Electrochemical Conversion of Biologically Produced Muconic Acid: Key Considerations for Scale-Up and Corresponding Technoeconomic Analysis

Abstract

We present muconic acid, an unsaturated diacid that can be produced from cellulosic sugars and lignin monomers by fermentation, emerges as a promising intermediate for the sustainable manufacture of commodity polyamides and polyesters including Nylon-6,6 and polyethylene terephthalate (PET). Current conversion schemes consist in the biological production of cis,cis-muconic acid using metabolically engineered yeasts and bacteria, and the subsequent diversification to adipic acid, terephthalic acid, and their derivatives using chemical catalysts. In some instances, conventional precious metal catalysts can be advantageously replaced by base metal electrocatalysts. Here, we show the economic relevance of utilizing a hybrid biological-electrochemical conversion scheme to convert glucose to trans-3-hexenedioic acid (t3HDA), a monomer used for the synthesis of bioadvantaged 6. Potential roadblocks to biological and electrochemical integration in a single reactor, including electrocatalyst deactivation due to biogenic impurities and low faradaic efficiency inherent to side reactions in complex media, have been studied and addressed. In this study, t3HDA was produced with 94% yield and 100% faradaic efficiency. With consideration of the high t3HDA yield and faradaic efficiency, a technoeconomic analysis was developed on the basis of the current yield and titer achieved for muconic acid, the figures of merit defined for industrial electrochemical processes, and the separation of the desired product from the medium. On the basis of this analysis, t3HDA could be produced for approximately $2.00 kg -1. The low cost for t3HDA is a primary factor of the electrochemical route being able to cascade biological catalysis and electrocatalysis in one pot without separation of the muconic acid intermediate from the fermentation broth. AbstractMuconic acid, an unsaturated diacid that can be produced from cellulosic sugars and lignin monomers by fermentation, emerges as a promising intermediate for the sustainable manufacture of commodity polyamides and polyesters including Nylon-6,6 and polyethylene terephthalate (PET). Current conversion schemes consist in the biological production of cis,cis-muconic acid using metabolically engineered yeasts and bacteria, and the subsequent diversification to adipic acid, terephthalic acid, and their derivatives using chemical catalysts.In some instances, conventional precious metal catalysts can be advantageously replaced by base metal electrocatalysts. Here, we show the economic relevance of utilizing a hybrid biological-electrochemical conversion scheme to convert glucose to trans-3-hexenedioic acid (t3HDA), a monomer used for the synthesis of bioadvantaged Nylon-6,6. Potential roadblocks to biological and electrochemical integration in a single reactor, including electrocatalyst deactivation due to biogenic impurities and low faradaic efficiency inherent to side reactions in complex media, have been studied and addressed. In this study, t3HDA was produced with 94% yield and 100% farad...

Identification of More Benign Cathode Materials for the Electrochemical Reduction of Levulinic Acid to Valeric Acid

“…A relatively low amount of metals was obtained in the electrolytes, except for Al of which a large amount was dissolved. Corrosion of the cathode, resulting in dissolution of metals prior and after electrolysis is possible, together with the elevated temperature of 50 °C this might resulted to somewhat higher Pb concentrations in the catholyte than reported elsewhere, although a similar amount of Pb being dissolved from the cathode, i. e. 0.1 % . Of the materials at which LA is not converted, corrosion of Ga and Sn is more pronounced then Ag and Ti, which is expected based on their Pourbaix diagrams .…”

Elektrobioraffinerien: Synergien zwischen elektrochemischen und mikrobiologischen Stoffumwandlungen nutzbar machen

“…[66] Bei der Betrachtung von elektrochemischen Oxidationen ist die Kolbe-Elektrolyse definitiv die bekannteste Reaktion zur Veredelung von Intermediaten. Beispiele mikrobielleru nd elektroorganischer Konversionen in Elektrobioraffinerien: A) für die Produktion von trans-3-Hexendisäure aus Glucose, das ein wichtiges Monomer fürdie Produktion von Nylon-6,6 ist (CE = Coulomb-Effizienz), [12,62] und B) fürdie Produktion von Drop-in-Kraftstoffadditiven aus fermentiertemMais (CSB = chemischer Sauerstoffbedarf;e nglisch:C hemicalo xygen demand (COD)). [69,70] Abbildung 4B zeigt den aktuell vorgestellten Elektrobioraffinerieprozess von Mais zu Drop-in-Kraftstoffadditiven,d er die Kolbe-Reaktion auf mikrobiell produzierte mittellangkettige Carbonsäuren anwendet.…”

“…[67,68] Diese erfolgt entweder durch Erzeugung von C-C-Bindungen zwischen aliphatischen organischen Säuren oder durch Kreuzkupplung mit anderen Reaktionspartnern wie Phenolen oder Thiofuranen. [73] Das Schlüsselintermediat fürdie Nylon-6,6-Produktion, trans-3-Hexendisäure, kann für 2.13 US$ kg À1 produziert werden, [12] und die Generierungvon Kraftstoffadditiven mit Ethanol und Acetat als Ausgangsstoffen gelang zu einem Preis von 1.37 US$ L À1 ). Zusätzlich kçnnen spezifischere Oxidationsreaktionen wie die Bildung von N-N-Bindungen [71] oder die elektrochemische Oxidation von Olefinen zu Enonen [59] einbezogen werden.…”

“…Beispiele mikrobielleru nd elektroorganischer Konversionen in Elektrobioraffinerien: A) für die Produktion von trans-3-Hexendisäure aus Glucose, das ein wichtiges Monomer fürdie Produktion von Nylon-6,6 ist (CE = Coulomb-Effizienz), [12,62] und B) fürdie Produktion von Drop-in-Kraftstoffadditiven aus fermentiertemMais (CSB = chemischer Sauerstoffbedarf;e nglisch:C hemicalo xygen demand (COD)). [73] Das Schlüsselintermediat fürdie Nylon-6,6-Produktion, trans-3-Hexendisäure, kann für 2.13 US$ kg À1 produziert werden, [12] und die Generierungvon Kraftstoffadditiven mit Ethanol und Acetat als Ausgangsstoffen gelang zu einem Preis von 1.37 US$ L À1 ). In beiden Fällen spielten die Preise fürdie elektrische Energie eine untergeordnete Rolle, jedoch kçnnen beträchtliche Kosten z.…”

Sustainable Carbon Sources and Renewable Energy: Challenges and Opportunities at the Interface of Catalysis and Reaction Engineering

“…Another example relates to the synthesis of an unsaturated nylon‐6,6 derivative. Therein, glucose was converted into muconic acid via fermentation followed by electrochemical hydrogenation to 3‐hexenedioic acid without prior isolation .…”