Carl Schietekat

Rapeseed oil methyl ester pyrolysis: On-line product analysis using comprehensive two-dimensional gas chromatography

Thermochemical conversion processes play a crucial role in all routes from fossil and renewable resources to base chemicals, fuels and energy. Hence, a fundamental understanding of these chemical processes can help to resolve the upcoming challenges of our society. A bench scale pyrolysis set-up has been used to study the thermochemical conversion of rapeseed oil methyl ester (RME), i.e. a mixture of fatty acid methyl esters. A GC×GC, equipped with both a flame ionization detector (FID) and a time-of-flight mass spectrometer (TOF-MS), allows quantitative and qualitative characterization of the reactor feed and product. Analysis of the latter is accomplished using a dedicated high temperature on-line sampling system. Temperature programmed analysis, starting at -40°C, permits effluent characterization from methane up to lignoceric acid methyl ester (C(25)H(50)O(2)), in a single run of the GC×GC. The latter combines a 100% dimethylpolysiloxane primary column with a 50% phenyl polysilphenylene-siloxane secondary column. Modulation is started when the oven temperature reaches 40°C, thus dividing the chromatogram in a conventional 1D and a comprehensive 2D part. The proposed quantification approach allows to combine the quantitative GC×GC analysis with 2 other on-line 1D GC analyses, resulting in a complete and detailed product composition including the measurement of CO, CO(2), formaldehyde and water. The GC×GC reveals that the product stream contains a huge variety of valuable products, such as linear alpha olefins, unsaturated esters and aromatics, that could not have been identified and quantified accurately with conventional 1D GC because of peak overlap.

GPU based simulation of reactive mixtures with detailed chemistry in combination with tabulation and an analytical Jacobian

Abstract Incorporating detailed chemistry in solvers still remains a daunting and intractable task due to the prohibitive computational cost. However the combination of advanced mathematical solution techniques such as tabulation and calculating the analytical Jacobian in combination with efficient computational techniques that use the graphical processing unit (GPU) to do calculations can drastically speedup the simulation. These techniques are not mutually exclusive as is demonstrated for an ordinary differential equation (ODE) problem describing the classical adiabatic, constant-volume ignition of an equimolar methane/air mixture. Acceleration with up to a factor 120 can be obtained with the new algorithm compared to the algorithm employed in the reference solver. Maximum speedup is obtained in the case where the analytical Jacobian and the rates are calculated using the GPU when using intrinsic compiler functions to calculate transcendental functions which are used to calculate thermodynamic and kinetic coefficients. This is because the GPU can calculate transcendental functions significantly more efficient than a CPU.