Two-Stage Peroxide Bleaching of Eucalypt-SGW with Chromium Catalysts

The addition of chromium nitrate to a two-stage hydrogen peroxide bleach of Eucalypt SGW can enhance the brightness of the pulp. It is proposed that radicals produced in the catalytic decomposition of hydrogen peroxide by chromium under acidic conditions participate in reactions which render the chromophores more susceptible to bleaching in the alkaline stage. This two-stage process, under optimised conditions, consumes no more peroxide than a traditional single stage alkaline bleach and allows the pulp to be bleached to a given brightness in a shorter time. Enhanced bleaching response was also observed for a two-stage acid/alkali peroxide bleaching sequence without the addition of chromium, and we have attributed this effect to catalytic effects of transition metal ions which occur naturally in the pulp.     

Acid Hydrogen Peroxide Treatment of Norway Spruce TMP: The Effect of an Extended pH Range when Catalyzed by Free Ferrous and Free or EDG/EDTA-Chelated Ferric Ions

The influence of different types of iron salts (i.e., ferrous or ferric cations with sulphate, nitrate or chloride anions) on the reaction between coarse thermomechanical pulp and acid hydrogen peroxide (Fenton chemistry) was studied when the initial pH was 3.2 and 5.3. Also, ferric ions chelated with EDTA or EDG at different molar ratios were compared with ferrous sulphate when the initial pH was extended from about 3 to 8. Different anions of ferric ion salt gave a similar catalytic effect. At an initial pH of 7–8, the ferric-EDTA catalyzed reaction resulted in similar or higher hydrogen peroxide consumption and more detectable hydroxyl radicals than the ferrous sulphate catalyzed reaction, but less reaction with the pulp was indicated. Between pH 5–8, using Fe-EDG as a catalyst gave higher hydrogen peroxide consumption and more detectable hydroxyl radicals than if using ferrous sulphate; however, the measured effect on the pulp was similar or less.     

The final bleaching of eucalypt kraft pulps with hydrogen peroxide: relationship with industrial ECF bleaching history and cellulose degradation

BACKGROUND: The process of chemical pulp bleaching is based for the most part in chlorine dioxide within elemental chlorine free (ECF) technologies. The use of greener alternatives such as bleaching with hydrogen peroxide (P stage) is not widely used owing to selectivity concerns related to transition metal‐catalyzed decomposition reactions. Even at the final stage where peroxide is recognized to boost brightness and improve the brightness stability of the bleached pulp, cellulose degradation often overcomes these advantages. This paper presents the results of studies intended to optimize final peroxide bleaching performance considering two standard ECF industrial bleaching sequences: the conventional DED and the ECF‐light OQ(PO)D (stages name: D—chlorine dioxide; E—alkaline extraction; O—oxygen; Q—chelation, (PO)—hydrogen peroxide pressurized with oxygen). RESULTS: The addition of sodium diethylenetriaminepentaacetate (DTPA) was the most effective option in terms of DED pulp bleachability and selectivity with hydrogen peroxide, as well as in terms of brightness reversion. As regards the OQ(PO)D pulp, a blend of DTPA and magnesium was the most beneficial in those properties. CONCLUSIONS: The choice of the best hydrogen peroxide stabilizer, among the different tested combinations of magnesium and chelants (EDTA and DTPA) studied, in terms of pulp bleachability, bleaching selectivity and brightness reversion is dependent on the impact of the previous bleaching stages on metallic nature and content. The pulp Mg/(Fe + Cu) ratio was highlighted as a process parameter controlling cellulose degradation in peroxide bleaching. Copyright © 2010 Society of Chemical Industry     

The role of platinum as the high voltage electrode in the enhancement of Fenton''s reaction in liquid phase electrical discharge

Pulsed electrical discharges in water produce a variety of oxidative and reductive species including hydroxyl radicals, hydrogen peroxide, and hydrogen. The reaction of ferrous ions with hydrogen peroxide (Fenton's reaction) provides additional hydroxyl radicals. Previous experiments with pulsed electrical discharges in water have shown that when ferrous sulfate is used as an electrolyte with a platinum high voltage electrode significantly higher organic compound degradation can be obtained in comparison to the case with an electrode made of nickel-chromium. In the work presented here, it is shown that particles emitted into solution from the platinum high voltage electrode enhance the production of hydroxyl radicals by forming a catalytic cycle between ferric and ferrous ions. The ferrous ions are converted to ferric ions by the Fenton's reaction utilizing hydrogen peroxide from the electrical discharge and the ferric ions are in turn converted to ferrous ions by reactions on the platinum particles emitted into solution from the high voltage electrode with molecular hydrogen formed by the electrical discharge. Based upon experiments with various scavengers it is concluded that the catalytic effect of the platinum particles is due to the presence of adsorbed hydrogen, while in contrast the nickel-chromium, which does not adsorb hydrogen, high voltage electrode and particles emitted by this electrode have no effect on the ferric ion regeneration.     

Hydrogen peroxide promoted wet air oxidation of phenol: influence of operating conditions and homogeneous metal catalysts

The promoted wet air oxidation of phenol has been investigated through the addition of hydrogen peroxide as a source of free radicals. The reaction has been shown to proceed in two stages, an initial fast reaction associated with hydrogen peroxide consumption and a second slower step that occurs at a rate comparable with conventional wet air oxidation. An increase in temperature has a positive effect on both stages, while oxygen partial pressure only influences the second slower stage. The influence of pH on phenol oxidation is shown to be significant with the highest efficiency achieved at very alkaline conditions when phenol is completely dissociated. The catalytic activity of homogeneous metal salts was investigated in both the presence and absence of hydrogen peroxide. The combined addition of hydrogen peroxide and a bivalent metal (ie copper, cobalt or manganese) is shown to enhance the rate of phenol removal. However, in the absence of hydrogen peroxide only copper exhibited catalytic activity. Finally, a reaction mechanism involving different radical species has been proposed. From the experimental results the apparent activation energy (96.9 ± 3.5 kJ mol⁻¹) and pre‐exponential factor (1.6 ± 0.2 10¹⁰ s⁻¹) were calculated for hydrogen peroxide decomposition into hydroxyl radicals. © 1999 Society of Chemical Industry     

Peroxide Bleaching Reactions Under Alkaline and Acidic Conditions

An examination of previously reported kinetic expressions describing peroxide bleaching of wood pulp under alkaline conditions reveals that the overall process can be considered as a combination of two parallel reaction routes. The first route corresponds to a reaction involving direct participation of the perhydroxyl anion in chromophore elimination. This mechanism can be identified with the classical explanation for peroxide bleaching. The second route can be associated with reactions in which chromophores are eliminated through the action of free radical intermediate species. New experimental evidence is presented to show that processes catalysed by transition metal ions can lead to enhancement of bleaching. A two stage peroxide bleaching sequence, initially under acidic conditions in the presence of chromium, followed by alkaline conditions produces an acceleration in bleaching rate, without significant additional consumption of peroxide.     

Use of zeolites in stabilising alkaline peroxide solutions and their application in the bleaching of a TMP pulp

Silicate‐based chemistry is a common industrial practice to improve peroxide bleaching, however, the transition metal ion‐induced peroxide decomposition is still inevitable. In this study, we investigated the potential to further decrease the peroxide decomposition by adding zeolites to the silicate‐based peroxide system. The peroxide decomposition results showed that the combined effect of zeolites and sodium silicate is more effective than sodium silicate alone in decreasing the manganese‐induced peroxide decomposition. Two types of zeolites, X and Y, were studied. The bleaching experiments showed that an improved peroxide bleaching performance was obtained by adding Y‐zeolites to the conventional peroxide process.     

Kinetics and mechanism of the reaction between ozone and hydrogen peroxide in aqueous solutions

A kinetic model has been developed, taking into account both decomposition of ozone molecules and interactions between ozone and hydrogen peroxide for formation of hydroxyl radical and subsequent reactions. Experiments were carried out at 25°C in the pH range of 3 to 13, indicating that the depletion rate of ozone increases with the concentrations of ozone, hydrogen peroxide and hydroxyl ion, as predicted by the kinetic model. Adverse scavenging reactions, however, also play significant roles at sufficient concentration ratios of hydrogen peroxide to ozone and high concentrations of hydroxyl ion in reducing the depletion rate. Results of this research suggest, that it is most desirable to conduct the peroxone oxidation for pollutant destruction by the hydroxyl radical reaction in alkaline solutions of pH below 11, while maintaining about the same concentration of ozone and hydrogen peroxide.     

2，4-二氯苯氧乙酸臭氧化过程中过氧化氢的生成

引言2,4-二氯苯氧乙酸(2,4-D,又名2,4-滴)是一种广泛使用的除草剂[1],应用历史较长,是我国主要的除草剂品种之一,用量也比较大。2,4-D属于苯氧羧酸类除草剂的一种,可有效去除阔叶杂草,目前仍广泛用于农作物除草和草坪养护[2]。2,4-D的水溶性较高,挥发性较低,在自然界中难以生物     

QUANTITATION OF PROTEIN DAMAGE IN METAL ION-CATALYZED OXIDATION SYSTEMS

The loss of enzymatic activity of lactate dehydrogenase was studied in several ascorbate, iron and hydrogen peroxide metal catalyzed oxidation solutions in which the initial concentration of each reactant was varied independently. Nonmonotonic concentration dependencies of enzymatic inactivation were observed for all three reactants. with minimum activity levels occurring in the 0·1 to 8 mM range. A first effort has been made to predict these concentration dependencies with a mathematical simulation model. The model consisted of the most commonly reported reactions and assumed that protein damage occurred through reaction with the hydroxyl radical. The simulation predicted nonmonotonic concentration dependencies of enzyme inactivation on each of the reactants. The predicted concentrations of the minima differed from the experimentally observed points by a factor of 2 to 4. Mathematically the minima occurred because each reactant was reported to react with hydroxyl radicals and form less reactive compounds. The plausibility that competition caused or contributed to the extrema was further explored with experimental competition studies between peroxide and the radical scavenger dimethylsulfoxide. A point of maximum hydroxyl radical formation was observed with increasing peroxide concentration. This maxima corresponded to the point of maximum lactate dehydrogenase damage observed with increasing peroxide concentration.     

Copper‐Catalyzed Peroxide Oxidation Testing for Tetraphenylborate Decomposition

Abstract

A new processing option, copper‐catalyzed hydrogen peroxide oxidation of tetraphenylborate under alkaline conditions, was demonstrated in laboratory testing. Laboratory‐scale tests were conducted to evaluate the use of copper‐catalyzed hydrogen peroxide oxidation to treat simulants of the Savannah River Site tank waste. The oxidation process involves the reaction of hydrogen peroxide with a copper catalyst to form hydroxyl free radicals. With an oxidation potential of 2.8 volts, the hydroxyl free radical is a very powerful oxidant, second only to fluorine, and will react with a wide range of organic molecules. The goal is to oxidize the tetraphenylborate completely to carbon dioxide, with minimal benzene generation. Testing was completed in a lab‐scale demonstration apparatus at the Savannah River National Laboratory. Greater than 99.8% tetraphenylborate destruction was achieved in less than three weeks. Offgas benzene analysis by a gas chromatograph demonstrated low benzene generation. Analysis of the resulting slurry demonstrated >82.3% organic carbon destruction. The only carbon compounds detected were formate, oxalate, benzene (vapor), carbonate, p‐terphenyl, quaterphenyl, phenol, and phenol 3‐dimethylamino.     

Mechanism and kinetics of chlorine dioxide reaction with hydrogen peroxide under acidic conditions

The reaction of chlorine dioxide with hydrogen peroxide was studied in a well stirred batch reactor in a pH range of 3.60 to 5.07, which is of interest for commercial chlorine dioxide bleaching of chemical pulp. The reaction rate was determined by following the consumption of chlorine dioxide and hydrogen peroxide and the formation of chlorite. The rate equation was established. It was found that the concentration dependencies of chlorine dioxide, hydrogen peroxide and hydroxide ion were all first-order. A reaction mechanism compatible with the rate equation was proposed. Since it was found in previous work that chlorite in chlorine dioxide solution by the addition of small amount of hydrogen peroxide potentially led to a decrease in the formation of organically bound chlorine during chlorine dioxide bleaching, two methods were suggested to implement this technique in a bleach plant.     

Zur Problematik des Blondierens menschlicher Haare

Problems Concerning Bleaching of Human Hair The bleaching of human hair using alkaline hydrogen peroxide involves a chemical change of the coloring pigments eumelanin and pheomelanin – the bleaching proper – as well as a chemical effect on the keratinous material – i. e. hair damage. The oxidation by alkaline hydrogen peroxide may proceed by different mechanisms and via different intermediates. It is discussed whether the reactions leading to bleaching or hair damage, respectively, show preferences for particular mechanisms of hydrogen peroxide decomposition.     

Greener method for high-quality polypyrrole

Conducting polypyrrole has been synthesized via a simple metal catalyzed process. The oxidative polymerization of pyrrole using hydrogen peroxide and a catalytic amount of iron(III) in an acidified aqueous medium afforded conducting polypyrrole in very good yield. The copper(II) or cerium(IV) catalyzed reactions under similar conditions gave poor yields. The iron(III) catalyzed reaction carried out in the absence of the acid produced low-quality polypyrrole that contain hydroxyl and carbonyl groups resulting from the nucleophilic attack of water or hydroxyl radicals.     

Graft copolymerization to cellulose in the presence of hydrogen peroxide with ultraviolet irradiation

The decomposition of hydrogen peroxide in the presence of cellulose with ultraviolet irradiation and graft copolymerization occurring upon addition of methyl methacrylate to this system was investigated. Graft copolymerization barely began in the hydrogen peroxide system without ultraviolet irradiation, but was markedly accelerated by ultraviolet irradiation. Ultraviolet light is capable of initiating the graft copolymerization even without addition of hydrogen peroxide, and this capability is enhanced further with the use of hydrogen peroxide. However, an increase in the hydrogen peroxide concentration was observed to exercise a zero or negative effect on the number of grafts. Such a phenomenon is absent in the ceric ion initiator system and, in the present study, is believed to be brought about by a characteristic enhancement of the stabilization of grafting sites effected by hydroxyl radicals. The number of grafts of copolymers obtained in the present initiator system is only approximately 0.085 mmole/100 g of cellulose at its maximum and is within the range of results obtained for the hydrogen peroxide initiator system in general.     

Low‐temperature bleaching of cotton fabric with a binuclear manganese complex of 1,4,7‐trimethyl‐1,4,7‐triazacyclononane as catalyst for hydrogen peroxide

Bleaching of cellulose fabric with hydrogen peroxide is traditionally conducted under alkaline conditions at high temperature, which leads to greater energy consumption and fibre damage. In this study, a binuclear manganese complex of the ligand 1,4,7‐trimethyl‐1,4,7‐triazacyclononane as the catalyst for hydrogen peroxide bleaching was synthesised via a simplified method. Low‐temperature bleaching of cotton fabric with the manganese complex and the effect of key bleaching variables on the bleaching performance were investigated. Hydrogen peroxide could be catalysed to bleach cotton knitted fabric at a temperature as low as 60 °C by incorporating the complex in the bleaching solution. The whiteness index of the fabric bleached at low temperature was lower than that of fabric bleached at high temperature, but the bursting strength retention is much better for the fabric bleached at low temperature. The low temperature is energy‐saving and has environment‐friendly advantages over the traditional high‐temperature method.     

Low‐temperature bleaching of cotton fabric using a copper‐based catalyst for hydrogen peroxide

Hydrogen peroxide can be catalysed to bleach cotton fibres at a temperature of 70 °C by incorporating the copper‐based catalyst [Cu(TPMA)Cl]ClO₄·1/2H₂O in the bleaching solution. The effects of pH, temperature, and concentration of catalyst and hydrogen peroxide on bleaching effectiveness were evaluated. The effects of other transition metal complexes of tris(2‐pyridylmethyl)amine were also examined. The bleaching mechanism was investigated by studying the active species. The results showed that a satisfactory whiteness index could be obtained at low temperature with the copper‐based catalyst, and it also had a competitive advantage in protecting cellulose from severe chemical damage. Cu(i )TPMA(OOH)^? was the active species in bleaching.     

Bleaching of Wool with Hydrogen Peroxide by Steaming in an Acidic Medium

The bleaching of wool by padding with hydrogen peroxide in an acidic medium and then steaming has been studied. Two different methods were used, depending on the stabiliser employed; the effects of the concentrations of hydrogen peroxide and stabiliser, the steaming time and the pH were examined in each case. The optimum conditions were compared withthose used in the method in which the bleaching solution is alkaline. A better and more permanent white is obtained if the bleaching solution is alkaline, although the degradation of the fibre is slightly higher.     

Comparison of wool bleaching with hydrogen peroxide in alkaline and acidic media

A merino wool top was bleached in both alkaline and acidic media, varying the hydrogen peroxide concentration in the bleaching bath. For the same peroxide concentration, bleaching in an alkaline medium leads to a whiter and more chemically attacked wool than bleaching in an acidic medium. For the same chemical attack, wool bleached in an alkaline medium is whiter than for bleaching in an acidic medium.     

Catalase and superoxide dismutase mimics for the treatment of inflammatory diseases

Conjugation of a metal ion chelator to aromatic amino acids generates a series of novel metal-binding anti-oxidant enzyme mimics. Our catalytic peptoids are designed to suppress oxidative damage via a number of routes. These include: (i) binding redox-active metal ions that further generate/activate RONS, (ii) removal of hydrogen peroxide by catalase activity, (iii) removal of superoxide by superoxide dismutase activity, and (iv) preventing the formation of hydroxyl radicals and peroxynitrite by removal of their precursors [as in (ii) and (iii)]. Thus, the redox-active metal ions are changed from detrimental RONS producers to beneficial RONS scavengers. In conclusion, we present a series of biomimetic peptoids that (i) bind redox-active metal ions, (ii) detoxify RONS and (iii) have potential therapeutic applications in inflammatory diseases.