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Branched Medium Chain Fatty Acids: Iso-Caproate Formation from Iso-Butyrate Broadens the Product Spectrum for Microbial Chain Elongation.

ABSTRACT: Chain elongation fermentation can be used to convert organic residues into biobased chemicals. This research aimed to develop a bioprocess for branched medium chain fatty acids (MCFAs) production. A long-term continuous reactor experiment showed that iso-caproate (4-methyl pentanoate, i-C6) can be produced via ethanol based chain elongation. The enriched microbiome formed iso-caproate from iso-butyrate at a rate of 44 ± 6 mmol C L-1 day-1 during the last phase. This amounted to 20% of all formed compounds based on carbon atoms. The main fermentation product was n-caproate (55% of all carbon), as a result of acetate and subsequent n-butyrate elongation. The microbiome preferred straight-chain elongation over branched-chain elongation. Lowering the acetate concentration in the influent led to an increase of excessive ethanol oxidation (EEO) into electron equivalents (e.g., H2) and acetate. The formed acetate in turn stimulated straight chain elongation, but the resulting lower net acetate supply rate towards straight chain elongation led to an increased selectivity towards and productivity of i-C6. The electrons produced via oxidation routes and chain elongation were apparently utilized by hydrogenotrophic methanogens, homoacetogens, and carboxylate-to-alcohol reducing bacteria. Further improvements could be achieved if the acetate-producing EEO was minimized and limitations of ethanol and CO2 were prevented.

SUBMITTER: de Leeuw KD

PROVIDER: S-EPMC6610548 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

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Branched Medium Chain Fatty Acids: Iso-Caproate Formation from Iso-Butyrate Broadens the Product Spectrum for Microbial Chain Elongation.

de Leeuw Kasper D KD Buisman Cees J N CJN Strik David P B T B DPBTB

Environmental science & technology 20190618 13

Chain elongation fermentation can be used to convert organic residues into biobased chemicals. This research aimed to develop a bioprocess for branched medium chain fatty acids (MCFAs) production. A long-term continuous reactor experiment showed that iso-caproate (4-methyl pentanoate, i-C6) can be produced via ethanol based chain elongation. The enriched microbiome formed iso-caproate from iso-butyrate at a rate of 44 ± 6 mmol C L-1 day-1 during the last phase. T ...[more]

PMID: 31244077

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Project description:Chain elongation fermentation allows for the synthesis of biobased chemicals from complex organic residue streams. To expand the product spectrum of chain elongation technology and its application range we investigated 1) how to increase selectivity towards branched chain elongation and 2) whether alternative branched carboxylates such as branched valerates can be used as electron acceptors. Elongation of isobutyrate elongation towards 4-methyl-pentanoate was achieved with a selectivity of 27% (of total products, based on carbon atoms) in a continuous system that operated under CO2 and acetate limited conditions. Increasing the CO2 load led to more in situ acetate formation that increased overall chain elongation rate but decreased the selectivity of branched chain elongation. A part of this acetate formation was related to direct ethanol oxidation that seemed to be thermodynamically coupled to hydrogenotrophic carboxylate reduction to corresponding alcohols. Several alcohols including isobutanol and n-hexanol were formed. The microbiome from the continuous reactor was also able to form small amounts of 5-methyl-hexanoate likely from 3-methyl-butanoate and ethanol as substrate in batch experiments. The highest achieved concentration of isoheptanoate was 6.4 ± 0.9 mM Carbon, or 118 ± 17 mg/L, which contributed for 7% to the total amount of products (based on carbon atoms). The formation of isoheptanoate was dependent on the isoform of branched valerate. With 3-methyl-butanoate as substrate 5-methylhexanoate was formed, whereas a racemic mixture of L/D 2-methyl-butanoate did not lead to an elongated product. When isobutyrate and isovalerate were added simultaneously as substrates there was a large preference for elongation of isobutyrate over isovalerate. Overall, this work showed that chain elongation microbiomes can be further adapted with supplement of branched-electron acceptors towards the formation of iso-caproate and iso-heptanoate as well as that longer chain alcohol formation can be stimulated.

Project description:Introduction: Medium chain fatty acids (MCFAs), such as n-caproate, are potential valuable platform chemicals. MCFAs can be produced from low-grade organic residues by anaerobic reactor microbiomes through two subsequent biological processes: hydrolysis combined with acidogenesis and chain elongation. Continuous chain elongation with organic residues becomes effective when the targeted MCFA(s) are produced at high concentrations and rates, while excessive ethanol oxidation and base consumption are limited. The objective of this study was to develop an effective continuous chain elongation process with hydrolyzed and acidified food waste and additional ethanol. Results: We fed acidified food waste (AFW) and ethanol to an anaerobic reactor while operating the reactor at long (4 d) and at short (1 d) hydraulic retention time (HRT). At long HRT, n-caproate was continuously produced (5.5 g/L/d) at an average concentration of 23.4 g/L. The highest n-caproate concentration was 25.7 g/L which is the highest reported n-caproate concentration in a chain elongation process to date. Compared to short HRT (7.1 g/L n-caproate at 5.6 g/L/d), long HRT resulted in 6.2 times less excessive ethanol oxidation. This led to a two times lower ethanol consumption and a two times lower base consumption per produced MCFA at long HRT compared to short HRT. Conclusions: Chain elongation from AFW and ethanol is more effective at long HRT than at short HRT not only because it results in a higher concentration of MCFAs but also because it leads to a more efficient use of ethanol and base. The HRT did not influence the n-caproate production rate. The obtained n-caproate concentration is more than twice as high as the maximum solubility of n-caproic acid in water which is beneficial for its separation from the fermentation broth. This study does not only set the record on the highest n-caproate concentration observed in a chain elongation process to date, it notably demonstrates that such high concentrations can be obtained from AFW under practical circumstances in a continuous process.

Dataset Information

Branched Medium Chain Fatty Acids: Iso-Caproate Formation from Iso-Butyrate Broadens the Product Spectrum for Microbial Chain Elongation.

Publications

Branched Medium Chain Fatty Acids: Iso-Caproate Formation from Iso-Butyrate Broadens the Product Spectrum for Microbial Chain Elongation.

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