A critical review of the production of hydroxyaromatic carboxylic acids as a sustainable method for chemical utilisation and fixation of CO<sub>2</sub>

Mohammad, Omar; Onwudili, Jude A.; Yuan, Qingchun

doi:10.1039/d2su00105e

Cited by 8 publications

(4 citation statements)

References 88 publications

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“…SA is industrially produced via the Kolbe-Schmidt reaction between phenol and CO2. 34 Therefore, it was possible to reproduce SA and poly-MBDO from phenol. Phenol is used as the starting material for the synthesis of various fine chemicals.…”

Section: Discussionmentioning

confidence: 99%

Carbon-Resource Recovery from Vinyl Polymers of Cyclic Ketene Acetal Esters Using High-Temperature Water

Kohsaka,

Kazama,

Matsuo

et al. 2024

Preprint

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Vinyl polymer prepared from 2-methylene-4H-benzo[d][1,3]dioxin-4-one (MBDO), a cyclic ketene acetal ester, is a chemically recyclable polymer that is hydrolyzed to salicylic acid (SA) and acetic acid (AA). Despite this potential, the polymer, poly-MBDO required a strong acid or base in organic solvent for the hydrolysis. In this study, we report the quantitative conversion of poly-MBDO to phenol by treatment in high-temperature water. Hydrolysis of poly-MBDO afforded SA, which underwent rapid decarboxylation to phenol. For example, poly-MBDO quantitatively afforded phenol upon heating in water at 300 °C for 5 min and freeze-drying. Although the hydrolysis of the main chain was incomplete, the products were volatile and removed by drying the reaction mixture, leaving the residue of pure phenol. Since SA is industrially synthesized from phenol and CO2, the synthesis of poly-MBDO from phenol is in principle possible. The quantitative conversion of poly-MBDO to phenol can also be considered as upcycling, since phenol is a raw material for various fine chemicals.

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Section: Discussionmentioning

confidence: 99%

Carbon-Resource Recovery from Vinyl Polymers of Cyclic Ketene Acetal Esters Using High-Temperature Water

Kohsaka,

Kazama,

Matsuo

et al. 2024

Preprint

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“…Among HACAs, salicylic acid is particularly of huge commercial interest [ 23 ]. Recent research suggests that salicylic acid and acetic acid could develop recyclable vinyl polymers, reducing reliance on polymer vinyl chloride (PVC), which has an annual global production of 44.2 million tonnes [ 24 ].…”

Section: Introductionmentioning

confidence: 99%

“…Yet, none of the developed methods have been applied at an industrial scale due to their limitations such as high production costs and low yields. More details and industrial limitations of those methods can be found in a recent review paper [ 23 ].…”

Section: Introductionmentioning

confidence: 99%

Potential Large-Scale CO2 Utilisation for Salicylic Acid Production via a Suspension-Based Kolbe–Schmitt Reaction in Toluene

Mohammad,

Onwudili,

Yuan

2024

Molecules

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Conversion of CO2 into organic chemicals offers a promising route for advancing the circularity of carbon capture, utilisation, and storage in line with the international 2050 Net Zero agenda. The widely known commercialised chemical fixation of CO2 into organic chemicals is the century-old Kolbe–Schmitt reaction, which carboxylates phenol (via sodium phenoxide) into salicylic acid. The carboxylation reaction is normally carried out between the gas–solid phases in a batch reactor. The mass and heat transfer limitations of such systems require rather long reaction times and a high pressure of CO2 and are often characterised by the low formation of undesirable side products. To address these drawbacks, a novel suspension-based carboxylation method has been designed and carried out in this present study, where sodium phenoxide is dispersed in toluene to react with CO2. Importantly, the addition of phenol played a critical role in promoting the stoichiometric conversion of phenoxide to salicylic acid. Under the optimal conditions of a phenol/phenoxide molar ratio of 2:1 in toluene, a reaction temperature of 225 °C, a CO2 pressure of 30 bar, a reaction time of 2 h, and stirring at 1000 rpm, an impressive salicylic acid molar yield of 92.68% has been achieved. The reaction mechanism behind this has been discussed. This development provides us with the potential to achieve a carboxylation reaction of phenoxide with CO2 more effectively in a continuous reactor. It can also facilitate the large-scale fixing of CO2 into hydroxy aromatic carboxylic acids, which can be used as green organic chemical feedstocks for making various products, including long-lived polymeric materials.

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“…This aromatic carboxylic acid is mostly used in the agricultural, medicinal, and cosmetic industries, while it holds its highest value in the production of acetylsalicylic and cosmetic industries, while it holds its highest value in the production of acetylsalicylic acid, an anti-inflammatory drug better known as aspirin [7,8]. Preparation of salicylic acid through carboxylation of phenol, a traditional Kolbe-Schmitt reaction, has been a standard procedure for over 100 years, and since then various Kolbe-Schmitt-type reactions have been used for the production of various aromatic hydroxyl acids [9,10]. Phenol, a lignin-derived model compound, is a great representative of other more complex aromatics and, as such, poses great potential for sustainable production of aromatic value-added products from renewable and currently poorly valorized biomass lignin.…”

Section: Introductionmentioning

confidence: 99%

Sustainable CO2 Fixation onto Bio-Based Aromatics

Kojčinović,

Likozar,

Grilc

2023

Sustainability

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Carboxylation reactions using carbon dioxide (CO2) as a reactant to produce new C-C bonds represent one of the most promising routes in carbon capture and utilization practices, which yield higher-atom and energy-efficient products. Kolbe–Schmitt-type reactions represent the carboxylation of aromatic compounds to their carboxylic acid derivatives. This study was the first and only to systematically investigate, thoroughly explain preparation procedures, and minutely describe the analytical methods of Kolbe–Schmitt and Marasse carboxylation of phenol. Most importantly, this study provides guidelines for the utilization of state-of-the-art technology in this century-old yet not sufficiently described reaction system. Kolbe–Schmitt carboxylation of phenol was found to be possible using sodium hydroxide (NaOH), potassium hydroxide (KOH), and sodium carbonate (Na2CO3), while the Marasse method was active only with potassium carbonate (K2CO3) as a reactant. The formation of metal phenoxide is the rate-determining step, which, however, could be more efficiently prepared under reflux. A new, simple, and repeatable HPLC method was described to identify and quantify all possible products of mono- and dicarboxylated phenols. It was found that all procedures result in the highest selectivity for salicylic acid (SA), followed by minor amounts of 4-hydroxybenzoic acid (4HBA) and 4-hydroxyisophthalic acid (4HiPh).

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A critical review of the production of hydroxyaromatic carboxylic acids as a sustainable method for chemical utilisation and fixation of CO₂

Abstract: Hydroxyaromatic carboxylic acids (HACAs) such as salicylic acids, hydroxynapthoic acids and their halogenated derivatives are essential feedstocks for the pharmaceutical, dye, fragrance, cosmetic and food industries. Large-scale production of HACAs...

Cited by 8 publications

References 88 publications

Carbon-Resource Recovery from Vinyl Polymers of Cyclic Ketene Acetal Esters Using High-Temperature Water

Carbon-Resource Recovery from Vinyl Polymers of Cyclic Ketene Acetal Esters Using High-Temperature Water

Potential Large-Scale CO2 Utilisation for Salicylic Acid Production via a Suspension-Based Kolbe–Schmitt Reaction in Toluene

Sustainable CO2 Fixation onto Bio-Based Aromatics

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A critical review of the production of hydroxyaromatic carboxylic acids as a sustainable method for chemical utilisation and fixation of CO2

Abstract: Hydroxyaromatic carboxylic acids (HACAs) such as salicylic acids, hydroxynapthoic acids and their halogenated derivatives are essential feedstocks for the pharmaceutical, dye, fragrance, cosmetic and food industries. Large-scale production of HACAs...

Cited by 8 publications

References 88 publications

Carbon-Resource Recovery from Vinyl Polymers of Cyclic Ketene Acetal Esters Using High-Temperature Water

Carbon-Resource Recovery from Vinyl Polymers of Cyclic Ketene Acetal Esters Using High-Temperature Water

Potential Large-Scale CO2 Utilisation for Salicylic Acid Production via a Suspension-Based Kolbe–Schmitt Reaction in Toluene

Sustainable CO2 Fixation onto Bio-Based Aromatics

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A critical review of the production of hydroxyaromatic carboxylic acids as a sustainable method for chemical utilisation and fixation of CO₂