte sich ferner, daß eine saure Wäsche (pH 2 bis 6, vorzugsweise 4 bis 5) oder Q-Stufe (pH-Wert 2 bis 6, vorzugsweise 4 bis 5) vor der Enzym-Mediatorstufe bei manchen Zellstoffen zu einer erheblichen Kappazahlerniedrigung im Vergleich zur Behandlung ohne diese spezielle Vorbehandlung führt. In der Q-Stufe werden als Chelatbildner die zu diesem Zwecke üblichen Substanzen (wie z.B. EDTA, DTPA) eingesetzt. Sie werden vorzugsweise in Konzentrationen von 0,1 % bis 1 % (w/w bezogen auf trockenen Zellstoff), besonders bevorzugt 0,1 % bis 0,5 % (w/w bezogen auf trockenen Zellstoff), eingesetzt.Surprisingly, it was also found that 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 in some Pulp to a significant Kappa reduction in Comparison to treatment without this special pretreatment leads. In the Q stage, the chelating agents become those Common substances (such as EDTA, DTPA) are used. They are preferably used in concentrations of 0.1% to 1% (w / w based on dry pulp), particularly preferably 0.1 % to 0.5% (w / w based on dry pulp) used.
Im erfindungsgemäßen Verfahren werden vorzugsweise 0,01 bis 100.000 IU Enzym pro g ligninhaltiges Material eingesetzt. Besonders bevorzugt werden 0,1 bis 100 insbesondere bevorzugt werden 1 bis 40 IU Enzym pro g ligninhaltiges Material eingesetzt (1 U entspricht dem Umsatz von 1 µmol 2,2'-Azino-bis(3-ethyl-benzothiazolin-6-sulfonsäure-diammonium salz) (ABTS) / min / ml Enzym In the process according to the invention, 0.01 to 100,000 IU enzyme used per g of lignin-containing material. Especially 0.1 to 100 are particularly preferred 1 to 40 IU enzyme are used per g of lignin-containing material (1 U corresponds to the conversion of 1 µmol 2,2'-Azino-bis (3-ethyl-benzothiazoline-6-sulfonic acid diammonium salt) (ABTS) / min / ml enzyme
Im erfindungsgemäßen Verfahren werden vorzugsweise 0,01 mg bis 100 mg Oxidationsmittel pro g ligninhaltigem Material eingesetzt. Besonders bevorzugt werden 0,01 bis 50 mg Oxidationsmittel pro g ligninhaltigem Material eingesetzt.In the process according to the invention, preferably 0.01 mg to 100 mg of oxidizing agent used per g of lignin-containing material. 0.01 to 50 mg of oxidizing agent are particularly preferred used per g of lignin-containing material.
Im erfindungsgemäßen Verfahren werden vorzugsweise 0,5 bis 80 mg Mediator pro g ligninhaltigem Material eingesetzt. Besonders bevorzugt werden 0,5 bis 40 mg Mediator pro g ligninhaltigem Material eingesetzt.In the process according to the invention, preferably 0.5 to 80 mg mediator used per g of lignin-containing material. Especially 0.5 to 40 mg mediator per g of lignin-containing are preferred Material used.
Gleichzeitig können Reduktionsmittel zugegeben werden, die zusammen mit den vorhandenen Oxidationsmitteln zur Einstellung eines bestimmten Redoxpotentials dienen.At the same time, reducing agents can be added together with the existing oxidizing agents for adjustment serve a certain redox potential.
Als Reduktionsmittel können Natrium-Bisulfit, Natrium-Dithionit, Ascorbinsäure, Thioverbindungen, Mercaptoverbindungen oder Glutathion etc. eingesetzt werden.Sodium bisulfite, sodium dithionite, Ascorbic acid, thio compounds, mercapto compounds or glutathione etc. can be used.
Die Reaktion läuft beispielsweise bei Laccase unter Luft- oder Sauerstoffzufuhr oder Sauerstoff- bzw. Luftüberdruck ab, bei den Peroxidasen (z.B. Ligninperoxidasen, Manganperoxidasen) mit Wasserstoffperoxid. Dabei können beispielsweise der Sauerstoff auch durch Wasserstoffperoxid + Katalase und Wasserstoffperoxid durch Glucose + GOD oder andere Systeme in situ generiert werden.In the case of laccase, for example, the reaction takes place under air or Oxygen supply or oxygen or air pressure from, at the peroxidases (e.g. lignin peroxidases, manganese peroxidases) with hydrogen peroxide. For example, the oxygen also by hydrogen peroxide + catalase and hydrogen peroxide by glucose + GOD or other systems in situ to be generated.
Außerdem können dem System Radikalbildner oder Radikalfänger (Abfangen von beispielsweise OH oder OOH Radikalen) zugesetzt werden. Diese können das Zusammenspiel innerhalb der Red/Ox- und Radikalmediatoren verbessern.Radical formers or radical scavengers can also be added to the system (Trapping OH or OOH radicals, for example) added become. These can influence the interaction within the Red / Ox and improve radical mediators.
Der Reaktionslösung können auch weitere Metallsalze zugegeben werden.Other metal salts can also be added to the reaction solution become.
Diese sind im Zusammenwirken mit Chelatbildnern als Radikalbildner oder Red/Ox-Zentren wichtig. Die Salze bilden in der Reaktionslösung Kationen. Solche Ionen sind u.a. Fe2+, Fe3+' Mn2+, Mn3+, Mn4+, Cu2+, Ca2+, Ti3+, Cer4+, Al3+. These are important in conjunction with chelating agents as radical formers or red / ox centers. The salts form cations in the reaction solution. Such ions include Fe 2+ , Fe 3+ , Mn 2+ , Mn 3+ , Mn 4+ , Cu 2+ , Ca 2+ , Ti 3+ , Cer 4+ , Al 3+ .
Die in der Lösung vorhandenen Chelate können darüber hinaus als Mimicsubstanzen für die Enzyme, beispielsweise für die Laccasen (Kupferkomplexe) oder für die Lignin- oder Manganperoxidasen (Hämkomplexe) dienen. Unter Mimicsubstanzen sind solche Stoffe zu verstehen, die die prosthetischen Gruppen von (hier) Oxidoreduktasen simulieren und z.B. Oxidationsreaktionen katalysieren können.The chelates present in the solution can also as mimic substances for the enzymes, for example for the Laccases (copper complexes) or for the lignin or manganese peroxidases (Heme complexes). Among mimic substances are such To understand substances that the prosthetic groups of (here) simulate oxidoreductases and e.g. Oxidation reactions can catalyze.
Weiterhin kann dem Reaktionsgemisch NaOCl zugesetzt werden. Diese Verbindung kann im Zusammenspiel mit Wasserstoffperoxid Singulettsauerstoff bilden.NaOCl can also be added to the reaction mixture. This compound can interact with hydrogen peroxide Form singlet oxygen.
Schließlich ist es auch möglich, unter Einsatz von Detergentien zu arbeiten. Als solche kommen nicht-ionische, anionische, kationische und amphotere Tenside in Betracht. Die Detergentien können die Penetration der Enzyme und Mediatoren in die Faser verbessern.Finally, it is also possible to use detergents to work. As such come non-ionic, anionic, cationic and amphoteric surfactants. The detergents can penetrate the enzymes and mediators into the fiber improve.
Ebenso kann es für die Reaktion förderlich sein, Polysaccharide und/oder Proteine zuzusetzen. Hier sind insbesondere als Polysaccharide Glucane, Mannane, Dextrane, Lävane, Pektine, Alginate oder Pflanzengummis und/oder eigene von den Pilzen gebildete oder in der Mischkultur mit Hefen produzierte Polysaccharide und als Proteine Gelantine und Albumin zu nennen.Polysaccharides can also be beneficial for the reaction and / or add proteins. Here are especially as Polysaccharides glucans, mannans, dextrans, levans, pectins, Alginates or plant gums and / or your own mushrooms polysaccharides formed or produced in mixed culture with yeasts and to name gelatin and albumin as proteins.
Diese Stoffe dienen hauptsächlich als Schutzkolloide für die Enzyme.These substances mainly serve as protective colloids for the Enzymes.
Weitere Proteine, die zugesetzt werden können, sind Proteasen wie Pepsin, Bromelin, Papain usw.. Diese können u.a. dazu dienen, durch den Abbau des im Holz vorhandenen Extensins C, hydroxyprolinreiches Protein, einen besseren Zugang zum Lignin zu erreichen.Other proteins that can be added are proteases such as pepsin, bromelin, papain etc. These can include serve by breaking down the extensin C present in the wood, Hydroxyproline-rich protein, better access to lignin to reach.
Als weitere Schutzkolloide kommen Aminosäuren, Einfachzucker, Oligomerzucker, PEG-Typen der verschiedensten Molekulargewichte, Polyethylenoxide, Polyethylenimine und Polydimethylsiloxane in Frage.Other protective colloids are amino acids, simple sugar, Oligomeric sugar, PEG types of the most varied Molecular weights, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes in question.
Das erfindungsgemäße Verfahren kann nicht nur bei der Delignifizierung (Bleiche) von Sulfat-, Sulfit-, Organosol-, o.a. Zellstoffen und von Holzstoffen eingesetzt werden, sondern auch bei der Herstellung von Zellstoffen allgemein, sei es aus Holz- oder Einjahrespflanzen, wenn eine Defibrillierung durch die üblichen Kochverfahren (verbunden eventuell mit mechanischen Verfahren oder Druck) d.h. eine sehr schonende Kochung bis zu Kappazahlen, die im Bereich von ca. 50 - 120 Kappa liegen können, gewährleistet ist.The method according to the invention can be used not only for delignification (Bleaching) of sulfate, sulfite, organosol, etc. Pulp and wood pulp are used, but also in the manufacture of cellulose in general, be it from Wood or annual plants when defibrillated by the usual cooking methods (possibly connected with mechanical Process or printing) i.e. a very gentle cooking up to kappa numbers that range from about 50 to 120 kappa can lie, is guaranteed.
Bei der Bleiche von Zellstoffen wie auch bei der Herstellung von Zellstoffen kann die Behandlung mehrfach wiederholt werden, entweder nach Wäsche und Extraktion des behandelten Stoffes mit NaOH oder ohne diese Zwischenschritte. Dies führt zu noch wesentlich weiter reduzierbaren Kappawerten und zu erheblichen Weißesteigerungen. Ebenso kann vor der Enzym/Mediatorbehandlung eine O2-Stufe eingesetzt werden oder auch wie bereits erwähnt eine saure Wäsche oder Q-Stufe (Chelatstufe) ausgeführt werden.In the bleaching of cellulose as well as in the production of cellulose, 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. Likewise, 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.
Im folgenden wird die Erfindung anhand von Beispielen näher erläutert:In the following, the invention will be explained in more detail by means of examples explains:
5 g atro Zellstoff (Softwood O2 delignifiziert), Stoffdichte
30% (ca. 17 g feucht) werden zu folgenden Lösungen gegeben:
Nach Zugabe des Zellstoffes wird für 2 min mit einem Teigkneter gemixt.
Danach wird der Stoff in eine auf 45°C vorgeheizte Reaktionsbombe gegeben und unter 1 - 10 bar Sauerstoffüberdruck für 1 - 4 Stunden inkubiert.
Danach wird der Stoff über einem Nylonsieb (30 Am) gewaschen und 1 Stunde bei 60°C, 2% Stoffdichte und 8% NaOH pro g Zellstoff extrahiert.
Nach erneuter Wäsche des Stoffes wird die Kappazahl bestimmt. Ergebnis vergl. Tabelle 15 g dry cellulose (Softwood O 2 delignified), consistency 30% (approx. 17 g wet) are added to the following solutions:
After the pulp has been added, it is mixed for 2 min with a dough kneader.
The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar oxygen pressure for 1-4 hours.
The material is then washed over a nylon sieve (30 Am) and extracted for 1 hour at 60 ° C., 2% consistency and 8% NaOH per g of pulp.
After washing the fabric again, the kappa number is determined. Result see Table 1
5 g atro Zellstoff (Softwood O2 delignifiziert), Stoffdichte
30% (ca. 17 g feucht) werden zu folgenden Lösungen gegeben:
Nach Zugabe des Zellstoffes wird für 2 min mit einem Teigkneter gemixt.
Danach wird der Stoff in eine auf 45°C vorgeheizte Reaktionsbombe gegeben und unter 1 - 10 bar Sauerstoffüberdruck für 1 - 4 Stunden inkubiert.
Danach wird der Stoff über einem Nylonsieb (30 µm) gewaschen und 1 Stunde bei 60°C, 2% Stoffdichte und 8% NaOH pro g Zellstoff extrahiert.
Nach erneuter Wäsche des Stoffes wird die Kappazahl bestimmt. Ergebnis vergl. Tabelle 15 g dry cellulose (Softwood O 2 delignified), consistency 30% (approx. 17 g wet) are added to the following solutions:
After the pulp has been added, it is mixed for 2 min with a dough kneader.
The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar oxygen pressure for 1-4 hours.
The material is then washed over a nylon sieve (30 μm) and extracted for 1 hour at 60 ° C., 2% consistency and 8% NaOH per g of pulp.
After washing the fabric again, the kappa number is determined. Result see Table 1
5 g atro Zellstoff (Softwood O2 delignifiziert), Stoffdichte
30% (ca. 17 g feucht) werden zu folgenden Lösungen gegeben:
Nach Zugabe des Zellstoffes wird für 2 min mit einem Teigkneter gemixt.
Danach wird der Stoff in eine auf 45°C vorgeheizte Reaktionsbombe gegeben und unter 1 - 10 bar Sauerstoffüberdruck für 1 - 4 Stunden inkubiert.
Danach wird der Stoff über einem Nylonsieb (30 Am) gewaschen und 1 Stunde bei 60°C, 2% Stoffdichte und 8% NaOH pro g Zellstoff extrahiert.
Nach erneuter Wäsche des Stoffes wird die Kappazahl bestimmt. Ergebnis vergl. Tabelle 1 5 g dry cellulose (Softwood O 2 delignified), consistency 30% (approx. 17 g wet) are added to the following solutions:
After the pulp has been added, it is mixed for 2 min with a dough kneader.
The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar oxygen pressure for 1-4 hours.
The material is then washed over a nylon sieve (30 Am) and extracted for 1 hour at 60 ° C., 2% consistency and 8% NaOH per g of pulp.
After washing the fabric again, the kappa number is determined. Result see Table 1
5 g atro Zellstoff (Softwood O2 delignifiziert), Stoffdichte
30% (ca. 17 g feucht) werden zu folgenden Lösungen gegeben:
Nach Zugabe des Zellstoffes wird für 2 min mit einem Teigkneter gemixt.
Danach wird der Stoff in eine auf 45°C vorgeheizte Reaktionsbombe gegeben und unter 1 - 10 bar Sauerstoffüberdruck für 1 - 4 Stunden inkubiert.
Danach wird der Stoff über einem Nylonsieb (30 µm) gewaschen und 1 Stunde bei 60°C, 2% Stoffdichte und 8% NaOH pro g Zellstoff extrahiert.
Nach erneuter Wäsche des Stoffes wird die Kappazahl bestimmt. Ergebnis vergl. Tabelle 15 g dry cellulose (Softwood O 2 delignified), consistency 30% (approx. 17 g wet) are added to the following solutions:
After the pulp has been added, it is mixed for 2 min with a dough kneader.
The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar oxygen pressure for 1-4 hours.
The material is then washed over a nylon sieve (30 μm) and extracted for 1 hour at 60 ° C., 2% consistency and 8% NaOH per g of pulp.
After washing the fabric again, the kappa number is determined. Result see Table 1
5 g atro Zellstoff (Softwood O2 delignifiziert), Stoffdichte
30% (ca. 17 g feucht) werden zu folgenden Lösungen gegeben:
Nach Zugabe des Zellstoffes wird für 2 min mit einem Teigkneter gemixt.
Danach wird der Stoff in eine auf 45°C vorgeheizte Reaktionsbombe gegeben und unter 1 - 10 bar Sauerstoffüberdruck für 1 - 4 Stunden inkubiert.
Danach wird der Stoff über einem Nylonsieb (30 Am) gewaschen und 1 Stunde bei 60°C, 2% Stoffdichte und 8% NaOH pro g Zellstoff extrahiert.
Nach erneuter Wäsche des Stoffes wird die Kappazahl bestimmt. Ergebnis vergl. Tabelle 15 g dry cellulose (Softwood O 2 delignified), consistency 30% (approx. 17 g wet) are added to the following solutions:
After the pulp has been added, it is mixed for 2 min with a dough kneader.
The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar oxygen pressure for 1-4 hours.
The material is then washed over a nylon sieve (30 Am) and extracted for 1 hour at 60 ° C., 2% consistency and 8% NaOH per g of pulp.
After washing the fabric again, the kappa number is determined. Result see Table 1
5 g atro Zellstoff (Softwood O2 delignifiziert), Stoffdichte
30% (ca. 17 g feucht) werden zu folgenden Lösungen gegeben:
Nach Zugabe des Zellstoffes wird für 2 min mit einem Teigkneter gemixt.
Danach wird der Stoff in eine auf 45°C vorgeheizte Reaktionsbombe gegeben und unter 1 - 10 bar Sauerstoffüberdruck für 1 - 4 Stunden inkubiert.
Danach wird der Stoff über einem Nylonsieb (30 Am) gewaschen und 1 Stunde bei 60°C, 2% Stoffdichte und 8% NaOH pro g Zellstoff extrahiert.
Nach erneuter Wäsche des Stoffes wird die Kappazahl bestimmt. Ergebnis vergl. Tabelle 15 g dry cellulose (Softwood O 2 delignified), consistency 30% (approx. 17 g wet) are added to the following solutions:
After the pulp has been added, it is mixed for 2 min with a dough kneader.
The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar oxygen pressure for 1-4 hours.
The material is then washed over a nylon sieve (30 Am) and extracted for 1 hour at 60 ° C., 2% consistency and 8% NaOH per g of pulp.
After washing the fabric again, the kappa number is determined. Result see Table 1
5 g atro Zellstoff (Softwood O2 delignifiziert), Stoffdichte
30% (ca. 17 g feucht) werden zu folgenden Lösungen gegeben:
Nach Zugabe des Zellstoffes wird für 2 min mit einem Teigkneter gemixt.
Danach wird der Stoff in eine auf 45°C vorgeheizte Reaktionsbombe gegeben und unter 1 - 10 bar Sauerstoffüberdruck für 1 - 4 Stunden inkubiert.
Danach wird der Stoff über einem Nylonsieb (30 µm) gewaschen und 1 Stunde bei 60°C, 2% Stoffdichte und 8% NaOH pro g Zellstoff extrahiert.
Nach erneuter Wäsche des Stoffes wird die Kappazahl bestimmt. Ergebnis vergl. Tabelle 1
After the pulp has been added, it is mixed for 2 min with a dough kneader.
The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar oxygen pressure for 1-4 hours.
The material is then washed over a nylon sieve (30 μm) and extracted for 1 hour at 60 ° C., 2% consistency and 8% NaOH per g of pulp.
After washing the fabric again, the kappa number is determined. Result see Table 1
Claims (8)
- Multi-component system for modifying, degrading or bleaching lignin, lignin-containing materials, comprisinga. at least one enzyme andb. at least one suitable oxidizing agent andc. at least one mediator, characterized in that the mediator is chosen from the group consisting of hydroxypyridines, aminopyridines, hydroxyquinolines, aminoquinolines, hydroxyisoquinolines and aminoisoquinolines, having nitroso or mercapto substituents ortho or para to the hydroxyl or amino groups, tautomers of the said compounds and salts, ethers and esters thereof.
- Multi-component system according to Claim 1, characterized in that, as the mediator (component c), at least one compound chosen from the group consisting of compounds of the general formula (I), (II) or (III)and tautomers, salts, ethers or esters thereof is present, where, in the formulae (I), (II) or (III), two radicals R1 which are ortho or para to one another are a hydroxyl and nitroso radical or a hydroxyl and mercapto radical or a nitroso radical and an amino radicaland the remaining radicals R1 are identical or different and are chosen from the group consisting of a hydrogen, halogen, hydroxyl, mercapto, formyl, cyano, carbamoyl or carboxyl radical, an ester and salt of the carboxyl radical, a sulphono radical, an ester and salt of the sulphono radical, a sulphamoyl, nitro, nitroso, amino, phenyl, aryl-C1-C5-alkyl, C1-C12-alkyl, C1-C5-alkoxy, C1-C10-carbonyl, carbonyl-C1-C6-alkyl, phospho, phosphono or phosphono-oxy radical and an ester and salt of the phosphonooxy radical, andwhere carbamoyl, sulphamoyl, amino, mercapto and phenyl radicals can be unsubstituted or mono- or polysubstituted by a radical R2 andthe aryl-C1-C5-alkyl, C1-C12-alkyl, C1-C5-alkoxy, C1-C10-carbonyl and carbonyl-C1-C6-alkyl radicals can be saturated or unsaturated, branched or unbranched and can be mono- or polysubstituted by a radical R2,R2 is identical or different and is a hydroxyl, formyl, cyano or carboxyl radical, an ester or salt of the carboxyl radical or a carbamoyl, sulphono, sulphamoyl, nitro, nitroso, amino, phenyl, C1-C5-alkyl or C1-C5-alkoxy radical or a C1-C5-alkylcarbonyl radical, andin each case two radicals R1 or two radicals R2 or R1 and R2 can be linked in pairs via a bridge [-CR3R4-]m, where m is 1, 2, 3 or 4, andR3 and R4 are identical or different and are a carboxyl radical, an ester or salt of the carboxyl radical or a phenyl, C1-C5-alkyl or C1-C5-alkoxy radical or a C1-C5-alkylcarbonyl radical, andone or more non-adjacent groups [-CR3R4-] can be replaced by oxygen, sulphur or an imino radical which is optionally substituted by C1-C5-alkyl, and two adjacent groups [-CR3R4-] can be replaced by a group [-CR3=CR4-].
- Multi-component system according to one of Claims 1 or 2, characterized in that the mediator employed is at least one compound selected from the group 2,6-dihydroxy-3-nitrosopyridine, 2,3-dihydroxy-4-nitrosopyridine, 2,6-dihydroxy-3-nitrosopyridine-4-carboxylic acid, 2,4-dihydroxy-3-nitrosopyridine, 3-hydroxy-2-mercaptopyridine, 2-hydroxy-3-mercaptopyridine, 2,6-diamino-3-nitrosopyridine, 2,6-diamino-3-nitrosopyridine-4-carboxylic acid, 2-hydroxy-3-nitrosopyridine, 3-hydroxy-2-nitrosopyridine, 2-mercapto-3-nitrosopyridine, 3-mercapto-2-nitrosopyridine, 2-amino-3-nitrosopyridine, 3-amino-2-nitrosopyridine, 2,4-dihydroxy-3-nitrosoquinoline, 8-hydroxy-5-nitrosoquinoline, 2,3-dihydroxy-4-nitrosoquinoline, 3-hydroxy-4-nitrosoisoquinoline, 4-hydroxy-3-nitrosoisoquinoline, 8-hydroxy-5-nitrosoisoquinoline, and tautomers of the compounds mentioned.
- A multi-component system according to one of Claims 1 to 3, characterized in that the mediator employed is at least one compound selected from the group
2,6-dihydroxy-3-nitrosopyridine, 2, 3-dihydroxy-4-nitrosopyridine, 2,6-dihydroxy-3-nitrosopyridine-4-carboxylic acid, 2,4-dihydroxy-3-nitrosopyridine, 3-hydroxy-2-mercaptopyridine, 2-hydroxy-3-mercaptopyridine, 2,6-diamino-3-nitrosopyridine, 2,6-diamino-3-nitrosopyridine-4-carboxylic acid, 2-hydroxy-3-nitrosopyridine, 3-hydroxy-2-nitrosopyridine, 2-mercapto-3-nitrosopyridine, 3-mercapto-2-nitrosopyridine, 2-amino-3-nitrosopyridine, 3-amino-2-nitrosopyridine, 2,4-dihydroxy-3-nitrosoquinoline, 8-hydroxy-5-nitrosoquinoline, 2,3-dihydroxy-4-nitrosoquinoline, 3-hydroxy-4-nitrosoisoquinoline, 4-hydroxy-3-nitrosoisoquinoline and 8-hydroxy-5-nitrosoisoquinoline, and tautomers of these compounds. - Multi-component system according to one of Claims 1 to 4, characterized in that laccase is employed as the enzyme.
- A multi-component system according to one of Claims 1 to 5, characterized in that air, oxygen, ozone, H2O2, organic peroxides, peracids, such as peracetic acid, performic acid, persulphuric acid, pernitric acid, metachloroperoxybenzoic acid or perchloric acid, a perborate, a peracetate, a persulphate, a peroxide or an oxygen species and free radicals thereof, such as OH·, OOH·, singlet oxygen, superoxide (O2 ·-), ozonide or the dioxygenyl cation (O2 +), a dioxirane, a dioxetane or a Fremy radical is employed as the oxidizing agent.
- Process for treatment of lignin, the particular components a) to c), as mentioned in claim 1, are mixed simultaneously or in any desired sequence with an aqueous suspension of the lignin-containing material.
- Use of mediators as mentioned in Claim 1 as component c for modifying, degrading or bleaching lignin or lignin-containing materials.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19651099 | 1996-12-09 | ||
DE19651099A DE19651099A1 (en) | 1996-12-09 | 1996-12-09 | Multi-component system for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances as well as methods for their use |
PCT/EP1997/006802 WO1998026127A1 (en) | 1996-12-09 | 1997-12-05 | Multicomponent system for modifying, decomposing or bleaching lignin, lignin-containing materials or similar substances, and process for using the same |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0943032A1 EP0943032A1 (en) | 1999-09-22 |
EP0943032B1 true EP0943032B1 (en) | 2000-09-13 |
Family
ID=7814116
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97952038A Expired - Lifetime EP0943032B1 (en) | 1996-12-09 | 1997-12-05 | Multicomponent system for modifying, decomposing or bleaching lignin or lignin-containing materials, and process for using the same |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0943032B1 (en) |
JP (1) | JP2000505844A (en) |
CN (1) | CN1240008A (en) |
AT (1) | ATE196331T1 (en) |
AU (1) | AU719140B2 (en) |
BR (1) | BR9714387A (en) |
CA (1) | CA2271937A1 (en) |
DE (2) | DE19651099A1 (en) |
ES (1) | ES2150797T3 (en) |
PT (1) | PT943032E (en) |
RU (1) | RU2154704C1 (en) |
WO (1) | WO1998026127A1 (en) |
Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6034047A (en) * | 1998-09-04 | 2000-03-07 | Au; Van | Bleach detergent compositions comprising nitrones and nitroso spin traps |
DE60122939T2 (en) | 2000-12-21 | 2007-01-11 | Nitromed, Inc., Bedford | SUBSTITUTED ARYL COMPOUNDS AS NEW, CYCLOOXYGENASE-2 SELECTIVE INHIBITORS, COMPOSITIONS, AND USE PROCESSES |
PT1362844E (en) | 2001-01-26 | 2008-03-10 | Btg Int Ltd | Benzylamine analogue |
US20100074949A1 (en) | 2008-08-13 | 2010-03-25 | William Rowe | Pharmaceutical composition and administration thereof |
EP1412367A4 (en) | 2001-06-21 | 2006-05-03 | Ariad Pharma Inc | Novel quinolines and uses thereof |
US7235560B2 (en) | 2002-08-19 | 2007-06-26 | Glaxo Group Limited | Pyrimidine derivative as selective COX-2 inhibitors |
GB0221443D0 (en) | 2002-09-16 | 2002-10-23 | Glaxo Group Ltd | Pyridine derivates |
FI20031904A (en) * | 2003-12-23 | 2005-06-24 | Kemira Oyj | Process for modifying a lignocellulosic product |
US8354427B2 (en) | 2004-06-24 | 2013-01-15 | Vertex Pharmaceutical Incorporated | Modulators of ATP-binding cassette transporters |
PL1773816T3 (en) | 2004-06-24 | 2015-06-30 | Vertex Pharma | Modulators of ATP-binding cassette transporters |
US8093273B2 (en) | 2004-10-20 | 2012-01-10 | Resverlogix Corp. | Flavanoids and isoflavanoids for the prevention and treatment of cardiovascular diseases |
EP2314295B1 (en) | 2005-07-29 | 2015-01-28 | Resverlogix, Inc | Pharmaceutical compositions for the prevention and treatment of complex diseases and their delivery by insertable medical devices |
CN101258142A (en) | 2005-08-02 | 2008-09-03 | 莱西肯医药有限公司 | 2-aminoaryl pyridines as protein kinases inhibitors |
WO2007079139A2 (en) | 2005-12-28 | 2007-07-12 | Vertex Pharmaceuticals, Inc. | Solid forms of n-[2,4-bis(1,1-dimethylethyl)-5-hydroxyphenyl]-1,4-dihydro-4-oxoquinoline-3-carboxamide |
HUE027273T2 (en) * | 2006-06-13 | 2016-10-28 | Helix Biomedix Inc | Peptide fragments for inducing synthesis of extracellular matrix proteins |
EP2046753A2 (en) | 2006-07-06 | 2009-04-15 | Brystol-Myers Squibb Company | Pyridone/hydroxypyridine 11-beta hydroxysteroid dehydrogenase type i inhibitors |
DK2118074T3 (en) | 2007-02-01 | 2014-03-10 | Resverlogix Corp | Compounds for the prevention and treatment of cardiovascular diseases |
JP5602728B2 (en) | 2008-06-26 | 2014-10-08 | レスバーロジックス コーポレイション | Method for producing quinazolinone derivative |
US8952021B2 (en) | 2009-01-08 | 2015-02-10 | Resverlogix Corp. | Compounds for the prevention and treatment of cardiovascular disease |
KR101709492B1 (en) | 2009-03-18 | 2017-02-23 | 리스버로직스 코퍼레이션 | Novel anti-inflammatory agents |
EP2408750B1 (en) | 2009-03-20 | 2015-08-26 | Vertex Pharmaceuticals Incorporated | Process for making modulators of cystic fibrosis transmembrane conductance regulator |
SI2421533T1 (en) | 2009-04-22 | 2019-01-31 | Resverlogix Corp. | Novel anti-inflammatory agents |
US8802700B2 (en) | 2010-12-10 | 2014-08-12 | Vertex Pharmaceuticals Incorporated | Modulators of ATP-Binding Cassette transporters |
JP5992049B2 (en) | 2011-11-01 | 2016-09-14 | レスバーロジックス コーポレイション | Oral immediate release formulations for substituted quinazolinones |
CA2865519C (en) | 2012-02-27 | 2018-01-02 | Vertex Pharmaceuticals Incorporated | Pharmaceutical compositions comprising a solid dispersion of n-[2,4-bis(1,1-dimethylethyl0-5-hydroxyphenyl-1]-1,4-dihydro-4-oxoquinolone-3-carboxamide for treating cystic fibrosis |
US9073878B2 (en) | 2012-11-21 | 2015-07-07 | Zenith Epigenetics Corp. | Cyclic amines as bromodomain inhibitors |
WO2014080291A2 (en) | 2012-11-21 | 2014-05-30 | Rvx Therapeutics Inc. | Biaryl derivatives as bromodomain inhibitors |
US9271978B2 (en) | 2012-12-21 | 2016-03-01 | Zenith Epigenetics Corp. | Heterocyclic compounds as bromodomain inhibitors |
CN105008347A (en) | 2013-03-11 | 2015-10-28 | 百时美施贵宝公司 | Isoquinolines as potassium ion channel inhibitors |
MX370450B (en) | 2014-10-07 | 2019-12-13 | Vertex Pharma | Co-crystals of modulators of cystic fibrosis transmembrane conductance regulator. |
CN107530356A (en) | 2015-03-13 | 2018-01-02 | 雷斯韦洛吉克斯公司 | For treating the composition and treatment method of complement-associated disease |
CN107245896A (en) * | 2017-06-21 | 2017-10-13 | 昆明理工大学 | A kind of method for improving pulp bleaching efficiency |
Family Cites Families (2)
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DK77393D0 (en) * | 1993-06-29 | 1993-06-29 | Novo Nordisk As | ENZYMER ACTIVATION |
EP0717143A1 (en) * | 1994-12-16 | 1996-06-19 | Lignozym GmbH | Multicomponents system for modifying decomposing or bleaching of lignin or materials containing it or similar components and the way to use it |
-
1996
- 1996-12-09 DE DE19651099A patent/DE19651099A1/en not_active Withdrawn
-
1997
- 1997-12-05 JP JP10526185A patent/JP2000505844A/en active Pending
- 1997-12-05 AU AU55603/98A patent/AU719140B2/en not_active Ceased
- 1997-12-05 CN CN97180387A patent/CN1240008A/en active Pending
- 1997-12-05 CA CA002271937A patent/CA2271937A1/en not_active Abandoned
- 1997-12-05 WO PCT/EP1997/006802 patent/WO1998026127A1/en active IP Right Grant
- 1997-12-05 PT PT97952038T patent/PT943032E/en unknown
- 1997-12-05 RU RU99114460/12A patent/RU2154704C1/en active
- 1997-12-05 BR BR9714387-1A patent/BR9714387A/en unknown
- 1997-12-05 EP EP97952038A patent/EP0943032B1/en not_active Expired - Lifetime
- 1997-12-05 AT AT97952038T patent/ATE196331T1/en not_active IP Right Cessation
- 1997-12-05 DE DE59702358T patent/DE59702358D1/en not_active Expired - Lifetime
- 1997-12-05 ES ES97952038T patent/ES2150797T3/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
AU5560398A (en) | 1998-07-03 |
EP0943032A1 (en) | 1999-09-22 |
WO1998026127A1 (en) | 1998-06-18 |
RU2154704C1 (en) | 2000-08-20 |
DE19651099A1 (en) | 1998-06-10 |
CA2271937A1 (en) | 1998-06-18 |
PT943032E (en) | 2000-12-29 |
ES2150797T3 (en) | 2000-12-01 |
BR9714387A (en) | 2000-05-16 |
AU719140B2 (en) | 2000-05-04 |
CN1240008A (en) | 1999-12-29 |
DE59702358D1 (en) | 2000-10-19 |
JP2000505844A (en) | 2000-05-16 |
ATE196331T1 (en) | 2000-09-15 |
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