Catalytic Methanol Carbonylation for Acetic Acid Synthesis

Catalytic methanol carbonylation is the cornerstone of modern acetic acid manufacture, enabling the large-scale transformation of methanol and carbon monoxide into acetic acid under controlled pressure and temperature. In the prevailing industrial routes, methanol is first converted to methyl iodide, which then undergoes rhodium- or iridium-catalysed insertion of CO to form an acetyl metal intermediate. Subsequent hydrolysis releases acetic acid and regenerates the active catalyst. This homogeneous process achieves high selectivity and turnover frequencies, producing millions of tonnes of acetic acid annually for applications in polymers, solvents and food preservatives. Recent efforts have focused on enhancing catalyst stability, reducing reliance on halide promoters and exploring earth-abundant alternatives. Innovations include heterogenised rhodium complexes on porous supports, bimetallic systems that modify electronic properties to accelerate key steps such as oxidative addition, and vapour-phase processes free of toxic co-catalysts. Advances in kinetic analysis and operando spectroscopy have deepened mechanistic insight, guiding rational design of catalysts with improved resistance to deactivation and leaching. The global drive towards sustainable chemistry has also stimulated interest in recycling carbon monoxide derived from biomass or waste streams, positioning catalytic methanol carbonylation as a platform for greener acetic acid production.

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Catalytic Methanol Carbonylation for Acetic Acid Synthesis publication trend

The graph below shows the total number of articles in catalytic methanol carbonylation for acetic acid synthesis across all publications each year (not limited to Nature Index journals).

Technical terms

Carbonylation: the chemical insertion of carbon monoxide into organic substrates to form carbonyl-containing products.

Homogeneous catalysis: catalysis in which the active species and reactants reside in the same phase, typically liquid.

Heterogeneous catalysis: catalysis where the active species are confined to a separate phase, often a solid support, facilitating separation and reuse.

Oxidative addition: a step in which a metal centre inserts into a covalent bond, increasing its oxidation state and coordination number.

Turnover frequency (TOF): the number of catalytic cycles achieved per active site per unit time, indicating catalyst activity.

References

1. Study on Rh(I)/Ru(III) Bimetallic Catalyst Catalyzed Carbonylation of Methanol to Acetic Acid. Materials (2020).
2. Heterogenisation of a carbonylation catalyst on dispersible microporous polymer nanoparticles. Catalysis Science & Technology (2022).
3. Парофазне карбонілювання метанолу на каталізаторах NiCl 2 -CuCl 2 (Sn)/AC(кордієрит). Himia Fizika ta Tehnologia Poverhni (2020).