Catalytic conversion of glycerol to value-added liquid chemicals

Abstract

Glycerol is one of the by-products of transesterification of fatty acids for the production of bio-diesel. Value-added products such as hydrogen, wood stabilizers and liquid chemicals from catalytic treatment of glycerol can improve the economics of the bio-diesel production process. Catalytic conversion of glycerol can be used for production of value-added liquid chemicals. In this work, a systematic study has been conducted to evaluate the effects of operating conditions on glycerol conversion to liquid chemical products in the presence of acid catalysts. Central composite design for response surface method was used to design the experimental plan. Experiments were performed in a fixed-bed reactor using HZSM-5, HY, silica-alumina and ã-alumina catalysts. The temperature, carrier gas flow rate and weight hourly space velocity (WHSV) were maintained in the range of 350-500 oC, 20-50 mL/min and 5.40-21.60 h -1, respectively. The main liquid chemicals detected in liquid product were acetaldehyde, acrolein, formaldehyde and hydroxyacetone. Under all experimental conditions complete glycerol conversion was obtained over silica-alumina and ã-alumina. A maximum liquid product yield of approximately 83 g/100g feed was obtained with these two catalysts when the operating conditions were maintained at 380 oC, 26 mL/min and 8.68 h-1. Maximum glycerol conversions of 100 wt% and 78.8 wt% were obtained in the presence of HY and HZSM-5 at temperature, carrier gas flow rate and WHSV of 470 oC, 26 mL/min and 8.68 h-1. HY and HZSM-5 produced maximum liquid product of 80.9 and 59.0 g/100 g feed at temperature of 425 and 470 oC, respectively.Silica-alumina produced the maximum acetaldehyde (~24.5 g/100 g feed) whereas ã-alumina produced the maximum acrolein (~25 g/100 g feed). Also, silica-alumina produced highest formaldehyde yield of 9g/100 g feed whereas HY produced highest acetol yield of 14.7 g/100 g feed. The effect of pore size of these catalysts was studied on optimum glycerol conversion and liquid product yield. Optimum conversion increased from 80 to 100 wt% and optimum liquid product increased from 59 to 83.3 g/100 g feed when the pore size of catalyst was increased from 0.54 in case of HZSM-5 to 0.74 nm in case of HY, after which the effect of pore size was minimal.