Production of 3-Methoxy,1,2,Propanediol and Hydroxyacetone by the Subcritical Hydrothermal Liquefaction of Glycerol

Date
2014-06
Authors
Jaffary, Bandar Ebraheem
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Faculty of Graduate Studies and Research, University of Regina
Abstract

Research on the use of crude glycerol, a byproduct of bio-diesel production has received strong interest within the last several years. The objective has been to add value to or utilize this byproduct, as a measure to remove one of the major obstacles encountered in the production and widespread application of bio-diesel. The present study was focused on the hydrothermal liquefaction of glycerol in subcritical water conditions for the production of 3-methoxy,1,2,propanediol and hydroxyacetone. The production of 3- methoxy, 1,2,propanediol was selected to be the major objective of this study because of its value as well as its importance in the medical sector. In the study, the molar ratio of water to glycerol in the feed to the process was in the range of 3 – 12 mol/mol. These experiments were performed at temperatures in the range of 200 – 325 oC, initial gauge pressure ranging from autogenous to 60 bar. The reaction retention time was recorded after the process had reached the desired temperature, which was typically in the range of 0 – 120 min. The liquid product was analyzed using GC-MS while an online GC was used to quantify the gas products. The results showed that as the temperature increased, the yield of 3-methoxy,1,2, propanediol increased until 225 oC before decreasing. Therefore, the optimum temperature for producing 3-methoxy,1,2, propanediol is 225 oC. Similarly, the yield of hydroxyacetone increased as the operating temperature increased until 250 oC and then decreased after this temperature. An increase in the retention time resulted in a decrease of the yield of 3-methoxy,1,2,propanediol while that of hydroxyacetone increased until 60 min then decreased. The optimum retention time for producing 3-methoxy,1,2, propanediol was 0 min. It was observed that the gas products started to appear at between 275 and 325 oC. The trend of the gas yield was: CO2>CO>H2 and zero yield for CH4 and C2H6. Furthermore, the optimum initial gauge pressure for producing 3-methoxy,1,2,propanediol and hydroxyacetone was 40 bar. On the other hand, the optimum molar feed ratio (water to glycerol) for 3-methoxy,1,2,propanediol and hydroxyacetone were 6 and 9, respectively. Two types of solid acid catalysts (H-ZSM-5 and γ–alumina) were investigated for the production of 3-methoxy,1,2, propanediol. It was observed that H-ZSM-5 inhibited the production of 3-methoxy,1,2, propanediol while γ–alumina increased the yield compared with the non-catalytic experiments. On the other hand, the yield of hydroxyacetone increased using the two acid catalysts with the trend: H-ZSM-5> γ–alumina> non-catalytic experiment. Compared with the non-catalytic experiments, the yields of the two target liquid products increased with γ–alumina within the range of catalyst weight used in the study (0.5 – 1 g). A non-catalytic kinetic study was performed using an empirical power-law rate model to interpret the kinetic data. Three temperatures (225, 275, 325 oC) at four different retention times (0, 60, 90, 120 min) were used to get the maximum glycerol conversion in the subcritical water condition. The feed molar ratio (water to glycerol) was fixed as 6 and the initial gauge pressure was kept autogenous in all of the kinetic experiments. The kinetic parameters (A, E, n) were regressed using NLREG software. The highest glycerol conversion in this study was observed at 325 oC as 65%. The values of the pre exponential factor, activation energy, and the overall reaction order were 1.61 min-1, 21.922 KJ/mol, and 3, respectively. The kinetic data were in a good fitness with the kinetic model with R2 of 90 %. The experimental and predicted rates were also in good agreement giving an AAD% of 10.9. The final form of the rate model with the substitution of the kinetic parameters is: −𝒓𝑨 = 𝒅𝑿𝑨 𝒅𝒕 = 𝟏. 𝟔𝟏 𝒆−𝟐𝟏𝟗𝟐𝟐/𝑹𝑻 ( 𝟏 − 𝑿𝑨)𝟑 .

Description
A Thesis Submitted to the Faculty of Graduate Studies and Research In Partial Fulfillment of the Requirements for the Degree of Master of Applied Science in Process Systems Engineering, University of Regina. xii, 87 p.
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