Recent developments in catalytic reduction with H2 of glycerol, which is a by-product of biodiesel manufacture, and the involved chemistry are summarized and reviewed. There are more than ten potential C3 products of glycerol reduction. Among them, 1,2-propanediol can be obtained in very high yield and the production from glycerol is now commercialized. Production of 1,3-propanediol, allyl alcohol and propylene are now possible in > 60%, > 90% and > 80% yield, respectively. Key reaction steps are metal-catalyzed dehydrogenation/hydrogenation, acid-catalyzed dehydration, carbonyl-induced dehydration, metal-catalyzed direct hydrogenolysis and deoxydehydration. The 2-Propanol and small-ring compounds (oxetane, propylene oxide) cannot be produced from glycerol by combinations of these key reaction steps, and no catalytic system is known at present, although the conversion reactions have minus ∆G°.
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