EP0717143A1 - Multicomponents system for modifying decomposing or bleaching of lignin or materials containing it or similar components and the way to use it - Google Patents

Abstract

System for transforming, degrading or bleaching lignin, lignin-contg. materials or similar materials, comprises a poly-component system comprising: (a) opt. ≥ 1 oxidation catalyst; (b) ≥ 1 oxidising agent; (c) ≥ 1 mediator selected from hydroxylamines, hydroxylamine derivs., hydroxamic acids, hydroxamic acid derivs. and aliphatic, cycloaliphatic, heterocyclic and aromatic cpds. which contain ≥ 1 N-hydroxy, oxime, N-oxy or N,N-dioxy function; (d) opt. ≥ 1 co-mediator selected from aryl-substd. alcohols, carbonyl cpds., aliphatic ethers, phenol ethers and alkenes; and (e) a small amt. of a free amine of one of the mediators used.

Description

The present invention relates to a multi-component system for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances, and methods for its use.

The sulfate and sulfite processes are the main processes used today for pulp production. Both methods produce pulp under cooking and under pressure. The sulfate process works with the addition of NaOH and Na₂S, while Ca (HSO₃) ₂ + SO₂ is used in the sulfite process.

The main aim of all processes is to remove the lignin from the plant material, wood or annual plants used.

The lignin, which is the main constituent of the plant material (stem or stem) with cellulose and hemicellulose, must be removed, otherwise it will not be possible to produce non-yellowing and mechanically heavy-duty papers.

The wood-based production processes work with stone grinders (wood sanding) or with refiners (TMP), which defibrillate the wood after grinding (chemical, thermal or chemical-thermal).

These wood materials still contain a large part of the lignin. You will v. a. used for the production of newspapers, magazines, etc.

For some years now, the possibilities of using enzymes for lignin degradation have been researched. The mechanism of action of such lignolytic systems was only elucidated a few years ago when it was possible to obtain sufficient amounts of enzyme from the white rot fungus Phanerochaete chrysosporium by means of suitable cultivation conditions and inductor additives. The previously unknown lignin peroxidases and manganese peroxidases were discovered. Since Phanerochaete chrysosporium is a very effective lignin degrader, attempts were made to isolate its enzymes and to use them in purified form for lignin degradation. However, this did not succeed because it turned out that the enzymes primarily lead to a repolymerization of the lignin and not to its degradation.

The same applies to other lignolytic enzyme species such as laccases, which oxidatively break down the lignin using oxygen instead of hydrogen peroxide. It was found that similar processes occur in all cases. This is because radicals are formed which react with one another again and thus lead to polymerization.

Today there are only processes that work with in vivo systems (mushroom systems). The main focus of optimization attempts is so-called biopulping and biobleaching.

Biopulping is the treatment of wood chips with living fungal systems.

• 1. Vorbehandlung von Hackschnitzeln vor dem Refinern oder Mahlen zum Einsparen von Energie bei der Herstellung von Holzstoffen (z.B. TMP oder Holzschliff).
  Ein weiterer Vorteil ist die meist vorhandene Verbesserung der mechanischen Eigenschaften des Stoffes, ein Nachteil die schlechtere Endweiße.
• 2. Vorbehandlung von Hackschnitzeln (Softwood/Hardwood) vor der Zellstoffkochung (Kraftprozeß, Sulfitprozeß).
  Hier ist das Ziel, die Reduzierung von Kochchemikalien, die Verbesserung der Kochkapazität und "extendet cooking".
  Als Vorteile werden auch eine verbesserte Kappareduzierung nach dem Kochen im Vergleich zu einem Kochen ohne Vorbehandlung erreicht.

There are 2 types of application forms:

• 1. Pretreatment of wood chips before refining or grinding to save energy in the production of wood materials (eg TMP or wood pulp).
  Another advantage is the mostly existing improvement in the mechanical properties of the fabric, a disadvantage the poorer final whiteness.
• 2. Pretreatment of wood chips (Softwood / Hardwood) before cellulose cooking (power process, sulfite process).
  The goal here is to reduce cooking chemicals, improve cooking capacity and "extendet cooking".
  As an advantage, improved kappa reduction after cooking compared to cooking without pretreatment is also achieved.

Disadvantages of these procedures are clearly the long treatment times (several weeks) and above all the unresolved risk of contamination during the treatment, if one wants to do without the inefficient sterilization of the wood chips.

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, usually carried out with immobilized fungal systems, is the treatment of pulp mill wastewater, especially bleaching mill wastewater to decolorize it and reduce the AOX (reduction of chlorinated compounds in the wastewater that cause chlorine or chlorine dioxide bleaching stages).

In addition, it is known that hemicellulases etc. Use xylanases, mannanases as "bleach boosters".

These enzymes are primarily intended to act against the reclaimed xylan, which partially covers the residual lignin after the cooking process, and by breaking down the lignin to make it more accessible to the bleaching chemicals used in the subsequent bleaching sequences (especially chlorine dioxide). The savings in bleaching chemicals demonstrated in the laboratory have only been partially confirmed on a large scale, so that this type of enzyme can only be classified as a bleaching additive.

Another, recently investigated possible use of lignolytic enzymes or fungi was identified in the "coal liquefaction". Preliminary investigations show the basic possibility of brown or hard coal using in vivo treatment with e.g. Attack and liquefy white rot fungi such as Phanerochaete chrysosporium (incubation period several weeks). (Bioengineering 4.92.8 year.)

The possible structure of hard coal shows a three-dimensional network of polycyclic, aromatic ring systems with a "certain" similarity to lignin structures.

In addition to the lignolytic enzymes, chelate substances (siderophores such as ammonium oxalate) and biosurfactants are believed to be cofactors.

The application PCT / EP87 / 00635 describes a system for removing lignin from lignin-cellulose-containing material with simultaneous bleaching, which works with lignolytic enzymes from white rot fungi with the addition of reducing and oxidizing agents and phenolic compounds as mediators.

In DE 4008893C2, in addition to the Red / Ox system, “mimic substances” which simulate the active center (prosthetic group) of lignolytic enzymes are added. In this way, a significant improvement in performance could be achieved.

In the application PCT / EP92 / 01086, a redox cascade is used as an additional improvement with the aid of phenolic or non-phenolic aromatics "matched" in the oxidation potential.

In all three processes, the limitation for large-scale use is the applicability with low consistencies (up to a maximum of 4%) and with the last two applications the risk of "leaching out" of metals when using the chelate compounds, which, above all, in the case of downstream peroxide bleaching stages can lead to the destruction of the peroxide.

Methods are known from WO / 12619, WO 94/12620 and WO 94/12621 in which the activity of peroxidase is promoted by means of so-called enhancer substances.

The enhancer substances are characterized in WO 94/12619 on the basis of their half-life.

According to WO 94/12620, enhancer substances are characterized by the formula A = NN = B, where A and B are each defined cyclic radicals.

According to WO 94/12620, enhancer substances are organic chemicals which contain at least two aromatic rings, at least one of which is substituted with defined radicals.

All three applications relate to "dye transfer inhibition" and the use of the respective enhancer substances together with peroxidases as a detergent additive or detergent composition in the detergent sector. In the description of the application, reference is made to the usability for treating lignin, but our own experiments with the substances specifically disclosed in the applications showed that they had no effect as mediators for increasing the bleaching effect of the peroxidases when treating materials containing lignin!

The object of the present invention is to provide a system for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances, which is more effective than known systems.

• a. ggf. mindestens einen Oxdiationskatalysator und
• b. mindestens ein geeignetes Oxdidationsmittel und
• c. mindestens einen Mediator auswählt aus der Gruppe der Hydroxylamine, Hydroxylaminderivate, Hydroxamsäuren, Hydroxamsäurederivate, der aliphatischen, cycloaliphatischen, heterocyclischen oder aromatischen Verbindungen, die mindestens eine N-Hydroxy-, Oxim-, N-Oxi-, oder N,N'-Dioxi- Funktion enhalten und
• d. ggf. mindestens einen Comediator aus der Gruppe der arylsubstituierten Alkohole, Carbonylverbindungen, aliphatische Ether, Phenolether und/oder Olefine (Alkene) und
• e. eine geringe Menge mindestens eines freien Amins eines jeweils eingesetzten Mediators
  umfaßt.

The problem is solved by a multi-component system, which is characterized in that it

• a. optionally at least one oxidation catalyst and
• b. at least one suitable oxidizing agent and
• c. at least one mediator selects from the group of hydroxylamines, hydroxylamine derivatives, hydroxamic acids, hydroxamic acid derivatives, aliphatic, cycloaliphatic, heterocyclic or aromatic compounds which contain at least one N-hydroxy, oxime, N-oxi, or N, N'-dioxi Contain function and
• d. optionally at least one comediator from the group of aryl-substituted alcohols, carbonyl compounds, aliphatic ethers, phenol ethers and / or olefins (alkenes) and
• e. a small amount of at least one free amine of each mediator used
  includes.

The multicomponent system according to the invention preferably comprises at least one oxidation catalyst.

The multicomponent system according to the invention preferably comprises at least one comediator.

Enzymes are preferably used as oxidation catalysts in the multicomponent system according to the invention. For the purposes of the invention, the term enzyme also encompasses enzymatically active proteins or peptides or prosthetic groups of enzymes.

In the multicomponent system according to the invention, oxidoreductases of classes 1.1.1. to 1.97 according to the International Enzyme Nomenclature, Committee of the International Union of Biochemistry and Molecular Biology (Enzyme Nomenclature, Academic Press, Inc., 1992, pp. 24-154).

Enzymes of the classes mentioned below are preferably used:
Class 1.1 enzymes which comprise all dehydrogenases which act on primary secondary alcohols and semiacetals and which are accepted as acceptors NAD + or NADP + (subclass 1.1.1), cytochromes (1.1.2), oxygen (O₂) (1.1.3), Disulfide (1.1.4), quinones (1.1.5) or other acceptors (1.1.99).

From this class, the enzymes of class 1.1.5 with quinones as acceptors and the enzymes of class 1.1.3 are particularly preferred. with oxygen as the acceptor.

Cellobiose: quione-1-oxidoreductase (1.1.5.1) is particularly preferred in this class.

Enzymes of class 1.2 are also preferred. This class of enzymes (1.1.5.1) includes those enzymes that aldehydes to the corresponding acids or oxo groups oxidize. The acceptors can be NAD +, NADP + (1.2.1), cytochrome (1.2.2), oxygen (1.2.3), sulfides (1.2.4), iron-sulfur proteins (1.2.5) or other acceptors (1.2.99 ) his.

The enzymes of group (1.2.3) with oxygen as the acceptor are particularly preferred here.

Enzymes of class 1.3 are also preferred.

This class includes enzymes that act on CH-CH groups of the donor.

The corresponding acceptors are NAD +, NADP + (1.3.1) cytochrome (1.3.2), oxygen (1.3.3), quinones or related compounds (1.3.5), iron-sulfur proteins (1.3.7) or other acceptors ( 1.3.99).

The enzymes of class (1.3.3) with oxygen as acceptor and (1.3.5) with quinones etc. as acceptor are also particularly preferred here.

Also preferred are class 1.4 enzymes which act on CH-NH₂ groups of the donor.

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).

Enzymes of class 1.4.3 with oxygen as the acceptor are also particularly preferred here.

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).

Here too, enzymes with oxygen (O₂) (1.5.3) and with quinones (1.5.5) are particularly preferred as acceptors.

Enzymes of class 1.6 which act on NADH or NADPH are also preferred.

The acceptors here are NADP + (1.6.1), heme proteins (1.6.2), disulfides (1.6.4), quinones (1.6.5), NO₂ groups (1.6.6), and a flavin (1.6.8) or some other acceptors (1.6.99).

Enzymes of class 1.6.5 with quinones as acceptors are particularly preferred here.

Also preferred are class 1.7 enzymes which act as donors on other NO2 compounds and acceptors as cytochromes (1.7.2), oxygen (O₂) (1.7.3), iron-sulfur proteins (1.7.7) or others ( 1.7.99).
Class 1.7.3 with oxygen as the acceptor is particularly preferred here.

Also preferred are class 1.8 enzymes which act as donors on sulfur groups and acceptors NAD +, NADP + (1.8.1), cytochromes (1.8.2), oxygen (O₂) (1.8.3), disulfides (1.8.4), Have quinones (1.8.5), iron-sulfur proteins (1.8.7) or others (1.8.99).

Class 1.8.3 with oxygen (O₂) and (1.8.5) with quinones as acceptors is particularly preferred.

Also preferred are class 1.9 enzymes which act as donors on heme groups and have oxygen (O₂) (1.9.3), NO₂ compounds (1.9.6) and others (1.9.99) as acceptors.

Group 1.9.3 with oxygen (O₂) as acceptor (cytochrome oxidases) is particularly preferred here.

Also preferred are class 1.12 enzymes which act on hydrogen as a donor.
The acceptors are NAD + or NADP + (1.12.1) or others (1.12.99).

Enzymes of class 1.13 and 1.14 (oxigenases) are also preferred.

Preferred enzymes are also those of class 1.15 which act as acceptors on superoxide radicals.

Superoxide dismutase (1.15.1.1) is particularly preferred here.

Enzymes of class 1.16 are also preferred.

NAD + or NADP + (1.16.1) or oxygen (O₂) (1.16.3) act as acceptors.

Enzymes of class 1.16.3.1 (ferroxidase, e.g. ceruloplasmin) are particularly preferred here.

Further preferred enzymes are those of group 1.17 (action on CH₂ groups which are oxidized to -CHOH-), 1.18 (action on reduced ferredoxin as donor), 1.19 (action on reduced flavodoxin as donor) and 1.97 (other oxidoreductases ) belong to.

The enzymes of group 1.11 are also particularly preferred. which act on a peroxide as an acceptor. This only subclass (1.11.1) contains the peroxidases.

The cytochrome C peroxidases (1.11.1.5), catalase (1.11.1.6), the peroxidase (1.11.1.6), the iodide peroxidase (1.11.1.8), the glutathione peroxidase (1.11.1.9) are particularly preferred here, chloride peroxidase (1.11.1.10), L-ascorbate peroxidase (1.11.1.11), phospholipid hydroperoxide glutathione peroxidase (1.11.1.12), manganese peroxidase (1.12.1.13), diarylpropane peroxidase (Ligninase, lignin peroxidase) (1.11.1.14).

Enzymes of class 1.10 which act on biphenols and related compounds are very particularly preferred. They catalyze the oxidation of biphenols and ascorbates. NAD +, NADP + (1.10.1), cytochrome (1.10.2), oxygen (1.10.3) or others (1.10.99) act as acceptors.

Of these in turn, enzymes of class 1.10.3 with oxygen (O₂) as the acceptor are particularly preferred.

Of the enzymes in this class, the enzymes are catechol oxidase (tyrosinase) (1.10.3.1), L-ascorbate oxidase (1.10.3.3), O-aminophenol oxidase (1.10.3.4) and laccase (benzenediol: oxigen oxidoreductase) (1.10.3.2 ) is preferred, with the laccases (benzenediol: oxigen oxidoreductase) (1.10.3.2.) being particularly preferred.

These enzymes are commercially available or can be obtained using standard methods. Plants, animal cells, bacteria and fungi, for example, come into consideration as organisms for the production of the enzymes. Basically, both naturally occurring and genetically modified organisms can be enzyme producers. Parts of unicellular or multicellular organisms are also conceivable as enzyme producers, especially cell cultures.

White rot fungi such as pleurotus, phlebia and trametes are used, for example, for the particularly preferred enzymes, such as those from group 1.11.1, but especially 1.10.3, and in particular for the production of laccases.

The multi-component system according to the invention comprises at least one oxidizing agent. The oxidizing agents that can be used are, for example, air, oxygen, ozone, H₂O₂ _, organic peroxides, peracids such as peracetic acid, performic acid, persulfuric acid, persitric acid, metachloroperoxidbenzoic acid, perchloric acid, perborates, peracetates, persulfates, peroxides or oxygen species and their radicals such as OH, OOH, superoxide (singlet oxygen) O₂⁻), ozonide, dioxygenyl cation (O₂⁺), Dioxrane, Dioxitane or Fremy radicals are used.

Preferably oxidizing agents are used which can either be generated by the corresponding oxidoreductases e.g. Dioxiranes from laccases plus carbonyls or which can chemically regenerate the mediator (e.g. Caro's acid + benzotriazole gives hydroxybenztriazole) or can directly convert it.

As a mediator (component C), the multicomponent system according to the invention preferably comprises at least one compound which contains at least one N-hydroxyl, oxime, N-oxi or N-dioxi function and / or one of the compounds of the formula I mentioned below , II, III, IV or V, the compounds of the formulas II, III, IV and V being preferred, the compounds of the formulas III, IV and V being particularly preferred and compounds of the formulas IV and V being particularly preferred.

Wobei in der allgemeinen Formel I die Substituenten R¹ und R², die gleich oder ungleich sein können, unabhängig voneinander eine der folgenden Gruppen darstellen: Wasserstoff, C₁-C₁₂-alkyl-, carbonyl-C₁-C₆-alkyl-, phenyl-, aryl-, deren C₁-C₁₂-alkyl-, carbonyl-C₁-C₆-alkyl-, phenyl-, aryl- unsubstituiert oder weiterhin ein oder mehrfach mit dem Rest R³ substituiert sein können und wobei der Rest R³ eine der folgenden Gruppen darstellen kann: Wasserstoff, Halogen, hydroxy-, formyl-, carboxy- sowie Salze und Ester davon, amino-, nitro-, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl-, phenyl-, sulfono-, deren Ester und Salze, sulfamoyl-, carbamoyl-, phospho-, phosphono-, phosphonooxy- und deren Salze und Ester wobei die amino-, carbamoyl- und sufamoyl-Gruppen des Restes R³ weiterhin unsubstitiert oder ein oder zweifach mit hydroxy-, C₁-C₃-alkyl-, C₁-C₃-alkoxy- substituiert sein können
und wobei die Reste R¹ und R² gemeinsam eine Gruppe -B- bilden können und -B-dabei eine der folgenden Gruppen darstellt: (-CHR⁴-)_n, (-CR⁴=CH-)_m und wobei R⁴ ein Substituent ist der wie R³ definiert ist und n eine ganze Zahl von 1 bis 6 darstellt und m eine ganze Zahl von 1 bis 3 darstellt.Hydroxylamines: (open-chain or cyclic, aliphatic or aromatic, heterocyclic) of the general formula I

Wherein in the general formula I the substituents R¹ and R², which may be the same or different, independently represent one of the following groups: hydrogen, C₁-C₁₂-alkyl, carbonyl-C₁-C₆-alkyl, phenyl, aryl- whose C₁-C₁₂-alkyl-, carbonyl-C₁-C₆-alkyl-, phenyl-, aryl- unsubstituted or further substituted one or more times with the radical R³ and where the radical R³ can be one of the following groups: hydrogen, Halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, sulfono-, whose Esters and salts, sulfamoyl, carbamoyl, phospho-, phosphono-, phosphonooxy and their salts and esters, the amino, carbamoyl and sufamoyl groups of the radical R³ still unsubstituted or can be substituted once or twice with hydroxy-, C₁-C₃-alkyl-, C₁-C₃-alkoxy-
and wherein the radicals R¹ and R² together can form a group -B- and -B-represents one of the following groups: (-CHR⁴-) _n , (-CR⁴ = CH-) _m and where R⁴ is a substituent like R³ is defined and n represents an integer from 1 to 6 and m represents an integer from 1 to 3.

Examples: Hydroxylamines

Wobei X für eine der folgenden Gruppen steht: (-N=N-), (-N=CR₁₀-)_p, (-CR₁₀=N-)_p, (-CR₁₁=CR₁₂-)_p

und p gleich 1 oder 2 ist,
wobei die Reste R⁹ bis R¹², R¹⁵ und R¹⁶ gleich oder ungleich sein können und unabhängig voneinander eine der folgenden Gruppen darstellen können: Wasserstoff, Halogen, hydroxy, formyl, carboxy sowie Salze und Ester davon, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, sulfono Ester und Salze davon, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy und deren Salze und Ester und wobei die amino-, carbamoyl- und sulfamoyl-Gruppen der Reste R⁹ bis R¹² , R¹⁵ und R¹⁶ weiterhin unsubstitiert oder ein oder zweifach mit hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy substituiert sein können,
und wobei die Reste R¹⁵ und R¹⁶ eine gemeinsame Gruppe -G- bilden können und -G-dabei eine der folgenden Gruppen repräsentiert: (-CR⁵=CR⁶-CR⁷=CR⁸-) oder (-CR⁸=CR⁷-CR⁶=CR⁵-).
Die Reste R⁵ bis R⁸ können gleich oder ungleich sein und unabhängig voneinander eine der folgenden Gruppen darstellen: Wasserstoff Halogen, hydroxy, formyl, carboxy sowie Salze und Ester davon, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, sulfono Ester und Salze davon, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy und deren Salze und Ester und wobei die amino-, carbamoyl- und sufamoyl-Gruppen der Reste R⁵ bis R⁸ weiterhin unsubstitiert oder ein- oder zweifach mit hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy substituiert sein können und wobei die C₁-C₁₂-alkyl-, C₁-C₆-alkyloxy-, carbonyl-C₁-C₆-alkyl-, phenyl-, aryl-Gruppen der Reste R⁵ bis R⁸ unsubstituiert oder weiterhin ein oder mehrfach mit dem Rest R¹⁸ substituiert sein können und wobei der Rest R¹⁸ eine der folgenden Gruppen darstellen kann: Wasserstoff, Halogen, hydroxy, formyl, carboxy sowie deren Salze und Ester, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, sowie deren Ester und Salze und wobei die carbamoyl, sulfamoyl, amino-Gruppen des Restes R¹⁸ unsubstituiert oder weiterhin ein oder zweifach mit dem Rest R¹⁹ substituiert sein können und wobei der Rest R¹⁹ eine der folgenden Gruppen darstellen kann: Wasserstoff, hydroxy, formyl, carboxy sowie deren Salze und Ester, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl.N, N-dipropylhydroxylamine
N, N-diisopropylhydroxylamine
N-hydroxyipyrrolidine
N-hydroxypiperidine
N-hydroxyhexahydroazepine
N, N-dibenzylhydroxylamine
Phenylhydroxylamine
3-hydroxylamino-3-phenylpropionic acid
2-hydroxylamino-3-phenylpropionic acid
N-sulfomethylhydroxylamine
Compounds of the general formula II are:

Where X stands for one of the following groups: (-N = N-), (-N = CR₁₀-) _p , (-CR₁₀ = N-) _p , (-CR₁₁ = CR₁₂-) _p

and p is 1 or 2,
where the radicals R⁹ to R¹², R¹⁵ and R¹⁶ can be identical or different and can independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and where the amino, carbamoyl and sulfamoyl groups of the radicals R⁹ to R¹², R¹⁵ and R¹⁶ can furthermore be unsubstituted or substituted once or twice with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy,
and wherein the radicals R¹⁵ and R¹⁶ can form a common group -G- and -G-represents one of the following groups: (-CR⁵ = CR⁶-CR⁷ = CR⁸-) or (-CR⁸ = CR⁷-CR⁶ = CR⁵-).
The radicals R⁵ to R⁸ can be the same or different and independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl -C₁-C₆-alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and where the amino, carbamoyl and sufamoyl groups of the radicals R⁵ to R⁸ continue to be unsubstituted or a - Or be substituted twice with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy and where the C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl -Groups of the radicals R⁵ to R⁸ are unsubstituted or can be substituted one or more times with the radical R¹⁸ and the radical R¹⁸ can be one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro , C₁-C₁₂ alkyl , C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, and their esters and salts, and the carbamoyl, sulfamoyl, amino groups of the radical R¹⁸ can be unsubstituted or can furthermore be mono- or disubstituted with the radical R¹⁹ and wherein the radical R¹⁹ can represent one of the following groups: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl.

Examples:

Wobei X für eine der folgenden Gruppen steht: (-N=N-), (-N=CR₁₀₋)_p,(-CR₁₀=N-)_p, (-CR₁₁=CR₁₂-)_p

und p gleich 1 oder 2 ist.1-hydroxy-1,2,3-triazole-4,5-dicarboxylic acid
1-phenyl-1H-1,2,3-triazole-3-oxide
5-chloro-1-phenyl-1H-1,2,3-triazole-3-oxide
5-methyl-1-phenyl-1H-1,2,3-triazole-3-oxide
4- (2,2Dimethylpropanoyl) -1-hydroxy-1H-1,2,3-triazole
4-hydroxy-2-phenyl-2H-1,2,3-triazole-1-oxide
2,4,5-triphenyl-2H-1,2,3-triazole-1-oxide
1-benzyl-1H-1,2,3-triazole-3-oxide
1-benzyl-4-chloro-1H-1,2,3-triazole-3-oxide
1-benzyl-4-bromo-1H-1,2,3-triazole-3-oxide
1-benzyl-4-methoxy-1H-1,2,3-triazole-3-oxide
Compounds of general structure III are:

Where X stands for one of the following groups: (-N = N-), (-N = CR₁₀₋) _p , (- CR₁₀ = N-) _p , (-CR₁₁ = CR₁₂-) _p

and p is 1 or 2.

The radicals R⁵ to R¹² can be the same or different and independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and wherein the amino, carbamoyl and sufamoyl groups of the radicals R⁵ to R¹² further unsubstituted or substituted one or two times with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy
and wherein the C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, aryl-C₁-C₆-alkyl groups of the radicals R⁵ to R¹² are unsubstituted or continue to be or can be substituted several times with the radical R¹³ and the radical R¹³ can represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆- alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and their esters and salts
and wherein the carbamoyl, sufamoyl, amino groups of the radical R¹³ can be unsubstituted or can furthermore be mono- or disubstituted with the radical R¹⁴ and the radical R¹⁴ can be one of the following groups: hydrogen, hydroxy, formyl, carboxy and salts thereof and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl.

Examples: 1-hydroxy-benzimidazole

1-hydroxybenzimidazole-2-carboxylic acid
1-hydroxybenzimidazole
2-methyl-1-hydroxybenzimidazole
2-phenyl-1-hydroxybenzimidazole

1-hydroxyindoles

Wobei X für eine der folgenden Gruppen steht: (-N=N-), (-N=CR¹⁰-)_m, (-CR¹⁰=N-)_m, (-CR¹¹=CR¹²-)_m

und m gleich 1 oder 2 ist.2-phenyl-1-hydroxyindole
Substances of the general formula IV are:

Where X stands for one of the following groups: (-N = N-), (-N = CR¹⁰-) _m , (-CR¹⁰ = N-) _m , (-CR¹¹ = CR¹²-) _m

and m is 1 or 2.

The above applies to the radicals R⁵ to R⁸ and R¹⁰ to R¹².

R¹⁷ can be: hydrogen, C₁-C₁₀-alkyl, C₁-C₁₀-carbonyl whose C₁-C₁₀-alkyl and C₁-C₁₀-carbonyl are unsubstituted or can be substituted one or more times with a radical R¹⁸ which is defined as R³.

Die Reste R⁵ bis R⁸ können gleich oder ungleich sein und unabhängig voneinander eine der folgenden Gruppen darstellen: Wasserstoff, Halogen, hydroxy, formyl, carboxy sowie Salze und Ester davon, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C1-C6-alkyl, phenyl, sulfono Ester und Salze davon, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy und deren Salze und Ester und wobei die amino-, carbamoyl- und sulfamoyl-Gruppen der Reste R⁵ bis R⁸ weiterhin unsubstitiert oder ein- oder zweifach mit hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy substituiert sein können und wobei die C₁-C₁₂-alkyl-, C₁-C₆-alkyloxy-, carbonyl-C₁-C₆-alkyl-, phenyl-, aryl-Gruppen der Reste R⁵ bis R⁸ unsubstituiert oder weiterhin ein oder mehrfach mit dem Rest R¹⁸ substituiert sein können und wobei der Rest R¹⁸ eine der folgenden Gruppen darstellen kann: Wasserstoff, Halogen, Hydroxy, Formyl, Carboxy sowie deren Salze und Ester, Amino, Nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, sulfono, sulfeno, sulfino sowie deren Ester und Salze und wobei die carbamoyl, sufamoyl, amino-Gruppen des Restes R¹⁸ unsubstituiert oder weiterhin ein oder zweifach mit dem Rest R¹⁹ substituiert sein können und wobei der Rest R¹⁹ eine der folgenden Gruppen darstellen kann: Wasserstoff, hydroxy, formyl, carboxy sowie deren Salze und Ester, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl.Of the substances of formula IV are, in particular, derivatives of 1-hydroxybenzotriazole and the tautomeric benzotriazole-1-oxide and their esters and salts are preferred (compounds of the formula V)

The radicals R⁵ to R⁸ can be identical or different and independently of one another represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C1-C6-alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and wherein the amino, carbamoyl and sulfamoyl groups of the radicals R⁵ to R⁸ continue to be unsubstituted or may be substituted once or twice with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy and where the C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl groups of the radicals R⁵ to R⁸ can be unsubstituted or can be substituted one or more times with the radical R¹⁸ and the radical R¹⁸ can be one of the following groups: hydrogen, halogen, hydroxyl, formyl, carboxy and their salts and esters, amino, Nitro, C₁-C₁₂ alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and their esters and salts and where the carbamoyl, sufamoyl, amino groups of the radical R¹⁸ are unsubstituted or furthermore one or two times with the rest R¹⁹ can be substituted and the radical R¹⁹ can represent one of the following groups: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆ -alkyl, phenyl, aryl.

Examples: 1H-hydroxybenzotriazoles

1-hydroxybenzotriazole
1-hydroxybenzotriazole, sodium salt.
1-hydroxybenzotriazole potassium salt
1-hydroxybenzotriazole, lithium salt
1-hydroxybenzotriazole, ammonium salt
1-hydroxybenzotriazole, calcium salt
1-hydroxybenzotriazole, magnesium salt
1-hydroxybenzotriazole-6-sulfonic acid
1-hydroxybenzotriazole-6-sulfonic acid, monosodium salt
1-hydroxybenzotriazole-6-carboxylic acid
1-hydroxybenzotriazole-6-N-phenylcarboxamide
5-ethoxy-6-nitro-1-hydroxybenzotriazole
4-ethyl-7-methyl-6-nitro-1-hydroxybenzotriazole
2,3-bis (4-ethoxyphenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole
2,3-bis (2-bromo-4-methylphenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole
2,3-bis (4-bromo-phenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole
2,3-bis (4-carboxyphenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole
4,6-bis (trifluoromethyl) -1-hydroxybenzotriazole
5-bromo-1-hydroxybenzotriazole
6-bromo-1-hydroxybenzotriazole
4-bromo-7-methyl-1-hydroxybenzotriazole
5-bromo-7-methyl-6-nitro-1-hydroxybenzotriazole
4-bromo-6-nitro-1-hydroxybenzotriazole
6-bromo-4-nitro-1-hydroxybenzotriazole
4-chloro-1-hydroxybenzotriazole
5-chloro-1-hydroxybenzotriazole
6-chloro-1-hydroxybenzotriazole
6-chloro-5-isopropyl-1-hydroxybenzotriazole
5-chloro-6-methyl-1-hydroxybenzotriazole
6-chloro-5-methyl-1-hydroxybenzotriazole
4-chloro-7-methyl-6-nitro-1-hydroxybenzotriazole
4-chloro-5-methyl-1-hydroxybenzotriazole
5-chloro-4-methyl-1-hydroxybenzotriazole
4-chloro-6-nitro-1-hydroxybenzotriazole
6-chloro-4-nitro-1-hydroxybenzotriazole
7-chloro-1-hydroxybenzotriazole
6-diacetylamino-1-hydroxybenzotriazole
2,3-dibenzyl-4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole
4,6-dibromo-1-hydroxybenzotriazole
4,6-dichloro-1-hydroxybenzotriazole
5,6-dichloro-1-hydroxybenzotriazole
4,5-dichloro-1-hydroxybenzotriazole
4,7-dichloro-1-hydroxybenzotriazole
5,7-dichloro-6-nitro-1-hydroxybenzotriazole
5,6-dimethoxy-1-hydroxybenzotriazole
2,3-di- [2] naphthyl-4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole
4,6-dinitro-1-hydroxybenzotriazole
4,6-dinitro-2,3-diphenyl-2,3-dihydro-1-hydroxybenzotriazole
4,6-dinitro-2,3-di-p-totolyl-2,3-dihydro-1-hydroxybenzotriazole
5-hydrazino-7-methyl-4-nitro-1-hydroxybenzotriazole
5,6-dimethyl-1-hydroxybenzotriazole
4-methyl-1-hydroxybenzotriazole
5-methyl-1-hydroxybenzotriazole
6-methyl-1-hydroxybenzotriazole
5- (1-methylyl) -1-hydroxybenzotriazole
4-methyl-6-nitro-1-hydroxybenzotriazole
6-methyl-4-nitro-1-hydroxybenzotriazole
5-methoxy-1-hydroxybenzotriazole
6-methoxy-1-hydroxybenzotriazole
7-methyl-6-nitro-1-hydroxybenzotriazole
4-nitro-1-hydroxybenzotriazole
6-nitro-1-hydroxybenzotriazole
6-nitro-4-phenyl-1-hydroxybenzotriazole
5-phenylmethyl-1-hydroxybenzotriazole
4-trifluoromethyl-1-hydroxybenzotriazole
5-trifluoromethyl-1-hydroxybenzotriazole
6-triflourmethyl-1-hydroxybenzotriazole
4,5,6,7-tetrachloro-1-hydroxybenzotriazole
4,5,6,7-tetraflour-1-hydroxybenzotriazole
6-tetraflourethyl-1-hydroxybenzotriazole
4,5,6-trichloro-1-hydroxybenzotriazole
4,6,7-trichloro-1-hydroxybenzotriazole
6-sulfamido-1-hydroxybenzotriazole
6-N, N-diethylsulfamido-1-hydroxybenzotriazole
6-N-methylsulfamido-1-hydroxybenzotriazole
6- (1H-1,2,4-triazol-1-ylmethyl) -1-hydroxybenzotriazole
6- (5,6,7,8-tetrahydroimidazo [1,5-a] pyridin-5-yl) -1-hydroxybenzotriazole
6- (Phenyl-1H-1,2,4-triazol-1-ylmethyl) -1-hydroxybenzotriazole
6 - [(5-methyl-1H-imidazo-1-yl) phenylmethyl] -1-hydroxybenzotriazole
6 - [(4-methyl-1H-imidazo-1-yl) phenylmethyl] -1-hydroxybenzotriazole
6 - [(2-methyl-1H-imidazo-1-yl) phenylmethyl] -1-hydroxybenzotriazole
6- (1H-Imidazol-1-yl-phenylmethyl) -1-hydroxybenzotriazole
5- (1H-Imidazol-1-yl-phenylmethyl) -1-hydroxybenzotriazole
6- [1- (1H-Imidazol-1-yl) ethyl] -1-hydroxybenzotriazole monohydrochloride

3H-benzotriazole-1-oxides

3H-benzotriazole-1-oxide
6-acetyl-3H-benzotriazole-1-oxide
5-ethoxy-6-nitro-3H-benzotriazole-1-oxide
4-ethyl-7-methyl-6-nitro-3H-benzotriazole-1-oxide
6-amino-3,5-dimethyl-3H-benzotriazole-1-oxide
6-amino-3-methyl-3H-benzotriazole-1-oxide
5-bromo-3H-benzotriazole-1-oxide
6-bromo-3H-benzotriazole-1-oxide
4-bromo-7-methyl-3H-benzotriazole-1-oxide
5-bromo-4-chloro-6-nitro-3H-benzotriazole-1-oxide
4-bromo-6-nitro-3H-benzotriazole-1-oxide
6.Bromine-4-nitro-3H-benzotriazole-1-oxide
5-chloro-3H-benzotriazole-1-oxide
6-chloro-3H-benzotriazole-1-oxide
4-chloro-6-nitro-3H-benzotriazole-1-oxide
4,6-dibromo-3H-benzotriazole-1-oxide
4,6-dibromo-3-methyl-3Hbenzotriazole-1-oxide
4,6-dichloro-3H-benzotriazole-1-oxide
4,7-dichloro-3H-benzotriazole-1-oxide
5,6-dichloro-3H-benzotriazole-1-oxide
4,6-dichloro-3-methyl-3H-benzotriazole-1-oxide
5,7-dichloro-6-nitro-3H-benzotriazole-1-oxide
3,6-dimethyl-6-nitro-3H-benzotriazole-1-oxide
3,5-dimethyl-6-nitro-3H-benzotriazole-1-oxide 3-methyl-3H-benzotriazole-1-oxide
5-methyl-3H-benzotriazole-1-oxide
6-methyl-3H-benzotriazole-1-oxide
6-methyl-4-nitro-3H-benzotriazole-1-oxide
7-methyl-6-nitro-3H-benzotriazole-1-oxide
5-chloro-6-nitro-3H-benzotriazole-1-oxide

2H-benzotriazole-1-oxide

2- (4-acetoxy-phenyl) -2H-benzotriazole-1-oxide
6-acetylamino-2-phenyl-2H-benzotriazole-1-oxide
2- (4-ethylphenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (3-aminophenyl) -2H-benzotriazole-1-oxide
2- (4-aminophenyl) -2H-benzotriazole-1-oxide
6-amino-2-phenyl-2H-benzotriazole-1-oxide
5-bromo-4-chloro-6-nitro-2-phenyl-2H-benzotriazole-1-oxide
2- (4-bromophenyl) -2H-benzotriazole-1-oxide
5-bromo-2-phenyl-2H-benzotriazole-1-oxide
6-bromo-2-phenyl-2H-benzotriazole-1-oxide
2- (4-bromophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (4-bromophenyl) -6-nitro-2H-benzotriazole-1-oxide
5-chloro-2- (2-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (3-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (2-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (3-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (2,4-dibromophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (2,5-dimethylphenyl) -2H-benzotriazole-1-oxide
5 chloro-2- (4-nitrophenyl) -2H-benzotriazole-1-oxide
5-chloro-6-nitro-2-phenyl-2H-2H-benzotriazole-1-oxide
2- [4- (4-Clor-3-nitro-phenylazo) -3-nitrophenyl] -4,6-dinitro-2H-benzotriazole-1-oxide
2- (3-chloro-4-nitro-phenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (4-chloro-3-nitrophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
4-chloro-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
5-chloro-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
6-chloro-4-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
2- (2-chlorophenyl) -2H-benzotriazole-1-oxide
2- (3-chlorophenyl) -2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2-phenyl-2H-benzotriazole-1-oxide
2- [4- (4-chlorophenylazo) -3-nitrophenyl] -4,6-dinitro-2H-benzotriazole-1-oxide
2- (2-chlorophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (3-chlorophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- {4- [N '- (3-chlorophenyl) hydrazino] -3-nitrophenyl} 4,6-dinitro-2H-benzotriazole-1-oxide
2- {4- [N '- (4-chlorophenyl) hydrazino] -3-nitrophenyl} 4,6-dinitro-2H-benzotriazole-1-oxide
2- (2-chlorophenyl) -6-methyl-2H-benzotriazole-1-oxide
2- (3-chlorophenyl) -6-methyl-2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -6-methyl-2H-benzotriazole-1-oxide
2- (3-chlorophenyl) -6-nitro-2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -6-nitro-2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -6-picrylazo-2H-benzotriazole-1-oxide
5-chloro-2- (2,4,5-trimethylphenyl) -2H-benzotriazole-1-oxide
4,5-dibromo-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
4,5-dichloro-6-nitro-2-phenyl-2H-benzotriazole-1-oxide
4,5-dichloro-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
4,7-dichloro-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
4,7-dimethyl-6-nitro-2-phenyl-2H-benzotriazole-1-oxide
2- (2,4-dimethylphenyl) -4,6-dinitro-benzotriazole-1-oxide
2- (2,5-dimethylphenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (2,4-dimethylphenyl) -6-nitro-2H-benzotriazole-1-oxide
2- (2,5-dimethylphenyl) -6-nitro-2H-benzotriazole-1-oxide
4,6-Dinitro-2- [3-nitro-4- (N'-phenylhydrazino) phenyl -] - 2H-benzotriazole-1-oxide
4,6-Dinitro-2- [4-nitro-4- (N'-phenylhydrazino) phenyl -] - 2H-benzotriazole-1-oxide
4,6-dinitro-2-phenyl-2H-benzotriazole-1-oxide
2- (2,4-dinitrophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (2,4-dinitrophenyl) -6-nitro-2H-benzotriazole-1-oxide
4,6-dinitro-2-o-tolyl-2H-benzotriazole-1-oxide
4,6-dinitro-2-p-tolyl-2H-benzotriazole-1-oxide
4,6-Dinitro-2- (2,4,5-trimethylphenyl) -2H-benzotriazole-1-oxide
2- (4-methoxyphenyl) -2H-benzotriazole-1-oxide
2- (4-methoxyphenyl) -6-methyl-2H-benzotriazole-1-oxide
5-methyl-6-nitro-2-m-tolyl-2H-benzotriazole-1-oxide
5-methyl-6-nitro-2-o-tolyl-2H-benzotriazole-1-oxide
5-methyl-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
6-methyl-4-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
6-methyl-2-phenyl-2H-benzotriazole-1-oxide
4-methyl-2-m-tolyl-2H-benzotriazole-1-oxide
4-methyl-2-o-tolyl-2H-benzotriazole-1-oxide
4-methyl-2-p-tolyl-2H-benzotriazole-1-oxide
6-methyl-2-m-tolyl-2H-benzotriazole-1-oxide
6-methyl-2-o-tolyl-2H-benzotriazole-1-oxide
6-methyl-2-p-tolyl-2H-benzotriazole-1-oxide
2- [1] naphthyl-4-6-dinitro-2H-benzotriazole-1-oxide
2- [2] naphthyl-4-6-dinitro-2H-benzotriazole-1-oxide
2- [1] naphthyl-6-nitro-2H-benzotriazole-1-oxide
2- [2] naphthyl-6-nitro-2H-benzotriazole-1-oxide
2- (3-nitrophenyl) -2H-benzotriazole-1-oxide
6-nitro - 2-phenyl-2H-benzotriazole-1-oxide
4-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
6-nitro-2-o-tolyl-2H-benzotriazole-1-oxide
6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
6-nitro-2- (2,4,5-trimethylphenyl) -2H-benzotriazole-1-oxide
2-phenyl-2H-benzotriazole-1-oxide
2-o-tolyl-2H-benzotriazole-1-oxide
2-p-tolyl-2H-benzotriazole-1-oxide
Also preferred are heterocycles which contain at least one N-hydroxy, oxime, N-oxy, N, N-dioxy function or a further heteroatom, such as O, S, Se, Te, such as:
Aziridines, diaziridines, pyrroles, dihydropyrroles, tetrahydropyrroles, pyrazoles, dihydropyrazoles, tetrahydropyrazoles, imidazoles, dihydroimidazoles, tetrahydroimidazoles, dihydroimidazoles, 1,2,3-triazoles, 1,2,4-triazoles, pyridine, pyridoles, pyridine Pyrimidines, pyrazines, piperazines, 1,2,3-triazines, 1,2,4-triazines, 1,2,3-triazines, tetrazines, azepines, oxazoles, isoxazole, thiazoles, isothiazoles, thiadiazoles, morpholines, and their benzocondensed derivatives such as: indoles, isoindoles, indolizines, indazoles, benzimidazoles, benztriazoles, quinolines, isoquinolines, phthalazines, quinazolines, quinoxalines, phenazines, benzazepines, benzothiazoles, benzoxazoles.

Likewise preferred are condensed N-heterocycles such as triazolo and tetrazolo compounds which have at least one N-hydroxy, oxime, N-oxi, N, N-dioxi function and in addition to N a further heteroatom such as O, S, Se, Te can contain.
[1,2,4] triazolo [4,3-a] pyridines
[1,2,4] triazolo [1,5-a] pyridines
[1,2,4] triazolo [4,3-a] quinolines
[1,2,4] triazolo [4,3-b] isoquinolines
[1,2,4] triazolo [3,4-a] isoquinolines
[1,2,4] triazolo [1,5-b] isoquinolines
[1,2,4] triazolo [5,1-a] isoquinolines
[1,2,3] triazolo [1,5-a] pyridines
[1,2,3] triazolo [4,5-b] pyridines
[1,2,3] triazolo [4,5-c] pyridines
[1,2,3] triazolo [1,5-a] quinolines
[1,2,3] triazolo [5,1-a] isoquinolines
[1,2,4] triazolo [4,3-b] pyridazines
[1,2,4] triazolo [1,5-b] pyridazines
[1,2,4] triazolo [4,5-d] pyridazines
[1,2,4] triazolo [4,3-b] cinnoline
[1,2,4] triazolo [3,4-a] phthalazines
[1,2,4] triazolo [4,3-a] pyrimidines
[1,2,4] triazolo [4,3-c] pyrimidines
[1,2,4] triazolo [1,5-a] pyrimidines
[1,2,4] triazolo [1,5-c] pyrimidines
[1,2,4] triazolo [4,3-c] quinazoline
[1,2,4] triazolo [1,5-a] quinazoline
[1,2,4] triazolo [1,5-c] quinazoline
[1,2,4] triazolo [5,1-b] quinazoline
[1,2,3] triazolo [1,5-a] pyrimidines
[1,2,3] triazolo [1,5-c] pyrimidines
[1,2,3] triazolo [4,5-d] pyrimidines
[1,2,3] triazolo [1,5-a] quinazoline
[1,2,3] triazolo [1,5-c] quinazoline
[1,2,4] triazolo [4,3-a] pyrazine
[1,2,4] triazolo [1,5-a] pyrazine
[1,2,4] triazolo [1,5-a] pyrazine
[1,2,3] triazolo [4,5-b] pyrazine
[1,2,4] triazolo [4,3-a] quinoxaline
[1,2,3] triazolo [1,5-a] quinoxaline
[1,2,4] triazolo [4,3-b] [1,2,4] triazine
[1,2,4] triazolo [3,4-c] [1,2,4] triazine
[1,2,4] triazolo [4,3-d] [1,2,4] triazine
[1,2,4] triazolo [3,4-f] [1,2,4] triazine
[1,2,4] triazolo [1,5-b] [1,2,4] triazine
[1,2,4] triazolo [5,1-c] [1,2,4] triazine
[1,2,4] triazolo [1,5-d] [1,2,4] triazine
[1,2,4] triazolo [4,3-a] [1,3,5] triazine
[1,2,4] triazolo [1,5-a] [1,3,5] triazine
Tetrazolo [1,5-a] pyridine
Tetrazolo [1,5-b] isoquinolines
Tetrazolo [1,5-a] quinoline
Tetrazolo [5,1-a] isoquinolines
Tetrazolo [1,5-b] pyridazines
Tetrazolo [1,5-b] cinnoline
Tetrazolo [5,1-a] phthalazines
Tetrazolo [1,5-a] pyrimidines
Tetrazolo [1,5-c] pyrimidines
Tetrazolo [1,5-a] quinazoline
Tetrazolo [1,5-c] quinazoline
Tetrazolo [1,5-a] pyrazine
Tetrazolo [1,5-a] quinoxaline
Tetrazolo [1,5-b] [1,2,4] triazines
Tetrazolo [5,1-c] [1,2,4] triazines
Tetrazolo [1,5-d] [1,2,4] triazines
Tetrazolo [5,1-f] [1,2,4] triazines

Other:

Quinoline N-oxide
Isoquinoline N-oxide
N-hydroxy-1,2,3,4-tetrahydro-isoquinoline
β- (N-oxy-1,2,3,4-tetrahydroisoquinolino) propionic acid
1,3-dihydroxy-2N-benzylimido-benzimidazoline
The multi-component system (d) according to the invention comprises, for example, aliphatic ethers, aryl-substituted alcohols such as, for example
2,3-dimethoxybenzyl alcohol
3,4-dimethoxybenzyl alcohol
2,4-dimethoxybenzyl alcohol
2,6-dimethoxybenzyl alcohol
Homovanillyl alcohol
Ethylene glycol monophenyl ether
2-hydroxybenzyl alcohol
4-hydroxybenzyl alcohol
4-hydroxy-3-methoxybenzyl alcohol
2-methoxybenzyl alcohol
2,5-dimethoxybenzyl alcohol
3,4-dimethoxybenzylamine
2,4-dimethoxybenzylamine hydrochloride
Veratryl alcohol
Coniferyl alcohol
Olefins (alkenes)
e.g.
2-allylphenol
2-allyl-6-methylphenol
Allylbenzene
3,4-dimethoxypropenylbenzene
p-methoxystyrene
1-allylimidazole
1-vinylimidazole
Styrene
Stilbene
Allylphenyl ether
Benzyl cinnamate
Cinnamic acid methyl ester
2,4,6-triallyloxy-1,3,5-triazine
1,2,4-trivinylcyclohexane
4-allyl-1,2-dimethoxybenzene
4-tert-Butylbenzoic acid vinyl ester
Squalene
Benzoin allyl ether
Cyclohexene
Dihydropyran
N-benzylcinnamic acid anilide
preferably phenol ether
such as
2,3-dimethoxybenzyl alcohol
3,4-dimethoxybenzyl alcohol
2,4-dimethoxybenzyl alcohol
2,6-dimethoxybenzyl alcohol
Homovanillyl alcohol
4-hydroxybenzyl alcohol
4-hydroxy-3-methoxybenzyl alcohol
2-methoxybenzyl alcohol
2,5-dimethoxybenzyl alcohol
3,4-dimethoxybenzylamine
2,4-dimethoxybenzylamine hydrochloride
Veratryl alcohol
Coniferyl alcohol
Veratrol
Anisole
preferably carbonyl compounds such as
4-aminobenzophenone
4-acetylbiphenyl
Benzophenone
Benzil
Benzophenone hydrazone
3,4-dimethoxybenzaldehyde
3,4-dimethoxybenzoic acid
3,4-dimethoxybenzophenone
4-dimethylaminobenzaldehyde
4-acetylbiphenylhydrazone
Benzophenone-4-carboxylic acid
Benzoylacetone
Bis (4,4'-dimethylamino) benzophenone
Benzoin
Benzoin oxime
N-benzoyl-N-phenyl-hydroxylamine
2-amino-5-chloro-benzophenone
3-hydroxy-4-methoxybenzaldehyde
4-methoxybenzaldehyde
Anthraquinone-2-sulfonic acid
4-methylaminobenzaldehyde
Benzaldehyde
Benzophenone-2-carboxylic acid
3,3'4,4'-benzophenonetetracarboxylic acid dianhydride
(S) - (-) - 2- (N-bezylpropyl) aminobenzophenone
Benzylphenylacetic anilide
N-benzylbenzanilide
4,4'-bis (dimethylamino) thiobenzophenone
4,4'-bis (diacetylamino) benzophenone
2-chlorobenzophenone
4,4'-dihydroxybenzophenone
2,4-dihydroxybenzophenone
3,5-dimethoxy-4-hydroxybenzaldehydrazine
4-hydroxybenzophenone
2-hydroxy-4-methoxybenzophenone
4-methoxybenzophenone
3,4-dihydroxybenzophenone
p-anisic acid
p-anisaldehyde
3,4-dihydroxybenzaldehyde
3,4-dihydroxybenzoic acid
3,5-dimethoxy-4-hydroxybenzaldehyde
3,5-dimethoxy-4-hydroxybenoic acid
4-hydroxybenzaldehyde
Salicylaldehyde
Vanillin
Vanillic acid
By adding the compounds of the multicomponent system mentioned under d) and e), the reaction is mediated in cascade form or the actual mediator compounds are recycled in situ, ie during the reaction, and surprisingly leads to a substantial improvement in the kappa reduction or reduction in the mediator dosage.

The additives mentioned under d) in claim 1 are preferably used in amounts of 0.01 to 0.5 mg per g of lignin-containing material. 0.01 to 0.1 mg per g of lignin-containing material are particularly preferably used.

The free amine of the respective mediator is preferably used in a mediator / amine ratio of 100: 1 to 1: 1, particularly preferably 20: 1 to 1: 1, particularly preferably 10: 1 to 2: 1.

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 Mg²⁺ ions are also present in addition to the components mentioned. The Mg²⁺ ions can be used, for example, as a salt, e.g. MgSO4 can be used. The concentration is in the range of 0.1-2 mg / g of lignin-containing material, preferably 0.2-0.6 mg / g.

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 Mg²⁺ ions also complexing agents such as e.g. Contains ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentametylenophosphonic acid (DTMPA), nitrilotriacetic acid (NTA), polyphosphoric acid (PPA) etc. The concentration is in the range of 0.2-5 mg / g of lignin-containing material, preferably 1-3 mg.

The merh component system according to the invention is used in a process for treating lignin, for example, by selected components a) to e) according to claim 1 simultaneously or in any order with an aqueous suspension of the lignin-containing material.

A process using the multicomponent system according to the invention is preferred in the presence of oxygen or air at atmospheric pressure up to 10 bar and in a pH range from 2 to 11, at a temperature from 20 to 95 ° C., preferably 40-95 ° C., and one Fabric density from 0.5 to 40% carried out.

A finding that is unusual and surprising for the use of enzymes in cellulose bleaching is that when the multicomponent system according to the invention is used, increasing the consistency enables a significant increase in the kappa reduction.

Surprisingly, an increased consistency led to better activity of the multi-component system.

For economic reasons, a process according to the invention is preferably carried out at consistencies of 12 to 15%, particularly preferably 14 to 15%.

Surprisingly, it was also found that an acidic 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 pulps led to a considerable reduction in the kappa number Comparison to treatment without this special pretreatment leads. The substances used for this purpose (such as EDTA, DTPA) are used as chelating agents in the Q stage. They are preferably used in concentrations of 0.1% / to 1% / to, particularly preferably 0.1% / to to 0.5% / to.

In the process according to the invention, preferably 100 to 100,000 IU enzyme per g lignin-containing material are used. 1,000 to 40,000 IU enzyme per g of lignin-containing material are particularly preferably used.

In the process according to the invention, preferably 0.01 mg to 100 mg of oxidizing agent are used per g of lignin-containing material. 0.01 to 50 mg of oxide ionizing agent per g of lignin-containing material are particularly preferably used.

In the method according to the invention, 0.5 to 80 mg of mediator per g of lignin-containing material is preferably used. 0.5 to 40 mg of mediator per g of lignin-containing material is particularly preferably used.

Using the multi-component system according to the invention, for example in the bleaching of sulfate pulps (Softwood), the completely surprising result of a reduction in the kappa number from approximately 30 to 10 within 1 to 4 hours could be achieved even with a high consistency in the range of approximately 15%, whereby by Addition of components d) and e) according to claim 1 enables a considerable reduction in the concentration of component c) (mediator).

At the same time, reducing agents can be added which, together with the oxidizing agents present, serve to set a certain redox potential.

Sodium bisulfite, sodium dithionite, ascorbic acid, thio compounds, mercapto compounds or glutation etc. can be used as reducing agents.

In the case of laccase, for example, the reaction takes place with the addition of oxygen or oxygen overpressure, with the peroxidases (e.g. lignin peroxidases, manganese peroxidases) with hydrogen peroxide. For example, the oxygen can also be generated in situ by hydrogen peroxide + catalase and hydrogen peroxide by glucose + GOD or other systems.

In addition, radical formers or radical scavengers (trapping, for example, OH or OOH radicals) 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.

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 Fe2 +, Fe3 +, Mn2 +, Mn3 +, Mn4 +, Cu 2+, Ca2 +, Ti3 +, Cer4 +, Al3 +.

The chelates present in the solution can also serve as mimic substances for the enzymes, for example for the laccases (copper complexes) or for the lignin or manganese peroxidases (heme complexes). Mimic substances are substances that simulate the prosthetic groups of (here) oxidoreductases and e.g. Can catalyze oxidation reactions.

NaOCl can also be added to the reaction mixture. In combination with hydrogen peroxide, this compound can form Sindulett oxygen.

Finally, it is also possible to work with dermatological agents. 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.

It may also be beneficial for the reaction to add polysaccharides and / or proteins. Glucans, mannans, dextrans, levans, pectins, alginates or plant gums and / or proprietary polysaccharides formed by the fungi or produced in a mixed culture with yeasts are to be mentioned here in particular as polysaccharides and gelatin and albumin as proteins.

These substances mainly serve as protective colloids for the enzymes.

Other proteins that can be added are proteases such as pepsin, bromelin, papain, etc. These can serve, inter alia, to achieve better access to lignin by breaking down the extensin chydroxypholine-rich protein present in the wood.

Amino acids, simple sugars, oligomer sugars, amino acids, PEG types of the most varied molecular weights, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes can be considered as further protective colloids.

The process according to the invention can be used not only in the delignification (bleaching) of sulfate, sulfite, organolsolv or the like. Pulp and wood pulp are used, but also in the production of pulp in general, whether from wood or annual plants, if defibrillation by the usual cooking methods (possibly connected with mechanical processes or pressure) i.e. a very gentle cooking up to kappa numbers, which can be in the range of approx. 50 - 120 kappa, is guaranteed.

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 O2 stage can be used before the enzyme / mediator treatment or, as already mentioned, an acid wash or Q stage (chelate stage) can be carried out.

A similar procedure is used for the "liquefaction" of coal (hard coal, lignite) as for the delignification (bleaching) of wood or annual plant pulp.

The invention is explained in more detail below with the aid of examples:

Example 1/2 Example: Enzymatic bleach and sulfate pulp. Example 1:

• i) 120 ml Leitungswasser werden mit 150 mg Hydroxybenzotriazol (HBT), 15 mg Benztriazol (BT) und 3 mg Benzophenon (B) unter Rühren versetzt, der pH-Wert mit 0,5 m H₂SO₄ so eingestellt, daß nach Zugabe des Zellstoffes und des Enzymes pH 4,5 resultiert. Dazu werden 4.000 IU (1 IU = Umsatz von 1 µM Syringaldazin/min/ml Enzym) Laccase von Coriolus versicolor pro g Stoff gegeben. Die Lösung wird auf 200 ml aufgefüllt und der Stoff zugegeben. Es wird für 2 min mit einem Teigkneter gemixt.

30 g dry cellulose (Softwood O₂ delignified), consistency 30% (∼ 100 g moist) are added to the following solutions:

• i) 120 ml of tap water are mixed with stirring with 150 mg of hydroxybenzotriazole (HBT), 15 mg of benzotriazole (BT) and 3 mg of benzophenone (B), the pH is adjusted with 0.5 m H₂SO₄ so that after adding the pulp and of the enzyme pH 4.5 results. For this purpose, 4,000 IU (1 IU = conversion of 1 µM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar pressure for 1-4 hours.

The substance is then washed over a nylon sieve (30 μm) and extracted for 1 hour at 60 ° C., 8% density and 2% NaOH per g substance.

After washing the fabric again, the kappa number is determined.
(see table 1)
(see table 2)

Changes to example / table 2:

with 75 mg hydroxybenzotriazole, 7.5 mg benzotriazole and 0.02 mg veratryl alcohol.

Example 3 Example: Enzymatic bleaching of sulfate pulp.

• 1. 120 ml Leitungswasser werden mit 60 mg DTPA und 15 mg MgSO₄ unter Rühren versetzt. Der pH-Wert wird mit 0,5 m H₂SO₄ so eingestellt, daß nach Zugabe des Zellstoffes und des Enzymes pH 4,5 resultiert. Dazu werden 4.000 IU (1 IU = Umsatz von 1 µM Syringaldazin/min/ml Enzym) Laccase von Coriolus versicolor pro g Stoff gegeben. Die Lösung wird auf 200 ml aufgefüllt und der Stoff zugegeben. Es wird für 2 min mit einem Teigkneter gemixt.

30 g dry cellulose (Softwood), consistency 30% (- 100 g wet) are added to the following solution:

• 1. 120 ml of tap water are mixed with 60 mg DTPA and 15 mg MgSO₄ with stirring. The pH is adjusted with 0.5 m H₂SO₄ so that pH 4.5 results after adding the pulp and the enzyme. For this purpose, 4,000 IU (1 IU = conversion of 1 µM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar overpressure for 1-4 hours.

The substance is then washed over a nylon sieve (30 μm) and extracted for 1 hour at 60 ° C., 8% density and 2% NaOH per g substance.

After washing the fabric again, the kappa number is determined.

The results are shown in Table 3.

Example 4 Example: Enzymatic bleaching of sulfate pulps with an upstream Q stage.

• 1) Q-Stufe: 120 ml Leitungswasser werden mit 90 mg DTPA versetzt und der pH-Wert mit 0,5 m H₂SO₄ so eingestellt, daß nach Zugabe des Zellstoffs pH 4,5 resultiert. Die Lösung wird auf 200 ml aufgefüllt und für 2 min mit einem Teigkneter gemixt.
  Anschließend wird der Stoff in einem verschlossenem Becherglas bei 90°C belassen.
  Anschließend wird gut gewaschen (Leitungswasser), der Stoff auf 30% Stoffdichte gebracht und zu folgender Lösung gegeben:
• 2) Laccase/Extraktionsstufe: 120 ml Leitungswasser werden mit
  300 mg Hydroxybenztriazol unter Rühren versetzt. Der pH-Wert wird mit 0,5 m H₂SO₄ so eingestellt, daß nach Zugabe des Zellstoffs und des Enzyms pH 4,5 resultiert. Dazu werden 4.000 IU (1 IU = Umsatz von 1 µM Syringaldazin/min/ml Enzym) Laccase von Coriolus versicolor pro g Stoff gegeben. Die Lösung wird auf 200 ml aufgefüllt und der Stoff zugegeben. Es wird für 2 min mit einem Teigkneter gemixt.

30 g dry cellulose (Softwood 1 and Softwood 2), consistency 30% (∼100 g wet) are added to the following solutions:

• 1) Q stage: 120 ml of tap water are mixed with 90 mg of DTPA and the pH is adjusted with 0.5 m H₂SO₄ so that pH 4.5 results after addition of the pulp. The solution is made up to 200 ml and mixed for 2 min with a dough kneader.
  The fabric is then left in a sealed beaker at 90 ° C.
  Then it is washed well (tap water), the fabric is brought to 30% consistency and added to the following solution:
• 2) Laccase / extraction stage: 120 ml of tap water are included
  300 mg of hydroxybenzotriazole were added with stirring. The pH is adjusted with 0.5 m H₂SO₄ so that pH 4.5 results after addition of the pulp and the enzyme. For this purpose, 4,000 IU (1 IU = conversion of 1 µM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar overpressure for 1-4 hours.

The substance is then washed over a nylon sieve (30 μm) and extracted for 1 hour at 60 ° C., 8% density and 2% NaOH per g substance

After washing the fabric again, the kappa number is determined. In parallel approaches, the kappa number is determined according to the Q level. The results are shown in Table 3.

Example 5 Example: Enzymatic bleach and sulfate pulp.

30 g dry cellulose (Softwood 1 / Softwood 2), consistency 30% (- 100 g moist) are added to the following solutions:
120 ml of tap water are mixed with 300 mg of hydroxybenztriazole (Softwood 1) and 150 or 300 mg of hydroxybenztriazole (Softwood 2) with stirring, the pH is adjusted with 0.5 m H2SO4 so that pH 4 after adding the pulp and the enzyme , 5 results. For this, 4,000 IU (1 IU = conversion of µM syringaldazine / min / ml enzyme) Laccase from Coriolus versicolor are added per g of substance. It is made up to 200 ml and the substance is added. It is for 2 min. mixed with a dough kneader.

At 15% consistency, 30 g dry = 100 g moist cellulose are added to 200 g total, i.e. 80 ml of tap water are specified and made up to 100 ml. Otherwise the procedure is as for 10% consistency.

The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar pressure for 1-4 hours.

The substance is then washed over a nylon sieve (30 μm) and extracted for 1 hour at 60 ° C., 8% density and 2% NaOH per g substance.

After washing the fabric again, the kappa number is determined.

The results are shown in Table 5.

Examples / tables: example 1 Enzymatic bleaching of sulfate pulp (Softwood) (O₂ delignified)

Table 1 system Kappa before extraction Kappa after extraction Lignin breakdown% 0 value 11 10th 9.1 L + 5 mg HBT / g 7.5 5.8 47.3 L + 5 mg HBT / g BT / B 6.9 4.9 54.5 L + 5 mg HBT / g 8.5 22.8 L + 5 mg HBT / g BT / B 6.1 44.6 2.) 3.) Under pressure 10 bar
4.) 5.) Air
B = benzophenone
L = laccase

Example 2 Enzymatic bleaching of sulfate pulp (Softwood) (0₂ delignified)

Table 2 system Kappa before extraction Kappa after extraction Lignin breakdown% 0 value 11 10th 9.1 L + 2.5 mg HBT / g 8.5 7.6 31 L + 2.5 mg HBT / g BT / VA 8.1 6.4 42 VA = veratryl alcohol
L = laccase

Example 3 Enzymatic bleaching of sulfate pulp (Softwood)

Table 3 system Kappa before extraction Kappa after extraction Lignin breakdown% 0 value 28.7 26.8 6.7 L + 10 mg HBT / g 21 17.8 38.2 L + 10 mg HBT / g + (A) 19.1 14.9 48.1 (A) = 2 mg / g substance DTPA
0.5 mg / g substance MgSO₄
L = laccase

Example 4

Table 4 system Kappa before Q Kappa after Q Kappa before extraction Kappa after extraction Kappa n. Q - E 0 value SW 1 28 23.5 28 24.4 22.4 L + 10 mg HBT / g (SW 1) 28 24.5 17.6 L + 10 mg HBT / g (SW 1) 28 23.5 18.6 14.8 0 value SW 2 22.7 21.6 22.7 21.5 21.6 L + 10 mg HBT / g (SW 2) 22.7 21.9 16.4 L + 10 mg HBT / g (SW 2) 22.7 21.6 16.1 14.4 L = laccase
kappa reduction:
SW1: 37.2% without Q and 47.2% with Q
SW2: 27.8% without Q and 36.6% with Q

Example 5:

Table 5 system Kappa before extraction Kappa after extraction Consistency Lignin removal% 0 value SW 1 28.7 26.8 6.6 10 mg HBT / g SW 1 21 17.8 10th 38 10 mg HBT / g SW 1 18.9 14.8 15 47.7 0 value SW 2 15 14.1 6 5 mg HBT / g SW 2 10.1 7.2 10th 52 5 mg HBT / g SW 2 7.8 5.4 15 64 10 mg HBT / g SW 2 7 5.1 10th 66

Example 7 Example: Enzymatic bleach and sulfate pulp.

• 1) 120 ml Leitungswasser werden mit 300 mg Hydroxybenzotriazol unter Rühren versetzt, der pH Wert mit 0,5 m H ₂ SO ₄ so eingestellt, daß nach Zugabe des Zellstoffes und des Enzyms pH 4,5 resultiert. Dazu werden 1000 bzw. 10.000 IU (IU=Umsatz von 1 µM Syringaldazin/min/ml Enzym Laccase von Coriolus versicolor pro g Stoff gegeben, 1000 IU Ligninperoxidase/g Stoff, 1000 IU Peroxidase (Meerrettich)/g Stoff, 1000 IU Tyrosinase/g Stoff jeweils in getrennten Ansätzen. Die Lösung wird auf 200 ml aufgefüllt und der Stoff zugegeben. Es wird für 2 min mit einem Teigkneter gemixt.

30 g dry cellulose (Softwood O₂ delignified), consistency 30% (-100 g moist) are added to the following solutions:

• 1) 120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole with stirring, the pH is adjusted with 0.5 m H ₂ SO ₄ so that pH 4.5 results after addition of the pulp and the enzyme. 1000 or 10,000 IU (IU = conversion of 1 µM syringaldazine / min / ml enzyme laccase from Coriolus versicolor per g substance, 1000 IU lignin peroxidase / g substance, 1000 IU peroxidase (horseradish) / g substance, 1000 IU tyrosinase / g of substance in separate batches, the solution is made up to 200 ml and the substance is added, and it is mixed with a dough kneader for 2 min.

The substance is then placed in a reaction bomb preheated to 45 ^° C. and incubated under 1-10 bar overpressure for 1-4 hours.

The pulp is then washed over a nylon screen (30 .mu.m) and 1- Std. Extracted per g of fabric at 60 ^° C, 8% consistency, and 2% NaOH.

After washing the fabric again, the kappa number is determined. (see table 7) Table 7 Enzymes Kappa (pulp) before treatment Kappa (pulp) after treatment Lignin peroxidase 15.2 11.3 Peroxidase (horseradish) 19036 Serva 15.2 11.75 Thyrosinase T-7755 Sigma 15.2 11.35 Laccase 10000 IU 15.2 5.5 Laccase 1000 IU 15.2 10.0

Example 8 Example: Enzymatic bleach and sulfate pulp.

• 1) 120 ml Leitungswasser werden mit 300 mg Hydroxybenzotriazol unter Rühren versetzt, der pH Wert mit 0.5 m H₂SO₄ so eingestellt, daß nach Zugabe des Zellstoffes und des Enzyms pH 4,5 resultiert. Dazu werden 20000 IU (IU=Umsatz von 1 m Syringaldazin/min/ml Enzym) Laccase von Coriolus versicolor pro g Stoff gegeben. Die Lösung wird auf 200 ml aufgefüllt und der Stoff zugegeben. Es wird für 2 min mit einem Teigkneter gemixt.

30 g dry cellulose (Softwood / Hardwood), consistency 30% (-100 g wet) are added to the following solutions:

• 1) 120 ml of tap water are mixed with stirring 300 mg of hydroxybenzotriazole, the pH is adjusted with 0.5 m H₂SO₄ so that pH 4.5 results after addition of the pulp and the enzyme. For this, 20,000 IU (IU = conversion of 1 m syringaldazine / min / ml enzyme) laccase from Coriolus versicolor are added per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ^° C. and incubated under 1-10 bar pressure for 1-4 hours.

The pulp is then washed over a nylon screen (30 .mu.m) and extracted per g of pulp 1 h. At 60 ^° C, 8% consistency, and 2% NaOH.

After washing the fabric again, the kappa number is determined.

A kappa reduction of 15 to 6 at Hardwood and from 30 to 15 at Softwood was achieved.

Example 9 Example: Enzymatic bleaching of straw pulp

• 1) 120 ml Leitungswasser werden mit 300 mg Hydroxybenzotriazol unter Rühren versetzt, der pH Wert mit 0,5 m H₂SO₄ so eingestellt, daß nach Zugabe des Zellstoffes und des Enzyms pH 4.5 resultiert. Dazu werden 20000 IU (IU=Umsatz von 1uM Syringaldazin/min/ml Enzym) Laccase von Coriolus versicolor pro g Stoff gegeben. Die Lösung wird auf 200 ml aufgefüllt und der Stoff zugegeben. Es wird für 2 min mit einem Teigkneter gemixt.

30 g dry straw pulp, consistency 30% (-100 g moist) are added to the following solutions:

• 1) 120 ml of tap water are mixed with stirring 300 mg of hydroxybenzotriazole, the pH is adjusted with 0.5 m H₂SO₄ so that pH 4.5 results after adding the pulp and the enzyme. For this, 20,000 IU (IU = conversion of 1uM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ^° C. and incubated under 1-10 bar overpressure for 1-4 hours.

The pulp is then washed over a nylon screen (30 .mu.m) and extracted per g of pulp 1 h. At 60 ^° C, 8% consistency, and 2% NaOH.

After washing the fabric again, the kappa number is determined.

A kappa number reduction from 65 to 14 was achieved.

Example 10 Example: Enzymatic bleach and sulfite pulp.

• 1) 120 ml Leitungswasser werden mit 300 mg Hydroxybenzotriazol unter Rühren versetzt, der pH Wert mit 0,5 m H₂ SO₄ so eingesellt, daß nach Zugabe des Zellstoffes und des Enzyms pH 4,5 resultiert. Dazu werden 20000 IU (IU=Umsatz von 1uM Syringaldazin/min/ml Enzym) Laccase von Coriolus versicolor pro g Stoff gegeben. Die Lösung wird auf 200 ml aufgefüllt und der Stoff zugegeben. Es wird für 2 min mit einem Teigkneter gemixt.

30 g dry cellulose (sulfite pulp), consistency 30% (-100 g moist) are added to the following solutions:

• 1) 120 ml of tap water are mixed with stirring 300 mg of hydroxybenzotriazole, the pH is adjusted with 0.5 m H₂ SO einges so that after adding the pulp and the enzyme pH 4.5 results. For this, 20,000 IU (IU = conversion of 1uM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ^° C. and our 1-10 bar overpressure is incubated for 1-4 hours.

The pulp is then washed over a nylon screen (30 .mu.m) and extracted per g of pulp 1 h. At 60 ^° C, 8% consistency, and 2% NaOH.

After washing the fabric again, the kappa number is determined.

A kappa number reduction from 15.5 to 5.2 was achieved.

Example 11 Enzymatic bleaching of sulfate pulp (Softwood / O₂ delignified / Hardwood (double treatment)

• 1) 120 ml Leitungswasser werden mit 300 mg Hydroxybenzotriazol unter Rühren versetzt, der pH Wert mit 0,5 m H₂SO₄ so eingestellt, daß nach Zugabe des Zellstoffes und des Enzyms pH 4,5 resultiert. Dazu werden 20000 IU (IU=Umsatz von 1uM Syringaldazin/min/ml Enzym) Laccase von Coriolus versicolor pro g Stoff gegeben. Die Lösung wird auf 200 ml aufgefüllt und der Stoff zugegeben. Es wird für 2 min mit einem Teigkneter gemixt.

30 g dry cellulose (Hardwood or Softwood), consistency 30% (-100 g wet) are added to the following solutions:

• 1) 120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole with stirring, the pH is adjusted with 0.5 m H₂SO₄ so that pH 4.5 results after addition of the pulp and the enzyme. For this, 20,000 IU (IU = conversion of 1uM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ^° C. and incubated under 1-10 bar overpressure for 1-4 hours.

• a) Direkt nach der Inkubation wird ohne Waschschritt Enzym + Mediator zugegeben, gemixt (2 min) und die Reaktion erneut durchgeführt (gleiche Zudosierung wie in der ersten Behandlung).
• b) Direkt nach der Inkubation wird nach dem Waschschritt und dem Auspressen des Stoffes auf 30% Stoffdichte die Reaktion durch Zuführen aller Komponenten nochmal durchgeführt.
• c) Nach erneuter Wäsche des Stoffes, nach Extraktion und Abpressen des Stoffes auf 30% Stoffdichte wird die Reaktion durch Zuführen aller Komponenten nochmals durchgeführt.

Hardwood: Kappazahlsenkung Softwood: Kappazahlsenkung a) 15 auf 5 a) 15,5 auf 4,2 b) 15 auf 3,5 b) 15,5 auf 3 c) 15 auf 2,5 c) 15,2 auf 2,2 The pulp is then washed over a nylon screen (30 .mu.m) and extracted per g of pulp 1 h. At 60 ^° C, 8% consistency, and 2% NaOH.

• a) Immediately after the incubation, enzyme + mediator is added without washing, mixed (2 min) and the reaction is carried out again (same metering as in the first treatment).
• b) Immediately after the incubation, after the washing step and the pressing of the substance to 30% density, the reaction is carried out again by adding all the components.
• c) After washing the fabric again, after extracting and pressing the fabric to 30% fabric density, the reaction is carried out again by adding all components.

Hardwood: Kappa number reduction Softwood: Kappa number reduction a) 15 on 5 a) 15.5 to 4.2 b) 15 to 3.5 b) 15.5 on 3 c) 15 to 2.5 c) 15.2 to 2.2

Example 12 Example: Enzymatic bleaching of wood pulp

• 1) 120 ml Leitungswasser werden mit 300 mg N-Hydroxyhexahydroacepin unter Rühren versetzt, der pH Wert mit 0.5 m H₂SO₄ so eingestellt, daß nach Zugabe des Zellstoffes und des Enzyms pH 4.5 resultiert. Dazu werden 1000 IU (IU=Umsatz von 1uM Syringaldazin/min/ml Enzym) Laccase von Coriolus versicolor pro g Stoff gegeben Die Lösung wird auf 200 ml aufgefüllt und der Stoff zugegeben Es wird für 2 min mit einem Teigkneter gemixt.

30 g dry wood pulp (spruce) 30% consistency (-100 g wet) are added to the following solutions:

• 1) 120 ml of tap water are mixed with stirring with 300 mg of N-hydroxyhexahydroacepine, the pH is adjusted with 0.5 m H₂SO₄ so that pH 4.5 results after addition of the pulp and the enzyme. For this, 1000 IU (IU = conversion of 1uM syringaldazine / min / ml enzyme) Laccase from Coriolus versicolor per g of substance are added. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ^° C. and incubated under 1-10 bar overpressure for 1-4 hours.

The fabric is then washed over a nylon sieve (30 µm).

A whiteness increase of 7% ISO whiteness was achieved.

Claims (49)

System for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances, which is characterized in that it is a multi-component system, a. optionally at least one oxidation catalyst and b. at least one suitable oxidizing agent and c. at least one mediator selects from the group of hydroxylamines, hydroxylamine derivatives, hydroxamic acids, hydroxamic acid derivatives, aliphatic, cycloaliphatic, heterocyclic or aromatic compounds which contain at least one N-hydroxy, oxime, N-oxi, or N, N'-dioxi Function included, and d. optionally at least one comediator from the group of aryl-substituted alcohols, carbonyl compounds, aliphatic ethers, phenol ethers or olefins (alkenes) and e. a small amount of at least one free amine of each mediator used
includes. Multi-component system according to claim 1,
characterized in that it also comprises Mg ²⁺ ions in addition to the components a) to e) mentioned. Multi-component system according to claim 1 or 2,
characterized in that an oxidation catalyst is used, preferably oxidoreductases of classes 1.1.1 - 1.97. Multi-component system according to claim 3,
characterized in that oxidoreductases which use oxygen, peroxides or quinones as electron acceptors are used. Multi-component system according to claim 3,
characterized in that laccase (1.10.3.2.) is used as the oxidoreductase. Multi-component system according to claim 1 or 2,
characterized in that as NO-NOH- or H-NR-OH-containing aliphatic, cycloaliphatic, heterocyclic or aromatic compounds N-hydroxy, oxime, N-oxi and N, N'-dioxi compounds, hydroxamic acid derivatives in mono- or multi-component systems are used. Multi-component system according to claim 6,
characterized in that hydroxylamines of the general formula I are used as NO, NOH or H-NR-OH-containing compounds.

Wherein in the general formula I, the substituents R¹ and R², which may be the same or different, independently of one another represent one of the following groups: hydrogen C₁-C₁₂-alkyl, carbonyl-C₁-C₆-alkyl, phenyl, aryl, whose C₁-C₁₂-alkyl, carbonyl-C₁-C₆-alkyl, phenyl, aryl- unsubstituted or can be substituted one or more times with the radical R³ and the radical R³ can be one of the following groups: hydrogen, halogen , Hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, sulfono-, their esters and salts, sulfamoyl, carbamoyl, phospho-, phosphono-, phosphonooxy and their salts and esters wherein the amino, carbamoyl and sulfamoyl groups of the radical R³ continue to be unsubstituted or once or twice with hydroxy-, C₁-C₃- be alkyl, C₁-C₃ alkoxy substituted can and wherein the radicals R¹ and R² together can form a group -B- and -B- represents one of the following groups: (-CHR⁴-) _n , (-CR⁴ = CH-) _m and where R⁴ is a substituent such as R³ is defined and n represents an integer from 1 to 6 and m represents an integer from 1 to 3. Multi-component system according to claim 6,
characterized in that substances of the general formula II are used as NO-NOH- or H-NR-OH-containing compounds

Where X stands for one of the following groups: (-N = N-),
(-N = CR10-) p, (-CR10 = N-) p, (-CR11 = CR12-) p

and p is 1 or 2.
wherein the radicals R⁹ to R¹², R¹⁵ and R¹⁶ may be the same or different and may independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁ -C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and where the amino, carbamoyl and sufamoyl groups of the radicals R⁹ to R¹², R¹⁵ and R¹⁶ may furthermore be unsubstituted or mono- or disubstituted by hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy, and the radicals R¹⁵ and R¹⁶ can form a common group -G- and -G- represents one of the following groups: (-CR⁵ = CR⁶-CR⁷ = CR⁸-) or
(-CR⁸ = CR⁷-CR⁶ = CR⁵-.
The radicals R⁵ to R⁸ can be identical or different and independently of one another represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C1-C6-alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and wherein the amino, carbamoyl and sufamoyl groups of the radicals R⁵ to R⁸ continue to be unsubstituted or can be substituted once or twice with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy
and wherein the C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl groups of the radicals R⁵ to R⁸ are unsubstituted or can be substituted one or more times with the radical R¹⁸ and wherein the radical R¹⁸ can be one of the following groups: hydrogen, halogen, hydroxy, formyl carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, and their esters and salts
and wherein the carbamoyl, sulfamoyl, amino groups of the radical R¹⁸ are unsubstituted or can furthermore be mono- or disubstituted with the radical R¹⁹ and the radical R¹⁹ can be one of the following groups: hydrogen hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl. Multi-component system according to claim 6,
characterized in that compounds of the general formula III are used as NO, NOH or H-NR-OH-containing compounds.

Where X stands for one of the following groups: (-N = N-), (N = CR₁₀-) _p , (-CR₁₀ = N-) _p , (-CR₁₁ = CR₁₂-) _p

and p is 1 or 2.
The radicals R⁵ to R¹² can be the same or different and independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C1-C6-alkyl, phenyl, aryl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and their amino, carbamoyl and sulfamoyl groups continue to be unsubstituted or once or twice may be substituted with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy and wherein the C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, aryl -C₁-C₆-alkyl groups of the radicals R⁵ to R¹² are unsubstituted or can be substituted one or more times with the radical R¹³ and the radical R¹³ can be one of the following groups: hydrogen, halogen, hydroxyl, formyl, carboxy and salts thereof and esters, amino, nitro, C₁-C₁₂ alkyl , C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and esters and wherein the carbamoyl, sulfamoyl, amino groups of the radical R¹³ are unsubstituted or can be substituted once or twice with the radical R¹⁴ and the radical R¹⁴ can be one of the following groups: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆ -alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl. Multi-component system according to claim 6,
characterized in that compounds of the general formula IV are used as NO-, NOH- or H-NR-OH-containing compounds.

Where X stands for one of the following groups: (-N = N-), (-N = CR¹⁰-) _p , (-CR¹⁰ = N-) _p , (-CR¹¹ = CR¹²-) _p

and p is 1 or 2.
The above applies to the radicals R⁵ to R⁸ and R¹⁰ to R¹².
R¹⁷ can be: hydrogen, C₁-C₁₀-alkyl, C₁-C₁₀ carbonyl, whose C₁-C₁₀-alkyl and C₁-C₁₀-carbonyl may be unsubstituted or substituted one or more times with a radical R¹⁸ which is defined as R³. Multi-component system according to claim 6,
characterized in that 1-hydroxybenzotriazole and the tautomeric benzotriazole-1-oxide, and their esters and salts according to the following formula V are used as NO, NOH or H-NR-OH-containing compounds.

The radicals R⁵ to R⁸ can be identical or different and independently of one another represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C1-C6-alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and where the amino, carbamoyl and sulfamoyl groups of the radicals R⁵ to R⁸ continue to be unsubstituted or a - Or be substituted twice with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy and where the C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl -Groups of the radicals R⁵ to R⁸ can be unsubstituted or can be substituted one or more times with the radical R¹⁸ and the radical R¹⁸ can be one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino , nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and esters and where the carbamoyl, sulfamoyl, amino groups of the radical R¹⁸ can be unsubstituted or can be substituted once or twice with the radical R¹⁹ and the radical R¹⁹ can be one of the following groups : Hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl. Multi-component system according to claim 6,
characterized in that those containing azoles are used as NO, NOH or H-NR-OH-containing compounds. Multi-component system according to claim 6,
characterized in that as NO-, NOH- or H-NR-OH-containing compounds those of condensed heterocycles which contain a triazolo or tetrazolo unit, such as
[1,2,4] triazolo [4,3-a] pyridines
[1,2,4] triazolo [1,5-a] pyridines
[1,2,4] triazolo [4,3-a] quinolines
[1,2,4] triazolo [4,3-b] isoquinolines
[1,2,4] triazolo [3,4-a] isoquinolines
[1,2,4] triazolo [1,5-b] isoquinolines
[1,2,4] triazolo [5,1-a] isoquinolines
[1,2,3] triazolo [1,5-a] pyridines
[1,2,3] triazolo [4,5-b] pyridines
[1,2,3] triazolo [4,5-c] pyridines
[1,2,3] triazolo [1,5-a] quinolines
[1,2,3] triazolo [5,1-a] isoquinolines
[1,2,4] triazolo [4,3-b] pyridazines
[1,2,4] triazolo [1,5-b] pyridazines
[1,2,4] triazolo [4,5-d] pyridazines
[1,2,4] triazolo [4,3-b] cinnoline
[1,2,4] triazolo [3,4-a] phthalazines
[1,2,4] triazolo [4,3-a] pyrimidines
[1,2,4] triazolo [4,3-c] pyrimidines
[1,2,4] triazolo [1,5-a] pyrimidines
[1,2,4] triazolo [1,5-c] pyrimidines
[1,2,4] triazolo [4,3-c] quinazoline
[1,2,4] triazolo [1,5-a] quinazoline
[1,2,4] triazolo [1,5-c] quinazoline
[1,2,4] triazolo [5,1-b] quinazoline
[1,2,3] triazolo [1,5-a] pyrimidines
[1,2,3] triazolo [1,5-c] pyrimidines
[1,2,3] triazolo [4,5-d] pyrimidines
[1,2,3] triazolo [1,5-a] quinazoline
[1,2,3] triazolo [1,5-c] quinazoline
[1,2,4] triazolo [4,3-a] pyrazine
[1,2,4] triazolo [1,5-a] pyrazine
[1,2,4] triazolo [1,5-a] pyrazine
[1,2,3] triazolo [4,5-b] pyrazine
[1,2,4] triazolo [4,3-a] quinoxaline
[1,2,3] triazolo [1,5-a] quinoxaline
[1,2,4] triazolo [4,3-b] [1,2,4] triazine
[1,2,4] triazolo [3,4-c] [1,2,4] triazine
[1,2,4] triazolo [4,3-d] [1,2,4] triazine
[1,2,4] triazolo [3,4-f] [1,2,4] triazine
[1,2,4] triazolo [1,5-b] [1,2,4] triazine
[1,2,4] triazolo [5,1-c] [1,2,4] triazine
[1,2,4] triazolo [1,5-d] [1,2,4] triazine
[1,2,4] triazolo [4,3-a] [1,3,5] triazine
[1,2,4] triazolo [1,5-a] [1,3,5] triazine
Tetrazolo [1,5-a] pyridine
Tetrazolo [1,5-b] isoquinolines
Tetrazolo [1,5-a] quinoline
Tetrazolo [5,1-a] isoquinolines
Tetrazolo [1,5-b] pyridazines
Tetrazolo [1,5-b] cinnoline
Tetrazolo [5,1-a] phthalazines
Tetrazolo [1,5-a] pyrimidines
Tetrazolo [1,5-c] pyrimidines
Tetrazolo [1,5-a] quinazoline
Tetrazolo [1,5-c] quinazoline
Tetrazolo [1,5-a] pyrazine
Tetrazolo [1,5-a] quinoxaline
Tetrazolo [1,5-b] [1,2,4] triazines
Tetrazolo [5,1-c] 1,2,4] triazines
Tetrazolo [1,5-d] [1,2,4] triazines
Tetrazolo [5,1-f] [1,2,4] triazines Multi-component system according to claim 1 or 2,
characterized in that the oxidizing agents are, for example, air, oxygen, ozone, H₂O₂, organic peroxides, peracids such as peracetic acid, peramic acid, persulfuric acid, perspalic acid, metachloroperoxobenzoic acid, perchloric acid, perchlorates, peracetates, persulfates, peroxides, oxygen species and radicals such as OH, OOH singlet Ozone, superoxide (O₂⁻), ozonide, dioxygenyl cation (O₂⁺), dioxirane, dioxitane, Fremy radical can be used. Multi-component system according to claim 1 or 2,
characterized in that compounds of component d) are aliphatic ethers, aryl-substituted alcohols, for example
2,3-dimethoxybenzyl alcohol
3,4-dimethoxybenzyl alcohol
2,4-dimethoxybenzyl alcohol
2,6-dimethoxybenzyl alcohol
Homovanillyl alcohol
Ethylene glycol monophenyl ether
2-hydroxybenzyl alcohol
4-hydroxybenzyl alcohol
4-hydroxy-3-methoxybenzyl alcohol
2-methoxybenzyl alcohol
2,5-dimethoxybenzyl alcohol
3,4-dimethoxybenzylamine
2,4-dimethoxybenzylamine hydrochloride
Veratryl alcohol
Coniferyl alcohol
are. Multi-component system according to claim 1 or 2,
characterized in that compounds of component d) olifins (alkenes), for example
2-allylphenol
2-allyl-6-methylphenol
Allylbenzene
3,4-dimethoxypropenylbenzene
p-methoxystyrene
1-allylimidazole
1-vinylimidazole
Styrene
Stilbene
Allylphenyl ether
Benzyl cinnamate
Cinnamic acid methyl ester
2,4,6-triallyloxy-1,3,5-triazine
1,2,4-trivinylcyclohexane
4-allyl-1,2-dimethoxybenzene
4-tert-Butylbenzoic acid vinyl ester
Squalene
Benzoin allyl ether
Cyclohexene
Dihydropyran are N-benzylcinnamic acid anilide. Multi-component system according to claim 1 or 2,
characterized in that compounds of component d) phenol ethers, for example
..2,3-dimethoxybenzyl alcohol
3,4-dimethoxybenzyl alcohol
2,4-dimethoxybenzyl alcohol
2,6-dimethoxybenzyl alcohol
Homovanillyl alcohol
4-hydroxybenzyl alcohol
4-hydroxy-3-methoxybenzyl alcohol
2-methoxybenzyl alcohol
2,5-dimethoxybenzyl alcohol
3,4-dimethoxybenzylamine
2,4-dimethoxybenzylamine hydrochloride
Veratryl alcohol
Coniferyl alcohol
Veratrol
Anisole
are. Multi-component system according to claim 1 or 2,
characterized in that compounds of component d) carbonyl compounds, for example 4-aminobenzophenone
4-acetylbiphenyl
Benzophenone
Benzil
Benzophenone hydrazone
3,4-dimethoxybenzaldehyde
3,4-dimethoxybenzoic acid
3,4-dimethoxybenzophenone
4-dimethylaminobenzaldehyde
4-acetylbiphenylhydrazone
Benzophenone-4-carboxylic acid
Benzoylacetone
Bis (4,4'-dimethylamino) benzophenone
Benzoin
Benzoin oxime
N-benzoyl-N-phenyl-hydroxylamine
2-amino-5-chloro-benzophenone
3-hydroxy-4-methoxybenzaldehyde
4-methoxybenzaldehyde
Anthraquinone-2-sulfonic acid
4-methylaminobenzaldehyde
Benzaldehyde
Benzophenone-2-carboxylic acid
3,3'4,4'-benzophenonetetracarboxylic acid dianhydride
(S) - (-) - 2- (N-bezylpropyl) aminobenzophenone
Benzylphenylacetic anilide
N-benzylbenzanilide
4,4'-bis (dimethylamino) thiobenzophenone
4,4'-bis (diacetylamino) benzophenone
2-chlorobenzophenone
4,4'-dihydroxybenzophenone
2,4-dihydroxybenzophenone
3,5-dimethoxy-4-hydroxybenzaldehyde hydrazine
4-hydroxybenzophenone
2-hydroxy-4-methoxybenzophenone
4-methoxybenzophenone
3,4-dihydroxybenzophenone
p-anisic acid
p-anisaldehyde
3,4-dihydroxybenzaldehyde
3,4-dihydroxybenzoic acid
3,5-dimethoxy-4-hydroxybenzaldehyde
3,5-dimethoxy-4-hydroxybenoic acid
4-hydroxybenzaldehyde
Salicylaldehyde
Vanillin
Are vanillic acid. Multi-component system according to claim 1 or 2,
characterized in that component e) is used as the free amine in the case of in situ generation or reaction mediation in cascade form with hydroxybenztriazole, benzotriazole. Process for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances,
characterized in that the respectively selected components a) to e) according to claim 1 are mixed simultaneously or in any order with an aqueous suspension of the lignin-containing material. Method according to 20,
characterized in that the reaction in a pH range of 2 to 11, at a temperature of 20 to 95 ° C, preferably 40 to 95 ° C, and a consistency of 0.5 to 40% and under air or oxygen at normal Pressure or 1-10 bar is carried out. A method according to claims 20 and 21,
characterized in that the consistency is preferably 13-15%. A method according to claim 20 or 21,
characterized in that an acid wash or Q stage is used before the reaction. The method of claim 23
characterized in that the acidic washing is carried out at 60-100 ° C at pH 4-5.5 for 30-90 min and 4-20% consistency. The method of claim 23
characterized in that the Q stage (with 0.05-1.0%, preferably 0.2-0.5% chelating agent) at 60-100 ° C at pH 4-5.5 for 30-90 min and 4- 20% consistency is carried out. The method of claim 23
characterized in that 1 hour at 90 ° C, pH 4.5-5 and 10% consistency are maintained for the acid wash and the Q stage. Method according to claims 20 and 21,
characterized in that hemicellulases, cellulases, amylases, pectinases or lipases or a mixture consisting of two or more of these enzymes are added to the reaction solution. Method according to claims 20 and 21,
characterized in that modified enzymes, enzyme components, prosthetic groups or mimic substances such as heme groups and compounds containing heme groups are used. Method according to claims 20 and 21,
characterized in that, in addition to these substances, phenolic compounds and / or non-phenolic compounds with one or more benzene nuclei are used. Method according to claims 20 and 21,
characterized in that reducing agents are added to the reaction solution. A method according to claim 30,
characterized in that sodium bisulfite, sodium dithionite, ascorbic acid, thiol compounds, mercapto compounds or glutathione are used as reducing agents. Method according to claims 20 and 21,
characterized in that oxygen is generated in situ by H2O2 + catalase or H2O2 by GOD + glucose. Method according to claims 20 and 21,
characterized in that cation-forming metal salts are added to the reducing solution. A method according to claim 33,
characterized in that the cations used are Fe2 +, Fe3 +, Mn2 +, Mn3 +, Mn4 +, Ca2 +, Cu2 +, Ti3 +, Ce4 +, Al3 +. Method according to claims 20 and 21,
characterized in that complexing agents are additionally added to the reaction solution. A method according to claim 35,
characterized in that the complexing agent is ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentametylenephosphonic acid (DTMPA), nitrilotriacetic acid (NTA), polyphosphoric acid (PPA) or other iron-amine complex, for example copper-manganese or other copper-amine complex, for example copper-manganese or other copper-amine complex, for example copper-manganese or other copper-amine complex, for example copper-manganese or Hydroxylamine can be used. Method according to claims 20 and 21,
characterized in that NaOCl is used. Method according to claims 20 and 21,
characterized in that detergents are additionally used. A method according to claim 38,
characterized in that non-ionic, ionic, anionic, cationic and amphoteric surfactants are added as detergents. Method according to claims 20 and 21,
characterized in that polysaccharides and / or proteins are additionally added to the reaction solution. A method according to claim 40,
characterized in that the polysaccharides used are glucans, mannans, dextrans, levans, pectins, alginates or plant gums and / or polysaccharides produced by the fungi or produced in the mixed culture with yeasts. A method according to claim 40,
characterized in that gelatin and / or albumin are used as proteins. Method according to claims 20 and 21,
characterized in that simple sugar, oligomer sugar, amino acids, polyethylene glycols, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes are used as additives. Method according to claims 20 and 21,
characterized in that radical formers or radical scavengers are added to the system. Method claims 1 and 2 and 20 and 21,
characterized in that it is used for the delignification or bleaching of cellulose by all known cooking methods. A method according to claim 45,
characterized in that sulfate, sulfite, organosolv, ASAM, enabatch, etc. are carried out as the cooking method. A method according to claim 46,
characterized in that it ect after or before all the usual bleaching stages and other sequences such as Q stage, acid washing. is carried out. A method according to claims 45-47,
characterized in that the process is carried out in several stages, washing or washing and extraction with alkali or neither washing nor extraction taking place between each stage. Multi-component system according to claim 1,
for coal liquefaction.