Oxidation of unsaturated carboxylic acids under hydrothermal conditions.

Hydrothermal oxidation pathways of high molecular weight unsaturated carboxylic acids were investigated for the potential use of chemoselectivity to improve the efficiency of the desired products from biomasses directly containing or easily producing unsaturated carboxylic acids. Hock cleavage, which frequently occur at general chemical, was observed in the absence of any acid catalyst and may be a potential major oxidation cleavage mechanism, which leads to the cleavage at both the carbon-carbon double bond and the single bond near a double bond. The addition of a peroxyl radical to the double bond may be also a potential major oxidation mechanism, which leads to the oxidation cleavage mainly at the carbon-carbon double bond. Cleavage at the carbon-carbon bond near the double bond by the addition of a peroxyl radical to the double bond may also occur. However, oxidation at either alpha-, beta-, or gamma-carbon to the -COOH group hardly occurred. These results may help to selectively produce desired products from biomasses, such as lignin and oils.

A new process for producing calcium acetate from vegetable wastes for use as an environmentally friendly deicer.

A new process for producing calcium acetate, a non-corrosive deicer, is proposed. The process consists of a two-step continuous-flow hydrothermal conversion of vegetable wastes into acetic acid and the production of calcium acetate, followed by the separation and condensation of the product. The experiments for acetic acid production showed that there were almost no significant differences in acetic acid yields for the five different kinds of vegetables selected for the batch experiments or for their mixture in batch and continuous-flow experiments. Electrodialysis was chosen as a satisfactory method for separating and condensing the calcium acetate produced from the acetic acid solution obtained from the vegetable wastes. After purification by reverse-osmosis, the residual, depleted acid solution could be safely discharged. The calculation of the carbon balance for the proposed process showed that 21.3% of the TOC from vegetable wastes could be used as calcium/magnesium acetate (CMA) and over 22% as an environmentally friendly deicer.

Impact of phenolic compounds on hydrothermal oxidation of cellulose.

The effect of phenolic compounds on hydrothermal oxidation of cellulose was studied using a batch reactor at 300 degrees C with H(2)O(2) as oxidant. Intermediate products, as well as the yields of acetic acid produced in the oxidation of cellulose, phenolic compounds, and cellulose-phenolic compound mixtures were examined. Phenolic compounds used were phenol, 1,4-benzenediol, 2-methoxy-4-methylphenol, and 2,6-di-tert-butyl-4-methylphenol. In the case of oxidation of cellulose-phenolic compound mixtures, (1) formic acid, a basic oxidation product from carbohydrates, decreased considerably, (2) 5-hydroxymethyl-2-furaldehyde and 2-furaldehyde, acid-catalyzed dehydration products from carbohydrates, appeared, and (3) the yield of acetic acid increased compared to that in the oxidation of cellulose. From these results, phenolic compounds seem to inhibit the oxidation of cellulose under hydrothermal conditions. The inhibition of the oxidation of cellulose by phenolic compounds seems to be related closer to the stability of phenolic compounds under oxidation conditions rather than the ease to remove phenolic hydrogen on the OH group.

Formation of lactic acid from glycolaldehyde by alkaline hydrothermal reaction.

Alkali hydrothermal experiments with glycolaldehyde were carried out at 300 degrees C. Glycolaldehyde was converted into lactic acid in a yield of 28% based on the starting carbon mass of glycolaldehyde. A conversion pathway for glycolaldehyde into lactic acid is proposed and our results suggest that the pathway via glycolaldehyde is also important in the conversion of glucose into lactic acid.

Controlling hydrothermal reaction pathways to improve acetic acid production from carbohydrate biomass.

A two-step hydrothermal process to improve the production of acetic acid was discussed. The first step was to accelerate the formation of 5-hydroxymethyl-2-furaldehyde (HMF), 2-furaldehyde (2-FA), and lactic acid (LA), and the second step was to further convert the furans (HMF, 2-FA) and LA produced in the first step to acetic acid by oxidation with newly supplied oxygen. The acetic acid obtained by the two-step process had not only a high yield but also better purity. The contribution of two pathways via furans and LA in the two-step process to convert carbohydrates into acetic acid was roughly estimated as 85-90%, and the ratio of the contributions of furans and LA to yield acetic acid was estimated as 2:1. The fact that WO of carbohydrates is not capable of producing a large amount of acetic acid, while the two-step process can enhance the acetic acid yield, can be explained because formic acid is a basic product of direct oxidation of carbohydrate, and acetic acid in WO of carbohydrates may come from the oxidation of dehydration products of aldose.

Oxidation reaction of high molecular weight carboxylic acids in supercritical water.

Stearic acid, being a model compound of high molecular weight carboxylic acids, was oxidized in a batch reactor by changing the oxygen supply with an insufficient oxygen supply at a constant reaction time at 420 degrees C. On the basis of the intermediate products identified by GC/MS, NMR, and HPLC analyses and the free-radical reaction mechanism, the oxidation pathways of high molecular weight carboxylic acids in supercritical water are discussed. The reaction of carboxylic acids in supercritical water proceeds with the consecutive oxidation of higher molecular weight carboxylic acids to lower molecular weight carboxylic acids through several major pathways. The attack of the hydroxyl radical occurs not only at the carbons in alpha-, beta-, gamma-positions to a --COOH group but also at the carbons ((omega-1)-carbon and/or omega-carbon) far in the alkyl chain from a --COOH group, which may lead to the formation of dicarboxylic acids.