BACKGROUND Hydrogenolysis of glycerol to glycols in continuous flow three phase reactors is of practical importance due to the need to give value to huge amounts of surplus glycerol. Thermodynamic and kinetic aspects must be revised for a proper design. The system was studied in a trickle‐bed reactor using copper chromite and Cu/Al2O3 as catalysts. RESULTS Phase equilibrium and flow pattern were verified. Solid, liquid and gas phases were present, with the liquid phase in ‘trickling’ flow. Catalysts were characterized by inductively coupled plasma (ICP), nitrogen sortometry, X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction (XRD), temperature programmed reduction (TPR) and pyridine thermal programmed desorption (TPD). The average reaction rate was found to be practically constant under different process conditions. A theoretical analysis indicated that the resistance to the transfer of hydrogen from the gas to the liquid phase dominated the overall kinetics. Selectivity to 1,2‐propanediol varied with temperature, with a maximum at 230 °C (97%). Selectivity was a function of the catalyst acidity. When the pressure was increased the selectivity to 1,2‐propanediol was increased, up to 97% at 14 bar. Higher pressures did not modify this value. CONCLUSIONS Optimum reaction conditions for maximum selectivity to 1,2‐propanediol with Cu‐based catalysts are 230 °C and 14 bar. System kinetics are, however, dominated by the gas–liquid mass transfer resistance. © 2017 Society of Chemical Industry
CATALYSTS. The glycerol hydrogenolysis reaction was performed in a continuous flow trickle bed reactor using a water glycerol feed and both copper chromite and Cu/Al 2 O 3 catalysts. The commercial copper chromite had a higher activity than the laboratory prepared Cu/Al 2 O 3 and was used for most of the tests. Propylene glycol was the main product with both catalysts, acetol being the main by-product. It was found that temperature is the main variable influencing the conversion of glycerol. When the state of the glycerol-water reactant mixture was completely liquid, at temperatures lower than 190 °C, conversion was low and deactivation was observed. At reaction temperatures of 210-230 °C the conversion of glycerol was complete and the selectivity to propylene glycol was stable at about 60-80% all throughout the reaction time span of 10 h, regardless of the hydrogen pressure level (1 to 20 atm). These optimal values could not be improved significantly by using other different reaction conditions or increasing the catalyst acidity. At higher temperatures (245-250 °C) the conversion was also 100%. Under reaction conditions at which copper chromite suffered deactivation, light by-products and surface deposits were formed. The deposits could be completely burned at 250 °C and the catalyst activity fully recovered.
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