Alkylene glycols and their ethers are obtained by contacting a mixture of CO and H2 with a catalyst system at a pressure of at least 35 bars (e.g. 135-625 bars) and at a temperature of at least 180 DEG C (e.g. 180-250 DEG C). The catalyst system comprises ruthenium(III) acetylacetonate and rhodium (III) acetylacetonate dispersed in a low melting quaternary phosphonium or ammonium base or salt. Using this catalyst system hydrocarbon formation is largely avoided and the catalyst may be recycled without loss of activity.
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