cis,cis-Muconic acid: separation and catalysis to bio-adipic acid for nylon-6,6 polymerization

Vardon, Derek R.; Rorrer, Nicholas A.; Salvachúa, Davinia; Settle, Amy E.; Johnson, Christopher W.; Menart, Martin J.; Cleveland, Nicholas S.; Ciesielski, Peter N.; Steirer, K. Xerxes; Dorgan, John R.; Beckham, Gregg T.

doi:10.1039/c5gc02844b

Cited by 156 publications

(145 citation statements)

References 90 publications

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“…[12] p-ctMA was prepared by reacting p-ccMA (1 g) in water (60 mL) that was adjusted to pH 2b ya ddition of concentrated sulfuric acid and heated to 60 8Cf or 3h.A fter cooling to room temperature, the precipitated solid, p-ctMA, was collected by filtration and washed with small amount of cold water. [12] p-ctMA was prepared by reacting p-ccMA (1 g) in water (60 mL) that was adjusted to pH 2b ya ddition of concentrated sulfuric acid and heated to 60 8Cf or 3h.A fter cooling to room temperature, the precipitated solid, p-ctMA, was collected by filtration and washed with small amount of cold water.…”

Section: Methodsmentioning

confidence: 99%

“…[1][2][3][4][5] One such example is cis,cis-muconic acid (ccMA), as ix-carbon, polyunsaturated dicarboxylic acidt hat can be produced biologically from both sugars and lignin-derived feedstocks. [1,4,8,12] Both TPAa nd DMT are oxygenated aromatic compounds that retain the oxygen functionality inherit in ccMA and have substantial value within the polymer industry. [1] From here, ccMA may be (i)used directly as a polymerp recursor or isomerized to its trans,trans-form fori mprovedm aterial properties, [11] (ii)undergo selective reduction to 3-hexenedioic acid, (iii)undergo complete chemo-catalytic reduction of the polyunsaturated backbonet oa dipic acid, or (iv) undergo as eries of transformationst op roduce the closely related platform chemicals terephthalic acid (TPA) and its methyle ster analog, dimethyl terephthalate (DMT).…”

Section: Introductionmentioning

confidence: 99%

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Iodine‐Catalyzed Isomerization of Dimethyl Muconate

et al. 2018

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cis,cis-Muconic acid is a platform bio-based chemical that can be upgraded to drop-in commodity and novel monomers. Among the possible drop-in products, dimethyl terephthalate can be synthesized via esterification, isomerization, Diels-Alder cycloaddition, and dehydrogenation. The isomerization of cis,cis-dimethyl muconate (ccDMM) to the trans,trans-form (ttDMM) can be catalyzed by iodine; however, studies have yet to address (i) the mechanism and reaction barriers unique to DMM, and (ii) the influence of solvent, potential for catalyst recycle, and recovery of high-purity ttDMM. To address this gap, we apply a joint computational and experimental approach to investigate iodine-catalyzed isomerization of DMM. Density functional theory calculations identified unique regiochemical considerations owing to the large number of halogen-diene coordination schemes. Both transition state theory and experiments estimate significant barrier reductions with photodissociated iodine. Solvent selection was critical for rapid kinetics, likely because of solvent complexation with iodine. Under select conditions, ttDMM yields of 95 % were achieved in <1 h with methanol, followed by high purity recovery (>98 %) with crystallization. Lastly, post-reaction iodine can be recovered and recycled with minimal loss of activity. Overall, these findings provide new insight into the mechanism and conditions necessary for DMM isomerization with iodine to advance the state-of-the-art for bio-based chemicals.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Iodine‐Catalyzed Isomerization of Dimethyl Muconate

et al. 2018

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“…Among these products, certain parts of the chemicals, such as medium‐chain‐length polyhydroxyalkanoates ( mcl‐ PHA), 2‐pyrone‐4,6‐dicarboxylic acid (PDC), l ‐lactate (LLA), and cis, cis ‐muconic acid (MA) can be used as building blocks for thermo‐degradable or biodegradable plastics . Specifically, MA that is derived from upper molecular catechols can be converted into adipic acid (AdA) and terephthalic acid monomers by chemical catalysis . These monomers can be used as building blocks to produce 100% bio‐based PET and other materials .…”

Section: Nanocellulosementioning

confidence: 99%

High value‐added monomer chemicals and functional bio‐based materials derived from polymeric components of lignocellulose by organosolv fractionation

Zhang

Cai

Qin

et al. 2019

Biofuels Bioprod Bioref

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Organosolv fractionation (OF) is a promising method for lignocellulosic biomass biorefining to produce biofuels, biochemicals, and biomaterials. The fractionated polymeric components may be good feedstocks to produce bio‐based materials such as green polymers via chemical or biological conversion. However, related work to specify the bio‐based materials production via organosolv fractionation of lignocellulosic biomass is relatively scarce. In this work we have provided a comprehensive review of typical organosolv fractionation for isolating cellulose, hemicelluloses, and lignin, as well as the high value‐added monomer chemicals and functional materials derived from the fractionated components and their potential applications developed in recent years, primarily including the modified cellulose fibers for polymer materials, cellulose nanocrystals (CNCs), polysaccharide‐derived platform precursors for synthesis of bio‐based polymers, lignin‐derived dispersants, surfactants, carbon materials, and hemicellulose‐derived functional materials, etc. This work suggests that organosolv fractionation of lignocellulosic biomass could be a good entry to biomass refinery for high value‐added and functional materials production. However, there are still many challenges that should be overcome in terms of the fundamental, technical, and economic aspects for the organosolv fractionation process, formation of precursor compounds, synthesis of the bio‐based materials, design of product properties and functions, and the integration of the entire process. © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd

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“…cis, cis ‐Muconic acid (MA) is a chemical of recognized industrial value. Primarily it serves as a precursor for the synthesis of adipic acid by hydrogenation (Salvachúa et al, 2018; Vardon et al, 2016). MA can also be converted into caprolactam and terephthalic acid (Pleissner et al, 2019).…”

Section: Introductionmentioning

confidence: 99%

Limited life cycle and cost assessment for the bioconversion of lignin‐derived aromatics into adipic acid

Duuren

Wild

Starck

et al. 2020

Biotech & Bioengineering

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Lignin is an abundant and heterogeneous waste byproduct of the cellulosic industry, which has the potential of being transformed into valuable biochemicals via microbial fermentation. In this study, we applied a fast‐pyrolysis process using softwood lignin resulting in a two‐phase bio‐oil containing monomeric and oligomeric aromatics without syringol. We demonstrated that an additional hydrodeoxygenation step within the process leads to an enhanced thermochemical conversion of guaiacol into catechol and phenol. After steam bath distillation, Pseudomonas putida KT2440‐BN6 achieved a percent yield of cis, cis‐muconic acid of up to 95 mol% from catechol derived from the aqueous phase. We next established a downstream process for purifying cis, cis‐muconic acid (39.9 g/L) produced in a 42.5 L fermenter using glucose and benzoate as carbon substrates. On the basis of the obtained values for each unit operation of the empirical processes, we next performed a limited life cycle and cost analysis of an integrated biotechnological and chemical process for producing adipic acid and then compared it with the conventional petrochemical route. The simulated scenarios estimate that by attaining a mixture of catechol, phenol, cresol, and guaiacol (1:0.34:0.18:0, mol ratio), a titer of 62.5 (g/L) cis, cis‐muconic acid in the bioreactor, and a controlled cooling of pyrolysis gases to concentrate monomeric aromatics in the aqueous phase, the bio‐based route results in a reduction of CO2‐eq emission by 58% and energy demand by 23% with a contribution margin for the aqueous phase of up to 88.05 euro/ton. We conclude that the bio‐based production of adipic acid from softwood lignins brings environmental benefits over the petrochemical procedure and is cost‐effective at an industrial scale. Further research is essential to achieve the proposed cis, cis‐muconic acid yield from true lignin‐derived aromatics using whole‐cell biocatalysts.

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cis,cis-Muconic acid: separation and catalysis to bio-adipic acid for nylon-6,6 polymerization

Abstract: cis,cis-Muconic acid for downstream separation and catalytic upgrading to adipic acid for nylon-6,6 polymerization.

Cited by 156 publications

References 90 publications

Iodine‐Catalyzed Isomerization of Dimethyl Muconate

Iodine‐Catalyzed Isomerization of Dimethyl Muconate

High value‐added monomer chemicals and functional bio‐based materials derived from polymeric components of lignocellulose by organosolv fractionation

Limited life cycle and cost assessment for the bioconversion of lignin‐derived aromatics into adipic acid

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