Efficient production of adipic acid from 2-methoxycyclohexanone by aerobic oxidation with a phosphotungstic acid catalyst

Hatakeyama, Kosuke; Nakagawa, Yoshinao; Tamura, Masazumi; Tomishige, Keiichi

doi:10.1039/d0gc01277g

Cited by 19 publications

(28 citation statements)

References 89 publications

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“…This can be the subject of further research to improve the kinetic understanding of the overall guaiacol ECH pathways. On a side note, 2-methoxycyclohexanone can be used as a precursor for adipic acid production, the monomer for nylon or polyurethane, via aerobic oxidation with phosphotungstic acid catalyst …”

Section: Resultsmentioning

confidence: 99%

Guaiacol Hydrogenation in Methanesulfonic Acid Using a Stirred Slurry Electrocatalytic Reactor: Mass Transport and Reaction Kinetics Aspects

Wijaya

Putra

Smith

et al. 2021

ACS Sustainable Chem. Eng.

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The electrocatalytic reduction of guaiacol, a lignin model compound, is investigated in a stirred slurry electrocatalytic reactor (SSER) under mild conditions (1 atm, 30−60 °C). Methanesulfonic acid (MSA) is used as an electrolyte due to its ecofriendly properties along with comparable ionic conductivity to the mineral acids (e.g., sulfuric acid and perchloric acid). Mass transport and kinetic aspects are investigated combining the experimental results obtained under either galvanostatic or potentiostatic control with reaction network kinetic models. The reactant mass transport rate to the catalyst particle surface, together with the collision rates among catalyst particles and the current collector, respectively, has a significant effect on guaiacol conversion and Faradaic efficiency. Therefore, optimum stirring is necessary to ensure good electric contact in the catalyst bed slurry to achieve substantial electrocatalytic hydrogenation (ECH) reaction rates. In the absence of mass transfer limitation, reaction network kinetic modeling based on the Langmuir−Hinshelwood mechanism was performed and validated by the experimental data. Rate constants and activation energies were calculated, and it was found that phenol hydrogenation was the fastest reaction, while 2methoxycyclohexanol demethoxylation was the slowest in the overall guaiacol ECH network. Furthermore, we show that the SSER can be operated at industrially relevant cathode superficial current densities (>100 mA cm −2 ), thereby, opening new and practical possibilities for the sustainable valorization of biomass-derived compounds.

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Section: Resultsmentioning

confidence: 99%

Guaiacol Hydrogenation in Methanesulfonic Acid Using a Stirred Slurry Electrocatalytic Reactor: Mass Transport and Reaction Kinetics Aspects

Wijaya

Putra

Smith

et al. 2021

ACS Sustainable Chem. Eng.

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“…Because of the enormous use of petroleum, hydrogen and nitric acid in the current process, the production of adipic acid from biomass has been intensively investigated in these days. Other production methods of adipic acid from biomass include (i) conversion of hydrocarbons produced by BTL (biomass to liquid; combination of biomass gasification and Fischer-Tropsch synthesis) [77] in petrochemical processes, (ii) production of K-A oil by reduction of biomass pyrolysis oil (bio-oil) [78][79][80][81][82][83], (iii) direct production of adipic acid by fermentation [84], (iv) hydrodeoxygenation of sugar acids produced by oxidation of sugars [85][86][87][88][89][90][91][92], (v) extension of carbon chain of C5 biomass-derived platform chemicals such as γ-valerolactone by hydroformylation or carboxylation [93][94][95][96], and (vi) oxidative cleavage of 1,2-difunctionalized cyclohexanes produced by reduction of bio-oil [97][98][99][100]. Low yield from raw biomass (methods (i), (ii), (iii) and (vi)) and large number of steps (methods (i), (ii), (9) (v) and (vi)) are the main problems of these methods.…”

Section: Comparison With Systems Using Other Biomass-derived Substratesmentioning

confidence: 99%

Reductive Conversion of Biomass-Derived Furancarboxylic Acids with Retention of Carboxylic Acid Moiety

Nakagawa

Yabushita

Tomishige

2021

Trans. Tianjin Univ.

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Catalytic reduction systems of 2-furancarboxylic acid (FCA) and 2,5-furandicarboxylic acid (FDCA) with H2 without reduction of the carboxyl groups are reviewed. FCA and FDCA are produced from furfural and 5-hydroxymethylfurfural which are important platform chemicals in biomass conversions. Furan ring hydrogenation to tetrahydrofuran-2-carboxylic acid (THFCA) and tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) easily proceeds over Pd catalysts. Hydrogenolysis of one C–O bond in the furan ring produces 5-hydroxyvaleric acid (5-HVA) and 2-hydroxyadipic acid. 2-Hydroxyvaleric acid is not produced in the reported systems. 5-HVA can be produced as the lactone form (δ-valerolactone; DVL) or as the esters depending on the solvent. These reactions proceed over Pt catalysts with good yields (~ 70%) at optimized conditions. Hydrogenolysis of two C–O bonds in the furan ring produces valeric acid and adipic acid, the latter of which is a very important chemical in industry and its production from biomass is of high importance. Adipic acid from FDCA can be produced directly over Pt-MoOx catalyst, indirectly via hydrogenation and hydrodeoxygenation as one-pot reaction using the combination of Pt and acid catalysts such as Pt/niobium oxide, or indirectly via two-step reaction composed of hydrogenation catalyzed by Pd and hydrodeoxygenation catalyzed by iodide ion in acidic conditions. Only the two-step method can give good yield of adipic acid at present.

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“…[127] Very recently, Kosuke and coworkers successfully prepared AA from bio-based guaiacol through the intermediate of 2-methoxycyclohexanone (2-MCO) by aerobic oxidation using phosphotungstic acid (H 3 PW 12 O 40 ) catalyst. [128] For the first step, Pd-based catalysts have been shown to be effective in selective hydrogenation of phenolic compounds and the conversion of guaiacol to 2-MCO over Pd/ HAP catalyst has been actually reported with 98 % high selectivity. [129] Analogously, the catalytic reduction of guaiacol to 2-MCO with formic acid as reducing agent over Pd/C has been also realized.…”

Section: Preparation Of Adipic Acid From Guaiacol and Catecholmentioning

confidence: 99%

“…Guaiacol, one of the central elements of softwood lignin, is a promising natural resource with great application and significance in industrial production [127] . Very recently, Kosuke and co‐workers successfully prepared AA from bio‐based guaiacol through the intermediate of 2‐methoxycyclohexanone (2‐MCO) by aerobic oxidation using phosphotungstic acid (H 3 PW 12 O 40 ) catalyst [128] . For the first step, Pd‐based catalysts have been shown to be effective in selective hydrogenation of phenolic compounds and the conversion of guaiacol to 2‐MCO over Pd/HAP catalyst has been actually reported with 98 % high selectivity [129] .…”

Section: Preparation Of Adipic Acid From Phenolic Compoundsmentioning

confidence: 99%

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Sustainable Routes for the Synthesis of Renewable Adipic Acid from Biomass Derivatives

Lang

2021

ChemSusChem

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Adipic acid (AA) is a key industrial dicarboxylic acid intermediate used in nylon manufacturing. Unfortunately, the traditional process technology is accompanied by serious environmental pollution. Given the growing demand for adipic acid and the desire to reduce its negative impact on the environment, considerable efforts have been devoted to developing more green and friendly routes. This Review is focused on the latest advances in the sustainable preparation of AA from biomassbased platform molecules, including 5-hydroxymethylfufural, glucose, γ-valerolactone, and phenolic compounds, through biocatalysis, chemocatalysis, and the combination of both.Additionally, the development of state-of-the-art catalysts for different catalytic systems systematically is discussed and summarized, as well as their reaction mechanisms. Finally, the prospects for all preparation routes are critically evaluated and key technical challenges in the development of green and sustainable processes for the manufacture of AA are highlighted. It is hoped that the green adipic acid synthesis pathways presented can provide insights and guidance for further research into other industrial processes for the production of nylon precursors in the future.

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Efficient production of adipic acid from 2-methoxycyclohexanone by aerobic oxidation with a phosphotungstic acid catalyst

Abstract:
A stable H₃PW₁₂O₄₀ catalyst can selectively convert 2-methoxycyclohexanone to adipic acid and methanol with O₂ as an oxidant in water.

Cited by 19 publications

References 89 publications

Guaiacol Hydrogenation in Methanesulfonic Acid Using a Stirred Slurry Electrocatalytic Reactor: Mass Transport and Reaction Kinetics Aspects

Guaiacol Hydrogenation in Methanesulfonic Acid Using a Stirred Slurry Electrocatalytic Reactor: Mass Transport and Reaction Kinetics Aspects

Reductive Conversion of Biomass-Derived Furancarboxylic Acids with Retention of Carboxylic Acid Moiety

Sustainable Routes for the Synthesis of Renewable Adipic Acid from Biomass Derivatives

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Efficient production of adipic acid from 2-methoxycyclohexanone by aerobic oxidation with a phosphotungstic acid catalyst

Abstract: A stable H3PW12O40 catalyst can selectively convert 2-methoxycyclohexanone to adipic acid and methanol with O2 as an oxidant in water.

Cited by 19 publications

References 89 publications

Guaiacol Hydrogenation in Methanesulfonic Acid Using a Stirred Slurry Electrocatalytic Reactor: Mass Transport and Reaction Kinetics Aspects

Guaiacol Hydrogenation in Methanesulfonic Acid Using a Stirred Slurry Electrocatalytic Reactor: Mass Transport and Reaction Kinetics Aspects

Reductive Conversion of Biomass-Derived Furancarboxylic Acids with Retention of Carboxylic Acid Moiety

Sustainable Routes for the Synthesis of Renewable Adipic Acid from Biomass Derivatives

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Resources

About

Abstract:
A stable H₃PW₁₂O₄₀ catalyst can selectively convert 2-methoxycyclohexanone to adipic acid and methanol with O₂ as an oxidant in water.