Mechanism and theory of d-glucopyranose homogeneous acid catalysis in the aqueous solution phase.

A detailed systematic theoretical study of the mechanism of the homogeneous Brønsted-acid catalysis of d-glucose in aqueous solution phase ("acid hydrolysis") is reported. G4MP2 with the SMD solvation model at B3LYP/6-31G(2df,p) are employed to compute the free energies of the molecular and ionic species pertaining to the isomerization, protonation, hydrogen cation transfer and decomposition processes of d-glucopyranose in aqueous solution phase. This information is used to hypothesise a reaction mechanism that is of improved accuracy and completeness from the existing art. It is found that rotation of the d-glucose alkyl carbon-carbon bond is a facile process and is very important to the subsequent catalytic mechanism. This rotation produces two rotameric isomers which are of notably different thermodynamic stability and reactivity, even with regard to the products of this acid catalysis. As a low energy process (ΔG‡ = ∼3.8-6.7 kcal mol-1), the alkyl carbon-carbon bond may rotate toward the hydroxyl group at the adjacent "4" position reducing the energy required to protonate that position by 3.0-7.2 kcal mol-1 (or 15-30%). The combination of two rotomeric isomers with the six structural isomers owing to the oxygen atoms, means that protonated d-glucose cations embark on a complex competition of interconversion and decomposition that is both thermodynamically and kinetically influenced. The calculations support the hypothesis that the acid-catalysed hydrolysis of d-glucose may yield a number of platform chemicals that have not previously been suggested. These include the prospect of three isomers of 5-hydroxymethylfurfural (HMF); 5-(hydroxymethyl)furan-2-carbaldehyde, 5-(hydroxymethyl)furan-3-carbaldehyde and 5-(hydroxymethyl)furan-4-carbaldehyde. Vibrational spectra of these HMF isomers are also computed and compared to experimentally determined infrared spectra of "humins". On this basis, it is cautiously speculated that the alternative HMF isomers, may be monomeric constituent of the polymeric "humins".

Energy recovery from thermal treatment of dewatered sludge in wastewater treatment plants.

Sewage sludge is a by-product generated from municipal wastewater treatment (WWT) processes. This study examines the conversion of sludge via energy recovery from gasification/combustion for thermal treatment of dewatered sludge. The present analysis is based on a chemical equilibrium model of thermal conversion of previously dewatered sludge with moisture content of 60-80%. Prior to combustion/gasification, sludge is dried to a moisture content of 25-55% by two processes: (1) heat recovered from syngas/flue gas cooling and (2) heat recovered from syngas combustion. The electricity recovered from the combined heat and power process can be reused in syngas cleaning and in the WWT plant. Gas temperature, total heat and electricity recoverable are evaluated using the model. Results show that generation of electricity from dewatered sludge with low moisture content (≤ 70%) is feasible within a self-sufficient sludge treatment process. Optimal conditions for gasification correspond to an equivalence ratio of 2.3 and dried sludge moisture content of 25%. Net electricity generated from syngas combustion can account for 0.071 kWh/m(3) of wastewater treated, which is up to 25.4-28.4% of the WWT plant's total energy consumption.

Biomass Pre-Extraction as a Versatile Strategy to Improve Biorefinery Feedstock Flexibility, Sugar Yields, and Lignin Purity.

Feedstock flexibility is highly advantageous for the viability of (solvent-based) biorefineries but comes with the considerable challenge of having to cope with the varying nature and typically high abundance of nonlignocellulose compounds in the most readily available residual biomass streams. Here, we demonstrate that mild aqueous acetone organosolv fractionation of various complex lignocellulosic raw materials (roadside grass, wheat straw, birch branches, almond shells, and a mixed stream thereof) is indeed negatively affected by these compounds and present a versatile strategy to mitigate this bottleneck in biorefining. A biomass pre-extraction approach has been developed to remove the detrimental extractives with (aqueous) acetone prior to fractionation. Pre-extraction removed organic extractives as well as minerals, primarily reducing acid dose requirements for fractionation and loss of hemicellulose sugars by degradation and improved the purity of the isolated lignin. We show how pre-extraction affects the effectiveness of the biorefinery process, including detailed mass balances for pretreatment, downstream processing, and product characteristics, and how it affects solvent and energy use with a first conceptual process design. The integrated biorefining approach allows for the improved compatibility of biorefineries with sustainable feedstock supply chains, enhanced biomass valorization (i.e., isolation of bioactive compounds from the extract), and more effective biomass processing with limited variation in product quality.

Effects of Soluble Lignin on the Formic Acid-Catalyzed Formation of Furfural: A Case Study for the Upgrading of Hemicellulose.

A comprehensive study is presented on the conversion of hemicellulose sugars in liquors obtained from the fractionation of Miscanthus, spruce bark, sawdust, and hemp by using formic acid. Experimental tests with varying temperature (130-170 °C), formic acid concentration (10-80 wt%), carbohydrate concentrations, and lignin separation were carried out, and experimental data were compared with predictions obtained by reaction kinetics developed in a previous study. The conversions of xylose and arabinose into furfural were inherently affected by the presence of polymeric soluble lignin, decreasing the maximum furfural yields observed experimentally by up to 24%. These results were also confirmed in synthetic mixtures of pentoses with Miscanthus and commercial alkali lignin. This observation was attributed to side reactions involving intermediate stable sugar species reacting with solubilized lignin during the conversion of xylose into furfural.

Conversion of hemicellulose sugars catalyzed by formic acid: kinetics of the dehydration of D-xylose, L-arabinose, and D-glucose.

The pre-treatment of lignocellulosic biomass produces a liquid stream of hemicellulose-based sugars, which can be further converted to high-value chemicals. Formosolv pulping and the Milox process use formic acid as the fractionating agent, which can be used as the catalyst for the valorisation of hemicellulose sugars to platform chemicals. The objective of this study was to investigate the reaction kinetics of major components in the hemicelluloses fraction of biomass, that is, D-xylose, L-arabinose and D-glucose. The kinetics experiments for each sugar were performed at temperatures between 130 and 170 °C in various formic acid concentrations (10-64 wt %). The implications of these kinetic models on the selectivity of each sugar to the desired products are discussed. The models were used to predict the reaction kinetics of solutions that resemble the liquid stream obtained from the fractionation process of biomass using formic acid.

Autothermal, single-stage, performic acid pretreatment of Miscanthus x giganteus for the rapid fractionation of its biomass components into a lignin/hemicellulose-rich liquor and a cellulase-digestible pulp.

A novel approach to the performic acid pulping of biomass enables effective delignification and fractionation in a time frame not achieved heretofore. An autothermal decomposition reaction was triggered when 100mg/L Fe(2)(SO(4))(3) in 4.0 M NaOH was added to 5% or 7.5% H(2)O(2) in aqueous formic acid containing chipped Miscanthus x giganteus. Peroxy-decomposition resulted in pressures of 19 and 35 bar in the 5% and 7.5% peroxide liquors and reduced the lignin content in the resulting pulps to <6% within 140 and 30 min, respectively. Solubilised lignin was available for recovery from the liquor by subsequent dilution with water. Hemicellulose removal to the liquor was 68% and 89% for the 5% and 7.5% peroxide solutions. Crystalline cellulose yields were >99% and >95% and the rate of glucose release from cellulase digestion of the pulps in 24h was more than 20-fold that for the raw Miscanthus.

An integrated process for the production of platform chemicals and diesel miscible fuels by acid-catalyzed hydrolysis and downstream upgrading of the acid hydrolysis residues with thermal and catalytic pyrolysis.

This study evaluates an integrated process for the production of platform chemicals and diesel miscible biofuels. An energy crop (Miscanthus) was treated hydrothermally to produce levulinic acid (LA). Temperatures ranging between 150 and 200 °C, sulfuric acid concentrations 1-5 wt.% and treatment times 1-12 h were applied to give different combined severity factors. Temperatures of 175 and 200 °C and acid concentration of 5 wt.% were found to be necessary to achieve good yield (17 wt.%) and selectivities of LA while treatment time did not have an effect. The acid hydrolysis residues were characterized for their elemental, cellulose, hemicellulose and lignin contents, and then tested in a small-scale pyrolyzer using silica sand and a commercial ZSM-5 catalyst. Milder pretreatment yielded more oil (43 wt.%) and oil O(2) (37%) while harsher pretreatment and catalysis led to more coke production (up to 58 wt.%), less oil (12 wt.%) and less oil O(2) (18 wt.%).