Abstract
Crude glycerol from biodiesel production is a biobased material capable of co-producing biofuels and chemicals. This study aimed to develop a line of Ni catalysts supported on cerium–magnesium (Ce–Mg) to improve the process efficiency of glycerol hydrogenolysis for ethanol and 1,2-propanediol (1,2-PDO). Results showed that catalytic activity was greatly improved by changing the preparation method from impregnation to deposition precipitation (DP), and by adjusting calcination temperatures. Prepared via DP, the catalysts of 25 wt % Ni supported on Ce–Mg (9:1 mol/mol) greatly improved the effectiveness in glycerol conversion while maintaining the selectivities to ethanol and 1,2-PDO. Calcination at 350 °C provided the catalysts better selectivities of 15.61% to ethanol and 67.93% to 1,2-PDO. Increases in reaction temperature and time improved the conversion of glycerol and the selectivity to ethanol, but reduced the selectivity to 1,2-PDO. A lower initial water content led to a higher conversion of glycerol, but lower selectivities to ethanol and 1,2-PDO. Higher hydrogen application affected the glycerol conversion rate positively, but the selectivities to ethanol and 1,2-PDO negatively. A comparison to the commercial Raney® Ni catalyst showed that the Ni/Ce–Mg catalyst developed in this study showed a better potential for the selective co-production of ethanol and 1,2-PDO from glycerol hydrogenolysis.
Highlights
Concerns of long term economic and energy securities, emergence of global warming and climate change have drastically increased the interest globally in utilizing renewable resources to produce fuels and valuable chemicals [1,2,3]
We reported a novel catalyst for the selective co-production of ethanol and 1,2-PDO from glycerol hydrogenolysis using a nickel (Ni) catalyst supported on cerium–magnesium (Ce–Mg) at a 9:1 Ce–Mg molar ratio
Resulted in a decline of both specific surface area and pore volume, and an increase in pore diameter. These properties remained approximately the same with a calcination temperature increase to 650 ◦ C. These observations are in agreement with others using supported Ni catalysts [27,28] and a deposition precipitation (DP)-prepared zirconia-supported Cu catalyst [26]
Summary
Concerns of long term economic and energy securities, emergence of global warming and climate change have drastically increased the interest globally in utilizing renewable resources to produce fuels and valuable chemicals [1,2,3]. The renewable alternative of diesel fuel [4], is typically produced from plant oils or animal fats via transesterification with an alcohol, usually methanol, under the aid of a catalyst and appropriate process conditions [4,5,6]. Based on the chemical reaction stoichiometry, approximately 10 kg of crude glycerol is produced for 100 kg of oil or fat feedstock. Biodiesel production has been increased dramatically in the past decade worldwide. Biodiesel production in the United States reached 1.568 billion gallons or 5.83 million m3 in 2016 [7], which yielded approximately 52 million kg of crude glycerol. US EIA has projected that worldwide biodiesel production is to rise to 33 million m3 by 2018 [8], which accounts for approximately
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