Effects of inorganic salts on the degradation of 2,5-dihydroxy-[1,4]-benzoquinone as a key chromophore in pulps by hydrogen peroxide under basic conditions
Abstract
2,5-Dihydroxy-[1,4]-benzoquinone (DHBQ) is one of the key chromophores in cellulosics. Due to its special resonance stabilization, it is a prime survivor of bleaching treatments and its degradation is essential in pulp bleaching. The clarification of the degradation mechanism of this compound is indispensable for targeting improvements of pulp bleaching processes. Previous studies revealed that DHBQ degradation by hydrogen peroxide (H2O2) is influenced by salts. This study addresses the effects of alkaline metal salts, alkaline earth metal salts, and Al2(SO4)3 on the degradation of DHBQ under simulated conditions of pulp bleaching in a peroxide stage. The degradation by excess H2O2 followed first-order kinetics in the presence of alkaline metal salts and alkaline earth metal salts, which enhanced and retarded the reaction, respectively. Kinetic studies and theoretical computations provided detailed mechanistic insights: Li+, Na+, and K+ stabilize several reaction intermediates by complex formation, causing the enhancement of the degradation, whereas Mg2+ and Ca2+ coordinate and stabilize the reactant, resulting in the observed retardation. Al2(SO4)3 exhibited a strong enhancing effect, but the degradation followed second-order kinetics with regard to DHBQ, suggesting a fundamentally different degradation mechanism.
Acknowledgments
We performed quantum chemical calculations with the workstation in the Sakaki Group, Fukui Institute for Fundamental Chemistry at Kyoto University, Japan, and we thank them for the access. The financial support from the Austrian Christian Doppler Research Society (CDG) through the CD-lab “Advanced Cellulose Chemistry and Analytics” and from the Austrian Research Promotion Agency (FFG; project 829443) is gratefully acknowledged.
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Articles in the same Issue
- Frontmatter
- Effect of hydroxide and sulfite ion concentration in alkaline sulfite anthraquinone (ASA) pulping – a comparative study
- Novel insight in carbohydrate degradation during alkaline treatment
- Activated hydrogen peroxide decolorization of a model azo dye-colored pulp
- Effects of inorganic salts on the degradation of 2,5-dihydroxy-[1,4]-benzoquinone as a key chromophore in pulps by hydrogen peroxide under basic conditions
- Analysis of degradation products in rayon spinning baths
- Effect of cellulase-assisted refining on the thermal degradation of bleached high-density paper
- Synthesis and characterization of functionalized 4-O-methylglucuronoxylan derivatives
- Hydrophobic materials based on cotton linter cellulose and an epoxy-activated polyester derived from a suberin monomer
- Depolymerization of cellulose during cold acidic chlorite treatment
- Enhanced stability of PVA electrospun fibers in water by adding cellulose nanocrystals
- Micro-nanoparticle gels obtained from bark for their use alone and with chitosan and Na-CMC in paper coatings
- Conversion of sulfur-free black liquor into fuel gas by supercritical water gasification
- Modification of acid hydrolysis lignin for value-added applications by micronization followed by hydrothermal alkaline treatment
- Preparation of lignin-containing porous microspheres through the copolymerization of lignin acrylate derivatives with styrene and divinylbenzene
- Wood-based activated carbons for supercapacitors with organic electrolyte
- Functionality and physico-chemical characteristics of wheat straw lignin, Biolignin™, derivatives formed in the oxypropylation process
- Antioxidant activity of various lignins and lignin-related phenylpropanoid units with high and low molecular weight
- Characterization of technical lignins by NMR spectroscopy: optimization of functional group analysis by 31P NMR spectroscopy
- Chemical composition of volatiles extracted from indigenous tree species of Uganda: composition of bark extracts from Psorospermum febrifugum and Milicia excelsa
Articles in the same Issue
- Frontmatter
- Effect of hydroxide and sulfite ion concentration in alkaline sulfite anthraquinone (ASA) pulping – a comparative study
- Novel insight in carbohydrate degradation during alkaline treatment
- Activated hydrogen peroxide decolorization of a model azo dye-colored pulp
- Effects of inorganic salts on the degradation of 2,5-dihydroxy-[1,4]-benzoquinone as a key chromophore in pulps by hydrogen peroxide under basic conditions
- Analysis of degradation products in rayon spinning baths
- Effect of cellulase-assisted refining on the thermal degradation of bleached high-density paper
- Synthesis and characterization of functionalized 4-O-methylglucuronoxylan derivatives
- Hydrophobic materials based on cotton linter cellulose and an epoxy-activated polyester derived from a suberin monomer
- Depolymerization of cellulose during cold acidic chlorite treatment
- Enhanced stability of PVA electrospun fibers in water by adding cellulose nanocrystals
- Micro-nanoparticle gels obtained from bark for their use alone and with chitosan and Na-CMC in paper coatings
- Conversion of sulfur-free black liquor into fuel gas by supercritical water gasification
- Modification of acid hydrolysis lignin for value-added applications by micronization followed by hydrothermal alkaline treatment
- Preparation of lignin-containing porous microspheres through the copolymerization of lignin acrylate derivatives with styrene and divinylbenzene
- Wood-based activated carbons for supercapacitors with organic electrolyte
- Functionality and physico-chemical characteristics of wheat straw lignin, Biolignin™, derivatives formed in the oxypropylation process
- Antioxidant activity of various lignins and lignin-related phenylpropanoid units with high and low molecular weight
- Characterization of technical lignins by NMR spectroscopy: optimization of functional group analysis by 31P NMR spectroscopy
- Chemical composition of volatiles extracted from indigenous tree species of Uganda: composition of bark extracts from Psorospermum febrifugum and Milicia excelsa