Ultrasound enhanced solubilization of forest biorefinery hydrolysis lignin in mild alkaline conditions.

In the forest biorefinery, hydrolysis lignin (HL) is often dissolved with high concentration NaOH solution, followed by acid precipitation to obtain purified HL. For the first time, this study evaluates the effect of ultrasound (US) on the dissolution of industrially produced HL in aqueous NaOH solutions and the acid precipitation yield of HL. The solubility of HL in mild aqueous NaOH solutions was studied with and without US treatment at 20 kHz concerning the solid-to-liquid ratio, molecular weight of dissolved fractions and structural changes in dissolved HL. Results showed that the solubility of HL at 25 °C was strongly dependent on NaOH concentration. However, the US treatment significantly improved the solubility of HL, reaching a solubility plateau at 0.1 NaOH/HL ratio. US treatment enhanced the solubilization of HL molecules with higher MW compared to conventional mixing. The increase of HL solubility was up to 30 % and the recovery yield of purified lignin with acid precipitation was 37 % higher in dilute NaOH solution. A significant result was that the Mw of dissolved HL in homogeneous alkali solutions decreased with US treatment. SEC, HSQC and 31P NMR analyses of dissolved HL characteristics showed that both, the mechanoacoustic and sonochemical solubilization pathways contribute to the dissolution process. However, US does not cause major changes in the HL structure compared to the native lignin. Indeed, US technology has the potential to advance the dissolution and purification of HL in biorefineries by reducing the amount of chemicals required; thus, more controlled and environmentally friendly conditions can be used in HL valorization.

Ameliorating effect of nitrate on nitrite inhibition for denitrifying P-accumulating organisms.

Lowered air supply and organic carbon need are the key factors to reduce wastewater treatment costs and thereby, avoid eutrophication. Denitrifying PO43-- removal (DPR) process using nitrate instead of oxygen for PO43- uptake was started up in the sequencing batch reactor (SBR) at a nitrate dosing rate of 20-25 mg N L-1 d-1. Operation with a real municipal wastewater supplied with CH3COONa, K2HPO4 and KNO3 succeeded in the cultivation of biomass containing denitrifying polyphosphate accumulating organisms (DPAOs). The durations of SBR process anaerobic/anoxic/oxic cycles were 1.5 h, 3.5 h and 1 h, respectively. SBR operation resulted in a maximum PO43--P uptake of 17 mg PO43--P g-1 MLSS. The highest TN and PO43- removal efficiencies were observed during the first half of reactor operation at 77 (±10) % and 71 (±5) %, respectively. An average COD removal rate of 172 (±98) mg g-1 MLSS and a high average removal efficiency of 89 (±4) % were achieved. Nitrite effect with/without nitrate as DPR electron acceptor was investigated in batch-scale to show possibilities to use high nitrite and nitrate contents simultaneously as electron acceptors for the anoxic phosphate uptake. Nitrate attenuation against nitrite toxicity can be economically justified in full-scale treatment applications in which wastewater has a high nitrogen content. Nitrate attenuated nitrite toxicity (caused by nitrite content at 5-100 mg NO2--N L-1) when using supplemental additions of nitrate (at concentrations of 45-200 mg NO3--N L-1) in batch tests. Illumina sequencing emphasized that during biomass adaption microbial community changed by lowered aerobic cycle length and by lowered nitrate dosing towards representation of key DPAO/PAO- organisms, such as Candidatus Accumulibacter, Xanthomonadaceae, Comomonadaceae, Saprospiraceae and Rhodocyclaceae. This study showed that DPAO biomass adaption to nitrate maintained an efficient COD, nitrogen and phosphorus removal and the biomass can be applied for treatment of wastewater containing high nitrite and nitrate content.

Route for Conversion of Furfural to Ethylcyclopentane.

A method for conversion of furfural, widely available platform chemical from biomass, to ethylcyclopentane, is reported. Ethylcyclopentane is a cyclic alkane with a relatively high octane number (RON 67, bp 103 °C) and could potentially serve as a drop-in biofuel. The synthetic route includes a transformation of furfural to 1-(furan-2-yl)propan-1-ol that is further subjected to Piancatelli rearrangement to give 5-ethyl-4-hydroxycyclopent-2-en-1-one. The subsequent hydrodeoxygenation affords ethylcyclopentane in 48% isolated yield.

Sonication effects on non-radical reactions. A sonochemistry beyond the cavitation?

The kinetics of pH-independent hydrolysis of 4-methoxyphenyl dichloroacetate were investigated under ultrasonic irradiation with an application of 10% of the maximum power of the equipment and without sonication in acetonitrile-water binary mixtures with a content of acetonitrile ranging from 0.008 to 35 wt.%. Similar kinetic investigations were performed at intensities corresponding to 10%, 20%, 30%, 40%, and 50% of the input energy in solvent mixtures containing 10 wt.% and 25 wt.% acetonitrile. In parallel, the responses of KI and terephthalic acid dosimeters at applied irradiation levels were registered under the same experimental conditions. Significant kinetic sonication effects were found at sound intensities presumably not inducing cavitation in the solution. This result provides an experimental evidence of kinetic effects of ultrasound in the absence of cavitation. A disturbing impact of cavitation on the ultrasonic acceleration of the reaction was found. The implications of these findings were discussed.

Kinetic sonication effects in aqueous acetonitrile solutions. Reaction rate levelling by ultrasound.

The kinetics of the pH-independent hydrolysis of 4-methoxyphenyl dichloroacetate were investigated with and without ultrasonic irradiation in acetonitrile-water binary mixtures containing 0.008 to 35 wt.% of acetonitrile and the kinetic sonication effects (kson/knon) were calculated. Molecular dynamics (MD) simulations of the structure of the solutions were performed with ethyl acetate as the model ester. The ester is preferentially solvated by acetonitrile. The excess of acetonitrile over water in the solvation shell grows fast with an increase in the co-solvent content in the bulk solution. In parallel, the formation of a second solvation shell rich in acetonitrile takes place. Significant kinetic sonication effects for the hydrolysis were explained with facile destruction of the diffuse second solvation shell followed by a rearrangement of the remaining solvent layer under sonication. The rate levelling effect of ultrasound was discussed. In an aqueous-organic binary solvent, independent of the solvent composition, the ultrasonic irradiation evokes changes in the reaction medium which result in an almost identical solvation state of the reagent thus leading to the reaction rate levelling.

Kinetic sonication effects in light of molecular dynamics simulation of the reaction medium.

Molecular dynamics (MD) simulation of the structure of ethyl acetate solutions in two water-ethanol mixtures was performed at 280 and 330K. The MD simulations revealed that ethyl acetate was preferentially solvated by ethanol, water being mainly located in the next solvation layer. With increasing temperature ethanol was gradually replaced by water in the first solvation shell. These findings explain the decrease in the rate of ester hydrolysis with increasing molar ratio of ethanol in the solution as the reaction rate was linearly dependent on the relative ethanol content in the first solvation shell of the ester. Predominance of ethanol results in decreased polarity and water activity in the shell and accordingly in a decreased reaction rate. Based on the results of the MD simulations, the principal conclusion of this work is that ultrasound enhances the kinetic energy (the effective temperature) of species in the solution and, in this way, evokes shifts in the solvation equilibria thus affecting the reaction rate. It appears that ultrasound does not completely break down the solvent shells or clusters in the solution as previously believed. Phenomena of thermo-solvatochromism and reaction rate levelling by ultrasound in binary solvents are described.

Ultrasonic evidence of hydrophobic interactions. Effect of ultrasound on benzoin condensation and some other reactions in aqueous ethanol.

The kinetics of KCN-catalyzed benzoin condensation of benzaldehyde in water and ethanol-water binary mixtures was investigated both under ultrasound at 22 kHz and without sonication. Thermodynamic activation parameters were calculated from kinetic data obtained at 35, 50, and 65 degrees C. Evidence that ultrasound can retard reactions is reported and hence a direct proof that sonochemical processes occur in the bulk solution. Former results and literature data for ester hydrolyses and tert-butyl chloride solvolysis are involved in the discussion. A quantitative relationship between sonication effects and the hydrophobicity of reagents is presented for the first time. Ultrasound affects hydrophobic interactions with the solvent, which are not manifested in conventional kinetics. When it suppresses the stabilization of the encounter complexes between reagents, sonication hinders the reaction but accelerates it when it perturbs the hydrophobic stabilization of the ground state of a reagent.

Impact of ultrasound on hydrophobic interactions in solutions: ultrasonic retardation of benzoin condensation.

Kinetics of the benzoin condensation of benzaldehyde in presence of KCN as the catalyst in water and in ethanol-water binary solutions were investigated without sonication and under ultrasound at 22 kHz. A statistically significant 20% decrease of the rate was observed in water. The retardation effect of ultrasound gradually decreases up to 45 wt% ethanol content. We report an evidence of ultrasonic retardation of reactions and thereby a direct evidence for sonochemical processes in the bulk solution. Ultrasound can disturb solvation of the species in the solution. If breaking down the stabilization of the encounter complexes between the reagents, sonication hinders the reaction while perturbation of the solvent-stabilization of the reagents accelerates the reaction.

Effect of ultrasound on the base-catalyzed hydrolysis of 4-nitrophenyl acetate in aqueous ethanol.

The kinetics of base-catalyzed hydrolysis of 4-nitrophenyl acetate was studied in water and water-ethanol mixtures under ultrasound (21.1 kHz) using a probe equipped with a quartz horn and, by comparison, without sonication. The ethanol concentration was varied from 0 to 50 wt % and pH from 7.5 to 9. The increase of reaction rate was inversely proportional to the strength of substrate interactions with the solvent structure. It was found that the effect of ultrasound could be related to the perturbation of solute-solvent interactions. This conclusion seems to apply to both acid-catalyzed and base-catalyzed hydrolysis reactions. Parallel experiments with a titanium horn revealed the catalytic action of undetermined chemical species formed from dispersed titanium metal.