First-principles kinetic modeling in heterogeneous catalysis: an industrial perspective on best-practice, gaps and needs

Electronic structure calculations have emerged as a key contributor in modern heterogeneous catalysis research, though their application in chemical reaction engineering remains largely limited to academia. This perspective aims at encouraging the judicious use of first-principles kinetic models in industrial settings based on a critical discussion of present-day best practices, identifying existing gaps, and defining where further progress is needed

Hydrogen radical additions to unsaturated hydrocarbons and the reverse β-scission reactions: modeling of activation energies and pre-exponential factors

The group additivity method for Arrhenius parameters is applied to. hydrogen-addition to alkenes and alkynes and the reverse beta-scission reactions, an important famliy of reactions in thermal processes based on radical chemistry. A consistent set of group additive values for 33 groups is derived to calculate the activation energy and pre-exponential factor for a broad range of hydrogen addition reactions. Thee;group additive values are determined from CBS-QB3 ab-initio-calculated rate coefficients. A mean factor of deviation of only two between CBS-QB3 and experimental rate coefficients for seven reactions in the range 300-1000 K is found. Tunneling. coefficients for these reactions were found to be significant;below 400 K and a correlation accounting for tunneling is presented. Application of the obtained group additive values to predict the kinetics for a set of 11 additions and beta-scissions yields rate coefficients within a factor of 3.5 of the CBS-QB3 results except for two beta-scissions with severe steric effects. The mean factor of deviation with respect to experimental rate coefficients of 2.0 shows that the group additive method with tunneling corrections can accurately predict the kinetics and is at least as accurate as the most commonly used density functional methods. The constructed group additive model can hence be applied to predict the kinetics of hydrogen radical additions for a broad range of unsaturated compounds

Kinetics of alpha hydrogen abstractions in thiols, sulfides and thiocarbonyl compounds

Hydrogen abstraction reactions involving organosulfur compounds play an important role in many industrial, biological and atmospheric processes. Despite their chemical relevance, little is known about their kinetics. In this work a group additivity model is developed that allows predicting the Arrhenius parameters for abstraction reactions of alpha hydrogen atoms from thiols, alkyl sulfides, alkyl disulfides and thiocarbonyl compounds by carbon-centered radicals at temperatures ranging from 300 to 1500 K. Rate coefficients for 102 hydrogen abstractions were obtained using conventional transition state theory within the high-pressure limit. Electronic barriers were calculated using the CBS-QB3 method and the rate coefficients were corrected for tunneling and hindered rotation about the transitional bond. Group additivity values for 46 groups are determined. To account for resonance and hyperconjugative stabilization in the transition state, 8 resonance corrections were fitted to a set of 32 reactions. The developed group additivity scheme was validated using a test set containing an additional 30 reactions. The group additivity scheme succeeds in reproducing the rate coefficients on average within a factor of 2.4 at 300 K and 1.4 at 1000 K. Mean absolute deviations of the Arrhenius parameters amount to, respectively, 2.5 kJ mol(-1) for E-a and 0.13 for log A, both at 300 and 1000 K. This work hence illustrates that the recently developed group additivity methods for Arrhenius parameters extrapolate successfully to hetero-element containing compounds

Study of n-butanol conversion to butenes : effect of Si/Al ratio on activity, selectivity and kinetics

As bio-butanol is gaining more and more interest as a commercially available bioresource, the dehydration of this alcohol towards butenes and higher carbons gains more of interest. In general HZSM-5 has shown to be the most promising catalyst for this conversion. The role of the zeolite’s Si/Al ratio in the butanol dehydration reaction is still not fully understood. Experimental data obtained for a series of HZSM-5 with decreasing Si/Al ratio revealed an increase in activity of the catalyst per active site without affecting the selectivity profile. To understand the underlying effects, a microkinetic model was constructed for H-ZSM-5 with a Si/Al ratio of 25, based on literature DFT calculations, and the model was further modified by fitting the key parameters to the measured data at the four different temperatures studied in this work. This resulted in an adequate model for the dehydration of butanol across the evaluated temperature range of 503K to 533K. Investigation of the occurring mechanisms indicated a inhibiting effect due to the strong adsorption of di-n-butylether. This ‘poisoning’ of the catalyst surface resulted in a peculiar S-like curve for the conversion site time relation, which was also experimentally observed. This newly fitted base model was used to obtain more insight in the effect of the Si/Al ratio by implementing an additional H parameter, which is related to the adsorption strength of n-butanol in the base model. H varies between -4.8 to +11.3 kJ/mol and provides a good fit for Si/Al ratios ranging from 15 to 140. The higher dehydration rates observed with decreasing Si/Al can be traced back to an increase in adsorption strength resulting in an overall increase in surface coverage. The constant selectivity-conversion profile can be explained by a similar dependency of all elementary steps on the adsorption strength. The model developed in this study enables to simulate and understand the experimentally observed effects of temperature and Si/Al ratio on the n-butanol dehydration

Renewable butene production through dehydration reactions over nano-HZSM-5/γ-Al2O3 hybrid catalysts

The development of new, improved zeolitic materials is of prime importance to progress heterogeneous catalysis and adsorption technologies. The zeolite HZSM-5 and metal oxide γ-Al2O3 are key materials for processing bio-alcohols, but both have some limitations, i.e., HZSM-5 has a high activity but low catalytic stability, and vice versa for γ-Al2O3. To combine their advantages and suppress their disadvantages, this study reports the synthesis, characterization, and catalytic results of a hybrid nano-HZSM-5/γ-Al2O3 catalyst for the dehydration of n-butanol to butenes. The hybrid catalyst is prepared by the in-situ hydrothermal synthesis of nano-HZSM-5 onto γ-Al2O3. This catalyst combines mesoporosity, related to the γ-Al2O3 support, and microporosity due to the nano-HZSM-5 crystals dispersed on the γ-Al2O3. HZSM-5 and γ-Al2O3 being in one hybrid catalyst leads to a different acid strength distribution and outperforms both single materials as it shows increased activity (compared to γ-Al2O3) and a high selectivity to olefins, even at low conversion and a higher stability (compared to HZSM-5). The hybrid catalyst also outperforms a physical mixture of nano-HZSM-5 and γ-Al2O3, indicating a truly synergistic effect in the hybrid catalyst