Sergio Gonzalez-Cortes

The Catalyst Selectivity Index (CSI): A Framework and Metric to Assess the Impact of Catalyst Efficiency Enhancements upon Energy and CO2 Footprints

Heterogeneous catalysts are not only a venerable part of our chemical and industrial heritage, but they also occupy a pivotal, central role in the advancement of modern chemistry, chemical processes and chemical technologies. The broad field of catalysis has also emerged as a critical, enabling science and technology in the modern development of “Green Chemistry”, with the avowed aim of achieving green and sustainable processes. Thus a widely utilized metric, the environmental E factor—characterizing the waste-to-product ratio for a chemical industrial process—permits one to assess the potential deleterious environmental impact of an entire chemical process in terms of excessive solvent usage. As the many (and entirely reasonable) societal pressures grow, requiring chemists and chemical engineers not only to develop manufacturing processes using new sources of energy, but also to decrease the energy/carbon footprint of existing chemical processes, these issues become ever more pressing. On that road to a green and more sustainable future for chemistry and energy, we note that, as far as we are aware, little effort has been directed towards a direct evaluation of the quantitative impacts that advances or improvements in a catalyst’s performance or efficiency would have on the overall energy or carbon (CO2) footprint balance and corresponding greenhouse gas (GHG) emissions of chemical processes and manufacturing technologies. Therefore, this present research was motivated by the premise that the sustainability impact of advances in catalysis science and technology, especially heterogeneous catalysis—the core of large-scale manufacturing processes—must move from a qualitative to a more quantitative form of assessment. This, then, is the exciting challenge of developing a new paradigm for catalysis science which embodies—in a truly quantitative form—its impact on sustainability in chemical, industrial processes. Towards that goal, we present here the concept, definition, design and development of what we term the Catalyst Sensitivity Index (CSI) to provide a measurable index as to how efficiency or performance enhancements of a heterogeneous catalyst will directly impact upon the fossil energy consumption and GHG emissions balance across several prototypical fuel production and conversion technologies, e.g. hydrocarbon fuels synthesized using algae-to-biodiesel, algae-to-jet biofuel, coal-to-liquid and gas-to-liquid processes, together with fuel upgrading processes using fluidized catalytic cracking of heavy oil, hydrocracking of heavy oil and also the production of hydrogen from steam methane reforming. Traditionally, the performance of a catalyst is defined by a combination of its activity or efficiency (its turnover frequency), its selectivity and stability (its turnover number), all of which are direct manifestations of the intrinsic physicochemical properties of the heterogeneous catalyst itself under specific working conditions. We will, of course, retain these definitions of the catalytic process, but now attempt to place discussions about a catalyst’s performance onto a new foundation by investigating the effect of improvements in the catalyst’s efficiency or performance on the resulting total energy and total CO2 footprint for these prototypical fuel production and fuel conversion processes. The CSI should help the academic and industrial chemical communities, not only to highlight the current ‘best practice catalysts’, but also draw specific conclusions as to what energy and CO2 emissions saving one could anticipate with higher efficiency/higher performance from heterogeneous catalysts in a particular fuel synthesis or conversion process or technology. Our aim is to place discussions about advances in the science and technology of catalysis onto a firm foundation in the context of GHG emissions. We believe that thinking about (and attempting to quantify) total energy and CO2 emissions reductions associated with advances in catalysis science from a complete energy life cycle analysis perspective is extremely important. The CSI will help identify processes where the most critical advances in catalyst efficiency are needed in terms of their potential impact in the transition to a more sustainable future for fuel production and conversion technologies.

Rapid Production of High‐Purity Hydrogen Fuel through Microwave‐Promoted Deep Catalytic Dehydrogenation of Liquid Alkanes with Abundant Metals

Hydrogen as an energy carrier promises a sustainable energy revolution. However, one of the greatest challenges for any future hydrogen economy is the necessity for large scale hydrogen production not involving concurrent CO2 production. The high intrinsic hydrogen content of liquid-range alkane hydrocarbons (including diesel) offers a potential route to CO2 -free hydrogen production through their catalytic deep dehydrogenation. We report here a means of rapidly liberating high-purity hydrogen by microwave-promoted catalytic dehydrogenation of liquid alkanes using Fe and Ni particles supported on silicon carbide. A H2 production selectivity from all evolved gases of some 98 %, is achieved with less than a fraction of a percent of adventitious CO and CO2 . The major co-product is solid, elemental carbon.

Advances in the study of coke formation over zeolite catalysts in the methanol-to-hydrocarbon process

Methanol-to-hydrocarbon (MTH) process over acidic zeolite catalysts has been widely utilised to yield many types of hydrocarbons, some of which are eventually converted into the highly dehydrogenated (graphitized) carbonaceous species (cokes). The coking process can be divided into two parallel pathways based on the accepted hydrocarbon pool theory. From extensive investigations, it is reasonable to conclude that inner zeollite cavity/channel reactions at acidic sites generate cokes. However, coke formation and accumulation over the zeolite external surfaces play a major role in reaction deactivation as they contribute a great portion to the total coke amount. Herein we have reviewed previous literatures and included some recent works from KOPRC in understanding the nature and mechanism of coke formation, particularly during an H-ZSM-5 catalysed MTH reaction. We specially conclude that rapid aromatics formation at the zeolite crystalite edges is the main reason for later stage coke accumulation on the zeolite external surfaces. Accordingly, the catalyst deactivation is in a great certain to arise at those edge areas due to having the earliest contact with the incoming methanol reactant. The final coke structure is therefore built up with layers of poly-aromatics, as the potential sp2 carbons leading to pre-graphite structure. We have proposed a coke formation model particularly for the acidic catalyst, which we believe will be of assistance in understanding—and hence minimising—the coke formation mechanisms.

Urea–matrix combustion method: A versatile tool for the preparation of HDS catalysts

Urea-matrix combustion method is an effective new approach for preparing highly active Ni-W, Co-Mo and Ni-Mo HDS catalysts. The improved activity is mainly associated with a very efficient interaction between the well-dispersed oxidic precursors on the alumina surface. This is reflected in a strong synergistic effect that markedly increases the C-S bond cleavage reaction whereas a less pronounced antagonistic effect affects the relative rate of hydrogen transfer reactions.

Methane Conversion Over Sr2+/La2O3 Catalyst Modified with Nickel and Copper

Methane transformation over Ni and Cu modified Sr2+/La2O3 catalysts has been studied. These species favor formation of reducible mixed oxides and change the surface reactivity of the Sr2+/La2O3 system, modifying the reaction mechanism, since Sr2+/La2O3 favors methane oxidative coupling but with copper methane combustion is favored and nickel favors partial oxidation.

Wax: A benign hydrogen-storage material that rapidly releases H2-rich gases through microwave-assisted catalytic decomposition

Hydrogen is often described as the fuel of the future, especially for application in hydrogen powered fuel-cell vehicles (HFCV’s). However, its widespread implementation in this role has been thwarted by the lack of a lightweight, safe, on-board hydrogen storage material. Here we show that benign, readily-available hydrocarbon wax is capable of rapidly releasing large amounts of hydrogen through microwave-assisted catalytic decomposition. This discovery offers a new material and system for safe and efficient hydrogen storage and could facilitate its application in a HFCV. Importantly, hydrogen storage materials made of wax can be manufactured through completely sustainable processes utilizing biomass or other renewable feedstocks.

Microwaves effectively examine the extent and type of coking over acid zeolite catalysts

Coking leads to the deactivation of solid acid catalyst. This phenomenon is a ubiquitous problem in the modern petrochemical and energy transformation industries. Here, we show a method based on microwave cavity perturbation analysis for an effective examination of both the amount and the chemical composition of cokes formed over acid zeolite catalysts. The employed microwave cavity can rapidly and non-intrusively measure the catalytically coked zeolites with sample full body penetration. The overall coke amount is reflected by the obtained dielectric loss (ε″) value, where different coke compositions lead to dramatically different absorption efficiencies (ε″/cokes’ wt%). The deeper-dehydrogenated coke compounds (e.g., polyaromatics) lead to an apparently higher ε″/wt% value thus can be effectively separated from lightly coked compounds. The measurement is based on the nature of coke formation during catalytic reactions, from saturated status (e.g., aliphatic) to graphitized status (e.g., polyaromatics), with more delocalized electrons obtained for enhanced Maxwell–Wagner polarization.Catalyst deactivation by coke deposition is a major drawback in industrial processes. Here, the authors show a non-intrusive microwave cavity perturbation technique as a powerful tool to determine the nature and extent of coke accumulation in industrially-relevant zeolite catalysts.

Advanced Solid Catalysts for Renewable Energy Production

Advanced Solid Catalysts for Renewable Energy Production provides emerging research on renewable energy production, catalysts, and environmental effects of increased productivity. While highlighting the challenges for future generations to develop in the sustainable energy age, readers will learn the importance of new approaches not only for synthesizing more active and selective (nano)catalysts, but also, for designing innovative catalytic processes that can eventually meet the growing energy efficiency demand and overcome the environmental issues. This book is an important resource for academicians, university researchers, technology developers, and graduate level students.

A research into the thermodynamics of methanol to hydrocarbon (MTH): conflictions between simulated product distribution and experimental results

Thermodynamic calculations and analysis were carried out for a rational understanding of the results from selected laboratory MTH reactions. Simulations without solid carbons (coke), CO, CO2 and light alkanes target on the yield of olefin and aromatic products, which has been found better referenced to the real experimental observations that occur in time-on-stream (TOS). The confliction between simulated data and real experimental results is presumably ascribed to the limited dwelling time of products in the reaction system. Hydrocarbon pool based reactions donate olefins and methyl-benzenes as primary products in a continuous-flow MTH reaction; when the dwelling time of product extends intra-conversions (H2 transfers) between products would further adjust the composition of MTH yield, in which case alkanes and aromatic products (cokes precursors) increase. In the case of intra-conversions are ignored due to limited product dwelling time, thermodynamic calculation on Gibbs free energy change of selected sub reactions shows fairly close results to the real experimental data, which well supports the above explanations. This work highlights the importance of proper choosing target products and/or sub reactions for a rational thermodynamic prediction of MTH product distribution obtained in time-on-stream.

Effect of urea/metal ratio on the performance of NiMoP/Al2O3 catalyst for diesel deep HDS

Alumina-supported NiMoPOx catalysts have been prepared using urea matrix combustion–decomposition method. The effect of urea/metal ratios on the metal oxide dispersion, the conversion of the metal precursor to oxide and the structure and catalyst performance for diesel HDS has been studied. It is shown that the addition of urea adjusts the metal–support interaction, leading to the easy reduction of the metal oxide over the catalyst surface. It also changes the surface cluster of the oxide and the oxide structure. The addition of urea to metal matrix significantly improves the catalytic diesel HDS performance and increases the catalyst stability. The urea to Ni metal ratio of 2 gives the highest sulfur removal rate in the real diesel HDS process.