Novel catalytic activities of oxidoreductases for oxidation and or bleaching

Abstract

A new enzyme-based process for oxidation and/or bleaching is described, comprising of oxidoreductases such as laccases and/or peroxidases—seperately or in combination—in the presence of their respective co-substrates like O 2 , air, H 2 O 2 , organic peroxides, peracids etc. and comprising of enhancer compounds from the class of oxocarbons, from the class of urazoles and hydrazides, from the class of hydantoins and the class of nitril (Cyan)-compounds, and comprising additionally of carbonyl compounds such as ketones, aldehyds, whereby the combination of enzyme, co-substrate, enhancer compound and carbonyl compound generate active oxygen species like dioxiranes, dioxetanes, peroxy-compounds etc. or form other reactive compounds or transition states like radicals (kation radicals, anion radicals) or reactive (red/ox-active) neutral compounds as oxidizing and/or bleaching agents.

1 ) New enzyme-based process for oxidation and/or bleaching comprising of 
 oxidoreductases such as laccases and/or peroxidases—seperately or in combination—in the presence of their respective co-substrates like O 2,  air, H 2 O 2 , organic peroxides, peracids etc. and comprising of    enhancer compounds from the class of oxocarbons, from the class of urazoles and hydrazides, from the class of hydantoins and the class of nitril (Cyan)-compounds, and comprising additionally of    carbonyl compounds such as ketones, aldehyds,    whereby the combination of enzyme, co-substrate, enhancer compound and carbonyl compound generate active oxygen species like dioxiranes, dioxetanes, peroxy-compounds etc. or form other reactive compounds or transition states like radicals (kation radicals, anion radicals) or reactive (red/ox-active) neutral compounds as oxidizing and/or bleaching agents.    
   
   
       2 ) New enzyme-based process for oxidation and/or bleaching according to  claim 1  comprising that the enhancer compounds belong to the group of oxocarbons like α-hydroxy-carbonyl compounds, α-dicarbonyl compounds, β-hydroxycarbonyl compounds and β-dicarbonyl compounds, linear compounds with double bonds (enols) and compounds from the group of cyclic oxocarbons like deltic acid, squaric acid, crocoic acid, rhodizonic acid, tetrahydroxy-p-hydroquinone and their salts and derivatives.  
   
   
       3 ) New enzyme-based process for oxidation and/or bleaching according to  claim 1  comprising that that the enhancer compounds belong to the group of amides such as hydrazides, cyclic hydrazides, urazoles and phthalhydrazides.  
   
   
       4 ) New enzyme-based process for oxidation and/or bleaching according to  claim 1  comprising that that the enhancer compounds belong to the group of imides like hydantoins, cyclic imides and hydantoin derivatives.  
   
   
       5 ) New enzyme-based process for oxidation and/or bleaching according to  claim 1   
   
   
       5 ) New enzyme-based process for oxidation and/or bleaching according to  claim 1  comprising that that the enhancer compounds belong to the group of nitril-(Cyan) compounds such as cyanamide or dicyandiamide.  
   
   
       6 ) New enzyme-based process for oxidation and/or bleaching according to  claim 1  comprising that additionally carbonyl compounds—mainly non-cyclic substances—are added.  
   
   
       7 ) New enzyme-based process for oxidation and/or bleaching according to  claim 1  comprising that as enzymes oxidoreductases of the classes 1.1.1. bis 1.97 are used.  
   
   
       8 ) New enzyme-based process for oxidation and/or bleaching according to  claim 1  comprising that as oxidoreductases laccases and peroxidases are used.  
   
   
       9 ) New enzyme-based process for oxidation and/or bleaching according to  claim 1  comprising that as additional enzyme-based systems HOS (hydrolase mediated oxidation system), peroxynitreous acid generating system, ferrocene/peroxide system, organosulfonic acid/peroxide/ketone system, activated sulfite/superoxide/ketone system and other state-of-the-art oxidoreductase mediator systems are added either simultaneously or successively in any order are added.  
   
   
       10 ) New enzyme-based process for oxidation and/or bleaching according to  claim 1  comprising that as co-substrates preferrably air, oxygen, ozone, peroxides, such as H 2 O 2 , organic peroxides, peracids such as peracetic, performic, persulfuric, pernitric, metachloroperoxybenzoic and perchloric acid, per compounds such as perborates, percarbonates or persulfates, or oxygen species and the radicals thereof such as the OH, OOH −  and OH +  radical, superoxide (O 2 —), dioxygenyl cation (O 2   + ), singlet oxygen are used.  
   
   
       11 ) Use of the enzymatic oxidation and/or bleaching system according to  claim 1  to  10  in a process for the delignification and/or modificaton and/or bleaching of pulps from wood and annual plants and high yield pulps and deinked pulps, whereby the reactions of the oxidation and/or bleaching systems are performed in a pH-range of pH 3 to 11, preferably pH 3 to 9, at a temperature of 20 to 95° C., preferably of 40 to 95° C., at a consistency of 0.5 to 40%, preferably of 4 to 15%, in the presence of oxygen or air at atmospheric pressure to a slight overpressure (up to 2 bar). The laccase concentrations or peroxidase concentrations lay in the range of 2-500 g pure enzyme per ton pulp, the concentrations of the enhancer compounds lay in the range of 1-15 kg per ton pulp, the H 2 O 2  concentrations in the range of 0.2 to 15 kg per ton pulp and the concentrations of carbonyl compounds in the range of 0.2 to 5 kg per ton pulp.  
   
   
       12 ) Use of the enzymatic oxidation and/or bleaching system according to  claim 1  to  11  in a process for the delignification and /or modificaton and/or bleaching of pulps from wood and annual plants and high yield pulps and deinked pulps whereby an acid wash or a Q-step is used before and/or after the reaction of the enzyme component system and the acid wash is carried out at 60-120° C., at pH 2 to 5.5, for 30-90 min and at 4-20% pulp consistency, and the Q-step is carried out with 0.05-1%, preferably with 0.2 to 0.5% of chelator at 60-100° C., at pH 2 to 5.5 for 30-90 min and a consistency of 4-20%.  
   
   
       13 ) Use of the enzymatic oxidation and/or bleaching system according to  claim 1  to  12  in a process for the delignification and /or modificaton and/or bleaching of pulps from wood and annual plants and high yield pulps and deinked pulps, whereby the acid wash and the Q-step are carried out for 1 hour at 60-90° C., at pH 2 to 5 and at 10% pulp consistency.  
   
   
       14  Use of the enzymatic oxidation and/or bleaching system according to  claim 1  to  13  in a process for the delignification and/or modificaton and/or bleaching of pulps from wood and annual plants and high yield pulps and recycling pulps whereby it can be applied once or several times, either before and/or after the washing and extraction of the treated material with NaOH etc., or without these intermediate steps, but also before and/or after pretreatment or post-treatment steps, such as acid washing, Q-steps, alkaline leaching or bleaching steps such as peroxide bleaching, O 2 -enhanced peroxide steps, pressurized peroxide steps, O 2 -delignification, Cl 2 -bleaching, CIO 2 -bleaching, Cl 2 /CIO 2 -bleaching, peracid bleaching, peracid-enhanced O 2 /peroxide bleaching, ozone bleaching, dioxirane bleaching, reductive bleaching steps, other treatments such as swelling steps, sulfonations, NO/NO 2  treatments, nitrosylsulfuric acid treatment, enzyme treatments, for example treatments with hydrolases, such as cellulases and/or hemicellulases (for example, xylanase, mannase etc) and/or amylases and/or pectinases and/or proteinases and/or lipases and/or amidases and/or oxidoreductases such as, for example, laccases and/or peroxidases etc., or several combined treatments.  
   
   
       15 ) Use of the enzymatic oxidation and/or bleaching system according to  claim 1  to  14  in a process for the delignification and /or modificaton and/or bleaching of pulps from wood and annual plants and high yield pulps and deinked pulps, said process being carried out in several steps and whereby between each step is applied a washing or washing and extraction step with alkaline hydroxide solution, or neither washing nor extraction takes place.  
   
   
       16 ) Use of the enzymatic oxidation and/or bleaching system according to  claim 1  bis  15  in the bleaching of cellulose/wood pulp, in the treatment of different wastewaters, in the preparation of lignin solutions or gels of the corresponding binders/adhesives and of wood-based composites, as enzymatic deinking system, as oxidation systems in organic synthesis, as bleaching agent in detergents, as bleaching and/or oxidation systems in textile industry, in coal liquefaction.