Kinetics of Triazabicyclodecene-Catalyzed Canola Oil Conversion to Glycerol-free Biofuel Using Dimethyl Carbonate

Abstract

In this study, transesterification kinetics of canola oil with dimethyl carbonate (DMC) was investigated, intending to produce glycerol-free biofuel using triazabicyclodecene (TBD) as a catalyst. The triglyceride/DMC reaction in a stirred batch reactor produces a mixture of fatty acid methyl esters (FAMEs) and fatty acid glycerol carbonates (FAGCs), which are soluble in FAMEs and can then be used as a motor fuel. The main factors affecting the yield of biofuel, such as the molar ratio of oil/DMC, catalyst loading, reaction temperature, and reaction time, are discussed. A reaction mechanism has been proposed for the TBDcatalyzed transesterification. For the conversion of triglycerides, a second-order reaction rate with rate constants of 1.09 × 10 −2 , 1.65 × 10 −2 , and 2.30 × 10 −2 L mol −1 min −1 at 50, 60, and 70 °C, respectively, was determined from the regression of the experimental data. The corresponding value of activation energy was 36.36 kJ mol −1 . The maximum yield of 97.99% from transesterification of canola oil was obtained within 120 min.

Environmentally-Benign Dimethyl Carbonate-Mediated Production of Chemicals and Biofuels from Renewable Bio-Oil

“…Basic catalysts like KOH, sodium methoxide, sodium hydride, and some amines are most widely used for DMC-based transesterification [15,[38][39][40][41][42][43]. Table 2 shows the use of alkaline catalysts for DMC-based biodiesel production.…”

One-pot synthesis of polyunsaturated fatty acid amides with anti-proliferative properties

“…20 Reaction optimization along various parameters, including solvent (neat, THF, DMSO, pyridine, water, acetonitrile or mixtures), temperature (0 100 o C), reagent and catalyst (5-20 mol%) did not produce clean mixtures. The reaction was generally very slow even under the best conditions (4 days for 50% conversion in DMSO at 100 o C).…”

Synthesis of azo carbonate monomers and biocompatibility study of poly(azo-carbonate-urethane)s

“…[32][33][34] The resulting intermediate from the reaction of DMC with DBU seems to be more electrophilic than DMC so it can be more reactive towards moderate or weak nucleophiles. 26 Scheme 2 shows the reported mechanism 32,34 for the reaction of DMC with DBU. In this mechanism DBU is used as both, Brønsted and Lewis base.…”

“…35 Use of TBD in methoxycarbonylation reactions with DMC was reported without a clear explanation of the TBD catalysis mechanism. 26,34,36 To investigate if TBD also acts as a nucleophilic catalyst, a direct reaction between DMC and TBD was carried out (Scheme 3). The reaction was followed by GC-MS analysis of aliquots of the reaction mixture.…”

“…This work reveals the use of 1,5,7-triazabicyclo[4.4.0]dec-5ene (TBD) and 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU) as organic catalysts and have been successfully used as catalysts for transesterication reactions of DMC. 26 The bis-carbonate was used for a coupling reaction generating azo carbonate monomers followed by a polycondensation reaction with an aminoalcohol for the formation of non-isocyanate poly(azocarbonate-urethane)s. Finally, the biocompatibility properties of monomers 4 and 6 and polymers PCU 1 and PCU 2 were investigated by liver, kidney and colon histological analyses.…”