Fluorspar to fluorochemicals upon low-temperature activation in water

Immo Klose, Calum Patel, Anirban Mondal, Andrew Schwarz, Gabriele Pupo and Véronique Gouverneur ()
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Immo Klose: Chemistry Research Laboratory
Calum Patel: Chemistry Research Laboratory
Anirban Mondal: Chemistry Research Laboratory
Andrew Schwarz: FluoRok
Gabriele Pupo: FluoRok
Véronique Gouverneur: Chemistry Research Laboratory

Nature, 2024, vol. 635, issue 8038, 359-364

Abstract: Abstract The dangerous chemical hydrogen fluoride sits at the apex of the fluorochemical industry, but the substantial hazards linked to its production under harsh conditions (above 300 degrees Celsius) and transport are typically contracted to specialists. All fluorochemicals for applications, including refrigeration, electric transportation, agrochemicals and pharmaceuticals, are prepared from fluorspar (CaF2) through a procedure that generates highly dangerous hydrogen fluoride1–5. Here we report a mild method to obtain fluorochemicals directly from fluorspar, bypassing the necessity to manufacture hydrogen fluoride. Acid-grade fluorspar (more than 97 per cent CaF2) is treated with the fluorophilic Lewis acid boric acid (B(OH)3) or silicon dioxide (SiO2), in the presence of oxalic acid, a Brønsted acid that is highly effective for Ca2+ sequestration. This scalable process carried out in water at low temperature (below 50 degrees Celsius) enables access to widely used fluorochemicals, including tetrafluoroboric acid, alkali metal fluorides, tetraalkylammonium fluorides and fluoro(hetero)arenes. The replacement of oxalic acid with sulfuric acid gave comparable results for B(OH)3, but was not as effective when the fluorophilic Lewis acid was SiO2. A similar process also works with the lower-purity metspar. The production of fluorochemicals directly from fluorspar offers the possibility of decentralized manufacturing—an attractive model for the fluorochemical industry. With the renewed interest in innovative methods to synthesize oxalic acid via carbon dioxide capture and biomass6,7, and the challenges posed by our dependence on fossil fuels for sulfur and therefore sulfuric acid supply8,9, our technology may represent a departure towards a sustainable fluorochemical industry.

Date: 2024
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DOI: 10.1038/s41586-024-08125-1

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