Valorization of tannery-derived FAMEs into bio-based epoxides via chemo-enzymatic synthesis
The urgent transition toward low-carbon chemical manufacturing has prompted the development of renewable alternatives to fossil-based epoxy intermediates. This study presents an integrated and resource-efficient chemoenzymatic route for the synthesis of epoxidized methyl oleate (EMO) from fatty acid...
| Authors: | , , , |
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| Format: | article |
| Status: | Published version |
| Publication Date: | 2025 |
| Country: | España |
| Institution: | Universitat de Lleida (UdL) |
| Repository: | Repositori Obert UdL |
| OAI Identifier: | oai:repositori.udl.cat:10459.1/469559 |
| Online Access: | https://doi.org/10.1016/j.clce.2025.100195 https://hdl.handle.net/10459.1/469559 |
| Access Level: | Open access |
| Keyword: | Chemo-enzymatic synthesis Circular bioeconomy Enzymatic epoxidation Epoxidized methyl oleate (EMO) Fatty acid methyl esters (FAMEs) Life cycle assessment (LCA) Techno-economic analysis (TEA) |
| Summary: | The urgent transition toward low-carbon chemical manufacturing has prompted the development of renewable alternatives to fossil-based epoxy intermediates. This study presents an integrated and resource-efficient chemoenzymatic route for the synthesis of epoxidized methyl oleate (EMO) from fatty acid methyl esters (FAMEs) derived from tannery waste—a lipid-rich but underutilized industrial residue. A single-step urea complexation achieved 86.7 ± 0.6 % methyl oleate purity with a 38.1 ± 0.9 % recovery yield, while the saturated-rich coproduct (~40 %) exhibited physicochemical properties suitable for biodiesel or lubricant applications. Subsequent epoxidation was carried out using immobilized Candida antarctica lipase B (Novozym® 435) and in situ generated performic acid, yielding an oxirane oxygen content of 6.42 ± 0.14 %, corresponding to >90 % conversion of double bonds under mild conditions. The enzyme retained 72 % of its initial activity after ten reuse cycles, significantly enhancing process circularity and reducing catalytic costs. Green chemistry metrics were favorable: atom economy reached 86 %, solvent recovery exceeded 85 %, and the E-factor remained as low as 0.86 kg waste/kg EMO. A cradle-to-gate life cycle assessment (LCA) estimated a global warming potential (GWP) of 1.92 kg CO₂-eq/kg EMO—representing a 63 % reduction compared to petrochemical benchmarks. Economic analysis at the 1000 t/year scale yielded a production cost of €1.57/kg with an internal rate of return (IRR) of 15 %. Overall, this work demonstrates how lipid-rich industrial residues can be converted into high-value bio-based epoxides through a scalable and environmentally sound chemo-enzymatic route, aligning with circular economy principles and green chemistry targets. |
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