scholarly journals A Biorefinery Cascade Conversion of Hemicellulose-Free Eucalyptus Globulus Wood: Production of Concentrated Levulinic Acid Solutions for γ-Valerolactone Sustainable Preparation

Catalysts ◽  
2018 ◽  
Vol 8 (4) ◽  
pp. 169 ◽  
Author(s):  
Sandra Rivas ◽  
Anna Raspolli Galletti ◽  
Claudia Antonetti ◽  
Domenico Licursi ◽  
Valentín Santos ◽  
...  

Eucalyptus globulus wood samples were subjected to preliminary aqueous processing to remove water-soluble extractives and hemicelluloses, and the resulting solid (mainly made up of cellulose and lignin) was employed as a substrate for converting the cellulosic fraction into mixtures of levulinic and formic acid through a sulfuric acid-catalyzed reaction. These runs were carried out in a microwave-heated reactor at different temperatures and reaction times, operating in single-batch or cross-flow modes, in order to identify the most favorable operational conditions. Selected liquid phases deriving from these experiments, which resulted in concentrated levulinic acid up to 408 mmol/L, were then employed for γ-valerolactone production by levulinc acid hydrogenation in the presence of the commercial 5% Ru/C catalyst. In order to assess the effects of the main reaction parameters, hydrogenation experiments were performed at different temperatures, reaction times, amounts of ruthenium catalyst and hydrogen pressure. Yields of γ-valerolactone in the range of 85–90 mol % were obtained from the hydrogenation of the wood-derived solutions containing levulinic acid, obtained by single-batch operation or by the cross-flow process. The negative effect of co-produced formic acid present in crude levulinic acid solutions was evidenced and counteracted efficiently by allowing the preliminary thermal decomposition of formic acid itself.

Author(s):  
Victoria V. Krupskaya ◽  
Sergey V. Zakusin ◽  
Ekaterina A. Tyupina ◽  
Olga V. Dorzhieva ◽  
Anatoliy P. Zhukhlistov ◽  
...  

The paper discusses the mechanism of montmorillonite structure alteration and bentonites properties modification (on the example of samples from clay deposit Taganka, Kazakhstan) due to the thermochemical treatment (treatment with inorganic acid solutions at different temperatures, concentrations and reaction times). With the use of the suit of methods certain processes were distinguished: transformation of montmorillonite structure, which appears in the leaching of interlayer and octahedral cations, protonation of the interlayer and OH groups at octahedral sheets. Changes in the structure of the 2:1 layer of montmorillonite and its interlayer result in significant changes in the properties – reduction of cation exchange capacity and an increase of specific surface area. The results of the work showed that bentonite clays retain a significant portion of its adsorption properties even after the long term and intense thermochemical treatment (6M HNO3, 60°C, 108 hours)


1983 ◽  
Vol 100 (1) ◽  
pp. 43-62 ◽  
Author(s):  
Elisabeth Grenet

SUMMARYThe digestibility, the voluntary intake and the nitrogen balance of 108 diets corresponding to 94 silages prepared from 20 fresh crops were measured in growing sheep. Series of silages were made from the same fresh forage. Each series included two controls: a direct-cut silage without additive and a direct-cut silage with formic acid, with a variable number of experimental silages with different additives.Rumen ammonia concentration, measured on rumen-fistulated sheep, decreased when an additive was used. It increased with nitrogen intake and was inversely related to the organic-matter digestibility and the crude-fibre digestibility. It varied with the silage composition.The crude-protein digestibility of direct-cut silages without additives was similar to or slightly higher than the crude-protein digestibility of the fresh crops. The addition of formic acid depressed the digestibility, but the addition of formaldehyde decreased it even more. The urinary nitrogen loss was higher for silages without additive than for the fresh crops and was decreased by the addition of formic acid. The addition of formaldehyde to formic acid had an additive effect.Retained nitrogen was lower in silages without additives (12% of nitrogen intake) than in parent crops (15·7%). It increased when formic acid (15·8%) was added. The addition of formaldehyde at a low rate (1·5 l/t green fodder) to the formic acid did not increase the nitrogen retention whether expressed in g/day or as percentage of nitrogen intake, but the addition of formaldehyde at a high rate (3·5 l/t green fodder) to formic acid decreased nitrogen retention. The other additives based on cereals or whey did not improve the nitrogen balance compared with formic acid. Nitrogen retention differed according to plant species.Retained nitrogen increased with digestible organic-matter intake and nitrogen intake. It increased with the silage water-soluble carbohydrate content. The higher the silage fermentation product content (ammonia, lactic acid, propionic acid), the lower the retained nitrogen. It appears that the nitrogen value of silages can be high provided that the silages are well preserved and that excessive protein breakdown is avoided.


1965 ◽  
Vol 43 (8) ◽  
pp. 2254-2258 ◽  
Author(s):  
C. C. Lee ◽  
Edward W. C. Wong

endo-Norbornyl-2-d p-bromobenzenesulfonate was synthesized and the isotope effects, as measured by kH/kD, were determined over a range of temperatures for solvolyses in 30% water – 70% dioxane, acetic acid, and formic acid. Values of kH/kD are of the order of 1.20. The data appear to indicate slightly higher isotope effects as the solvents are changed from aqueous dioxane to acetic acid to formic acid, as well as somewhat higher isotope effects at lower temperatures. Possible mechanistic implications of these results are presented. Relative titrimetric acetolysis rates, kexo/kendo, at different temperatures, and enthalpies and entropies of activation for these acetolyses are evaluated and discussed.


2018 ◽  
Vol 42 (2) ◽  
pp. 1423-1430 ◽  
Author(s):  
Firdaus Parveen ◽  
Tanmoy Patra ◽  
Sreedevi Upadhyayula

The catalytic conversion of biomass-derived carbohydrates to value-added chemicals, such as 5-hydroxymethylfurfural, levulinic acid, and formic acid, is a commercially important reaction and requires the use of both Lewis and Bronsted acids.


2021 ◽  
pp. 118256
Author(s):  
Enchen Yang ◽  
Hanbo Zheng ◽  
Tao Yang ◽  
Wei Yao ◽  
Zijian Wang ◽  
...  

2014 ◽  
Vol 16 (3) ◽  
pp. 1305-1315 ◽  
Author(s):  
Yang Qiu ◽  
Le Xin ◽  
David J. Chadderdon ◽  
Ji Qi ◽  
Changhai Liang ◽  
...  

1932 ◽  
Vol 7 (2) ◽  
pp. 149-161 ◽  
Author(s):  
W. H. Hatcher ◽  
E. W. R. Steacie ◽  
Frances Howland

The kinetics of the oxidation of gaseous acetaldehyde have been investigated from 60° to 120 °C. by observing the rate of pressure decrease in a system at constant volume. A considerable induction period exists, during which the main products of the reaction are carbon dioxide, water, and formic acid. The main reaction in the subsequent stages involves the formation of peroxides and their oxidation products. The heat of activation of the reaction is 8700 calories per gram molecule. The indications are that the reactions occurring during the induction period are heterogeneous. The subsequent reaction occurs by a chain mechanism. The chains are initiated at the walls of the reaction vessel, and are also largely broken at the walls.


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