Interest in recovery of carboxylic acids from their aqueous solutions and production media has been growing with the improvements in the production techniques. Reactive extraction is proposed as a promising method to achieve high distribution coefficients with good selectivity. In the present study, equilibrium and kinetic studies, needed for the design of a recovery unit were carried out. Reactive extraction of pyruvic, acetic and lactic acids from their single and mixed acid solutions were carried out with tertiary amines, Alamine 336 and trioctylamine, dissolved in diluents, 1-octanol and oleyl alcohol. The kinetic parameters such as reaction order and rate constant were calculated by using the aqueous solution of pyruvic acid with 1-octanol solution of trioctylamine.
The distribution coefficient of pyruvic acid was obtained as 0.30 and 0.07 with 1-octanol and oleyl alcohol respectively. The trend did not change after the addition of the extractants to the diluents. As expected, the more polar diluent extracted more acid than the less polar one. The extractant was observed to be the limiting reagent of the reversible complexation reaction in the organic phase. It was seen that loading ratio was not affected by the concentration of the extractant in the organic phase but increased with the equilibrium concentration of the acid in the aqueous phase. The results showed that mainly (1-1) acid-amine reaction occurred in the organic phase. Because tertiary amines can react with only undissociated acids, the increase in the initial pH of the aqueous phase caused a decrease in the distribution coefficients of the carboxylic acids studied. The effect of the concentration of the organic phase disappeared when the initial pH of the aqueous phase was 4.0 and a distribution coefficient value of 0.1 was achieved for all concentration levels of organic phase. Similar results were obtained for acetic and lactic acids and this behavior was used to propose a selective recovery of the acids from their mixed acid solutions.
The presence of acetic acid prevented the extraction of pyruvic acid. The increase in the concentration of the extractant in the organic phase caused an increase in the distribution coefficient of pyruvic acid. During the extraction process, lactic acid could not be recovered from ternary acid solutions because of its high hydrophilicity. The results of reactive extraction of lactic and pyruvic acids from their binary acid solutions showed that at higher concentration of lactic acid, the distribution of pyruvic acid was negatively affected. On the other hand, the presence of lactic acid at a low concentration level did not affect the distribution of pyruvic acid.
It was found that the reaction between pyruvic acid and trioctylamine in 1-octanol was first order with respect to the reactants with a second order rate constant of 0.94 L mol-1 s-1. The enhancement factor of the system was obtained as 25.
| Identifer | oai:union.ndltd.org:METU/oai:etd.lib.metu.edu.tr:http://etd.lib.metu.edu.tr/upload/12612261/index.pdf |
| Date | 01 July 2010 |
| Creators | Marti, Mustafa Esen |
| Contributors | Gurkan, Turker |
| Publisher | METU |
| Source Sets | Middle East Technical Univ. |
| Language | English |
| Detected Language | English |
| Type | Ph.D. Thesis |
| Format | text/pdf |
| Rights | To liberate the content for public access |
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