The Kinetics of Lignin Reactions During Oxygen Bleaching. IV. The Reactivities of Different Lignin Model Compounds and the Influence of Metal Ions on the Rate of Degradation

1994 ◽  
Vol 14 (4) ◽  
pp. 507-525 ◽  
Author(s):  
Eva Johansson ◽  
Sten Ljunggren
Holzforschung ◽  
1999 ◽  
Vol 53 (3) ◽  
pp. 292-298 ◽  
Author(s):  
M. Ragnar ◽  
T. Eriksson ◽  
T. Reitberger

Summary Using different independent methods, the kinetics of ozone consumption and the initial radical yield in reactions of ozone with lignin and carbohydrate model compounds were investigated. It was demonstrated that ozone reacts with phenolates several orders of magnitude more rapidly than with corresponding undissociated phenols. The pH dependence of the radical yield does not completely follow the pK a-value of the phenols. In fact, the radical yield starts to increase at pH 3 for all the phenolic model compounds investigated. Several indications suggest that superoxide rather than the hydroxyl radical is initially formed when ozone reacts with lignin model compounds. In contrast to lignin model compounds no radicals were detected in ozone reactions with carbohydrate model compounds or olefins. On the basis of this study, it may be concluded that ozone bleaching should preferably be performed at pH 3 and at a higher consistency. No significant effect of metal ions was observed.


Holzforschung ◽  
2008 ◽  
Vol 62 (2) ◽  
pp. 169-175 ◽  
Author(s):  
Krishna K. Pandey ◽  
Tapani Vuorinen

Abstract The etherification of phenolic groups has been found to inhibit photodegradation in wood and lignin rich pulps. The precise understanding of kinetics of chemical reaction between lignins or their model compounds and the etherifying agent is the first step for developing a viable modification procedure. In this study, we have investigated the reaction of lignin model compounds (namely, phenol and guaiacol) with propylene oxide in aqueous media. The kinetics of etherification reaction was studied under varying pH conditions in the temperature range 30–60°C. The etherified reaction products were characterized by gas chromatogram-mass spectrum (GC-MS). The extent of etherification of phenols and the rate of chemical reaction was followed by UV-Visible absorption spectroscopy. The reaction between lignin model compounds and propylene oxide was indicated by a rapid reduction in the absorbance accompanied by the development of a new band corresponding to etherified products. The reaction kinetics was investigated at pH ∼12 under the condition of excess concentration of propylene oxide. The reaction followed first order kinetics and rate constants increased linearly with an increase in the temperature and concentration of propylene oxide. The MS fragment data of reaction product support the proposed reaction scheme. The activation energy of the reaction of propylene oxide with phenol and guaiacol, calculated with the Arrhenius equation, was 56.2 kJ mol-1 and 45.4 kJ mol-1, respectively.


1972 ◽  
Vol 2 (3) ◽  
pp. 271-275 ◽  
Author(s):  
G. E. Troughton ◽  
J. F. Manville

Rates of formation were measured for the base-catalyzed condensation reactions occurring between 4-alkylguaiacol compounds and their 6-methylol derivatives over the temperature range 85.5–100 °C. It was found that both the intercondensation reaction between the 4-alkylguaiacol compound and its 6-methylol derivative and the self-condensation reaction of the latter compound occurred at significant rates. In the 4-propylguaiacol – 4-methyl-6-methylolguaiacol system, the above two condensation reactions occurring in this system had the same activation energies, 35 kcal/mol. Similarly, in the 4-methylguaiacol – 4-propyl-6-methylolguaiacol system these two condensation reactions had equivalent activation energies, but slightly lower than in the former system, 32 kcal/mol. The kinetic results found for the model guaiacol compounds in this study demonstrate the possibility that a lignin-derived compound having more than one reactive position can be developed into a phenolic-type resin.


2013 ◽  
Vol 641-642 ◽  
pp. 215-218
Author(s):  
Sheng Guo ◽  
De Yi Huang ◽  
Ji Feng She ◽  
Xiang Qun Liang

The bleaching efficiency of hydrogen peroxide can be promoted by using suitable activator. In our research, two methods were applied to compare the activating ability of three activators, TAED (tetraacetylethylenediamine), acetamide and dicyandiamide. The first part was hydrogen peroxide bleaching. TAED was excellent, because the brightness improvement was the maximum; the viscosity was acceptable. Acetamide was an applied activator in peroxide bleaching,for it could get same effects as TAED if the bleaching process had enough time and enough dosage. In the last part our study was about the kinetics of a lignin model compounds, acetovanillone, in peroxide-alone system, TAED/H2O2 system, acetamide/H2O2 system and dicyandiamide/H2O2 system. The rate constant, k and half-life period, t1/2 can be used to compare the rate of oxidation of acetovanilone. Compared to peroxide-alone system, three systems with activator and H2O2 could accelerate the reactions of hydrogen peroxide and acetovanillone. The t1/2 of TAED/H2O2 system was least of them. It was just 1/5 of t1/2 of peroxide-alone system, 1/4 of t1/2 of acetamide/H2O2 system and dicyandiamide/H2O2 system. The activating ability order of activators was: TAED> acetamide> dicyandiamide.


2020 ◽  
Vol 16 ◽  
Author(s):  
Mahdieh Sharifi ◽  
Ramyakrishna Pothu ◽  
Rajender Boddula ◽  
Inamuddin

Background: There is a developing demand for innovation in petroleum systems replacements. Towards this aim, lignocellulosic biomass suggested as a possible sustainable source for the manufacturing of fuels and produced chemicals. The aims of this paper are to investigate different kinds of β-O-4 lignin model compounds for the production of value-added chemicals in presence of ionic liquids. Especially, a cheap β-O-4 lignin model Guaiacol glycerol ether (GGE) (Guaifenesin) is introduced to produce valuable chemicals and novel products. Methods: Research related to chemical depolymerization of lignocellulosic biomass activity is reviewed, the notes from different methods such as thermal and microwave collected during at least 10 years. So, this collection provides a good source for academic research and it gives an efficient strategy for the manufacturing of novel value-added chemicals at an industrial scale. Results: This research presented that ionic liquid microwave-assisted is a power saving, cost efficient, fast reaction, and clean way with high selectively and purity for production of high value chemicals rather that conversional heating. Guaiacol and catechol are some of these valuable chemicals that is produced from β-O-4 lignin model compounds with high word demands that are capable to produce in industry scale. Conclusion: The β-O-4 lignin model compounds such as Guaiacol glycerol ether (GGE) (Guaifenesin) are good platform for developing food materials, perfumery, biorefinery, and pharmaceutical industry by ionic liquids-assisted lignin depolymerization method.


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