Kinetic Modelling of the Hydrosilylation Reaction of Co2 Using Iridium (III) Complex Catalyst
Abdallah Al-Shammari , أولاد يبو حبيب الله بوسن
كلية الهندسة-جامعة الملك فهد للبترول والمعادن · السعودية
The valorization of carbon dioxide, which is a major green-house gas, has been studied in this report. The higher global demand for energy has increased the amount of the carbon dioxide released into the atmosphere from 275 ppm before the industrial revolution to 375 ppm in the year 2000 and 400 ppm in the year 2015. The further increase in the emitted carbon dioxide gave rise to one degree rise in the average temperature of the earth between the year 1960 and 2010 and 0.3 degree rise from 2010 to 2015.Catalytic CO2 hydrosilylation is a thermodynamically favored chemical process that could be potentially applied to large-scale transformations of this greenhouse gas. There have been an increasing number of experimental studies during the last decade regarding metal-catalyzed CO2 hydrosilylation processes. Ruthenium and Iridium catalysts are the first examples of catalytic systems used for CO2 hydrosilylation. Presently, there are several examples of other catalysts, including transition metal species acting alone or together with B(C6F5)3 and organocatalysts which are able to perform this reaction.In the hydrosilylation reaction, a relatively cheap silicon compound, 1,1,1,3,5,5,5-heptamethyl trisiloxane (HMTS), was catalytically converted to silylformate, which can be hydrolyzed to a more important compound, i.e. formic acid. The study has focused basically on two type of the Iridium (III) complex type [Ir(H)(CF3SO3)(NSiN)(coe)] (Catalyst 1) and [Ir(H)(CF3OCO)(NSiN)(coe)] (Catalyst 2) (NSiN = bis(pyridine-2-yloxy)methylsilyl, coe = cyclooctene) for the selective formation of silylformate by solvent free hydrosilylation of CO2 with 1,1,1,3,5,5,5-heptamethyltrisiloxane (HMTS). The activity of this catalytic system depends on the reaction temperature and the CO2-pressure. This work includes a kinetic study at variable temperature (from 25 oC to 75 oC) and pressure (from 1 bar to 8 bar) together with a kinetic modelling of this catalytic reaction. The best catalytic performances have been achieved at 75 oC and 8 bar of CO2.The Arrhenius equation was used for the kinetic modelling and non-linear regression of the experimental data used in predicting the kinetic parameters i.e. rate constant and the activation energy. The average activation energies estimated for the catalyst 1 and 2 were 72.1 kJ/mol and 47.5 kJ/mol respectively, thereby giving an indication that catalyst 2 is more efficient than catalyst 1.