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Preface for the special Issue: Sustainable Fuels and Chemicals
Catalysis Today 237 (2014) 1–2
Contents lists available at ScienceDirect
Catalysis Today journal homepage: www.elsevier.com/locate/cattod
Preface for the special Issue: Sustainable Fuels and Chemicals
This special issue of Catalysis Today was possible due to the encouragement and assistance of Professor James Spivey, the Chief Editor of this esteemed journal. This issue contains the contributions of authors at the 23rd North American Catalysis Society Conference, Louisville, Lexington, USA. This conference was the premier scientific event in the field of catalysis research in 2013 which dealt with the technological challenges, breakthrough and discoveries and state-of-the-art of industrial research in catalysis. All 19 papers in this special issue were accepted with due process developed by the editorial board of Catalysis Today. The papers are sub-grouped as follows: esterification and trans-esterification reactions; glycerol valorization, oxidation and reforming reactions; methanol/ethanol reforming, oxidation, and cracking reactions; biomass gasification reactions; hydrodeoxygenation and acetalization of ethylene glycol; glycerolysis and deoxygenation of triglycerides; hydrodeoxygenation of biomass derived molecules; Fischer–Tropsch and isopropylation reactions. The major products are either fuel or value-added chemicals created through novel catalytic processes. In most of the cases, catalysts were synthesized, characterized in great details and their properties were correlated with the catalysts’ activities, and reaction mechanism and reaction kinetics were examined. Mesoporous sulfated Ti-SBA-15 catalysts were synthesized, extensively characterized and applied for biodiesel production from unrefined canola oil by Dalai et al. Sulfation of catalyst by chlorosulfonic acid and the effects of reaction time and temperature were the most significant parameters for high quality biodiesel synthesis. Canola oil was transesterified using various acidic and basic solid catalysts in a capillary fluidized bed by Patience et al. This process was developed to collect high quality biofuel synthesis with periodic oxidation of coke built on the catalyst surface. Esterification of levulinic acid with alcohols using sulfated zirconosilicates was conducted by Kuwahara et al. to produce ethyl levulinate and the influences of preparation method and structural properties on the catalyst performances were evaluated. Optimum catalyst composition was established and the process was extended for the direct conversion of cellulosic sugars into levulinate esters. Biodiesel from acid oil containing high free fatty acid (FFA) was synthesized by Maheria et al. using sulfonic acid functionalized mesostructured SBA-15 catalyst. The process parameters were optimized for 99% FFA and the reaction followed pseudo first order kinetic law. Glycerol to chemicals such as ketones, alcohols and carboxylic acid via glycerol carbonate formation were produced by Passos
http://dx.doi.org/10.1016/j.cattod.2014.08.004 0920-5861/© 2014 Elsevier B.V. All rights reserved.
et al. during its liquid phase reaction with carbon dioxide using Ni/␥-Al2 O3 . A novel catalyst method was developed for its use also for hydrocarbons and oxygenates of higher value in a batch reaction system. Also, glycerol carbonate from glycerol was produced by Yadav et al. using calcined hydrotalcite supported on hexagonal silica catalyst as a solid base catalyst. The catalyst was quite effective exhibiting a second order kinetics for glycerol carbonate formation. Glycerol conversion to synthesis gas via autothermal partial oxidation was performed by Lin and Liu using LaMnO3 and LaNiO3 perovskites. Hydrogen selectivity was improved by water addition especially for LaMnO3 . Also, Yadav et al. performed selective mono-isopropylation of 1,3-propanediols to 3-isopropyl1-propanol using cesium based catalyst and have optimized the process conditions, and developed reaction kinetics. In situ XANES studies of methanol decomposition and partial oxidation to synthesis gas over Pt/SrTiO3 nanotubes were conducted by Marshall et al. Extensive catalyst surface characterization indicated that CO adsorbed on the Pt sites was the only observed surface species which was oxidized to CO2 when O2 was present. Detailed experiments were performed by Pradhan et al. on the steam reforming of ethanol over alumina supported nano-NiO/SiO2 catalyst which was extensively characterized. A power-law model rate equation was derived for this process. Ethanol conversion to hydrocarbons, especially to aromatics and paraffin, on HZSM-5 with different Si/Al ratios was examined by Wang and Ramasamy at wide range of process conditions. Catalyst deactivation for this process was also examined. The effects of La2 O3 promoted Ni/␥-Al2 O3 fluidizable catalysts on steam gasification of a cellulose surrogate (glucose) and a lignin surrogate (2-methoxy-4-methylphenol) on the quality of synthesis gas was studied by de Lasa and Mazumdar in great detail. Ni dispersion was largely favored by the addition of 5 wt.% La2 O3 . The catalysts were characterized in great detail. Catalyst composition and process conditions were optimized for large conversion of feed stocks. Mahinpey and Mostafavi developed a mixed catalystsorbent for steam gasification of coal chars with in situ CO2 capture. During gasification process, catalyst enhanced the gasification and water-gas-shift reaction rates, whereas CO2 capture shifted the WGS equilibrium forward, favoring hydrogen production. Hydrodeoxygenation and selective acetalization of ethylene glycol using tungstated zirconia supported palladium and several cesium based solid acid catalysts were studied by Wang et al. and Yadav and Katole respectively. The catalysts were characterized and the reactions were correlated to metal particles and their
2
Preface for the special Issue: Sustainable Fuels and Chemicals / Catalysis Today 237 (2014) 1–2
sizes. Reaction mechanism and kinetic studies were performed by Yadav et al whereas Wang et al. correlated product selectivity with the Bronsted acid sites and electron deficient Pd particle species present in the catalyst. Hydrodeoxygenation of triglycerides and fatty acids over Ni–Al layered double hydroxide to fuel-like hydrocarbons was investigated by Santillan-Jimenez et al which indicated that this process is more effective on strong basic sites and the process produces intermediate fatty acids which then proceeds via aldehyde and/or fatty acid ester intermediates. Naik and Naik investigated on the enzymatic glycerolysis for conversion of sunflower oil to food based emulsifiers at mild reaction conditions and have recommended Fermase 10000 enzyme for such reaction in industrial scale. Abatzoglou and Blanchard experimented with iron carbide particles for Fischer–Tropsch synthesis and examined the role of iron loading and K, Cu promoters on the H2 + CO conversion, catalyst deactivation. Vohs et al. conducted fundamental studies of the glyceraldehyde and glucose reaction on Zn-modified Pt surfaces, and have demonstrated that the modification of catalyst properties through alloy formation affects the adsorption of these feeds thus influencing the formation and stability of adsorbed intermediates.
In summary, most of papers published in this special issue of Catalysis Today deal with materials synthesis, extensive physic-chemical characterizations, activity and reaction mechanism studies and development of reaction kinetics, especially for the sustainable fuels and chemicals production. Ajay K. Dalai ∗ Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical and Biological Engineering, College of Engineering, University of Saskatchewan, Saskatoon, SK, Canada S7N 5A9 Yong Wang Voiland School of Chemical Engineering and Bioengineering, Washington State University/Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, WA 99354, USA ∗ Corresponding
author. E-mail address: [email protected] (A.K. Dalai)
Contents lists available at ScienceDirect
Catalysis Today journal homepage: www.elsevier.com/locate/cattod
Preface for the special Issue: Sustainable Fuels and Chemicals
This special issue of Catalysis Today was possible due to the encouragement and assistance of Professor James Spivey, the Chief Editor of this esteemed journal. This issue contains the contributions of authors at the 23rd North American Catalysis Society Conference, Louisville, Lexington, USA. This conference was the premier scientific event in the field of catalysis research in 2013 which dealt with the technological challenges, breakthrough and discoveries and state-of-the-art of industrial research in catalysis. All 19 papers in this special issue were accepted with due process developed by the editorial board of Catalysis Today. The papers are sub-grouped as follows: esterification and trans-esterification reactions; glycerol valorization, oxidation and reforming reactions; methanol/ethanol reforming, oxidation, and cracking reactions; biomass gasification reactions; hydrodeoxygenation and acetalization of ethylene glycol; glycerolysis and deoxygenation of triglycerides; hydrodeoxygenation of biomass derived molecules; Fischer–Tropsch and isopropylation reactions. The major products are either fuel or value-added chemicals created through novel catalytic processes. In most of the cases, catalysts were synthesized, characterized in great details and their properties were correlated with the catalysts’ activities, and reaction mechanism and reaction kinetics were examined. Mesoporous sulfated Ti-SBA-15 catalysts were synthesized, extensively characterized and applied for biodiesel production from unrefined canola oil by Dalai et al. Sulfation of catalyst by chlorosulfonic acid and the effects of reaction time and temperature were the most significant parameters for high quality biodiesel synthesis. Canola oil was transesterified using various acidic and basic solid catalysts in a capillary fluidized bed by Patience et al. This process was developed to collect high quality biofuel synthesis with periodic oxidation of coke built on the catalyst surface. Esterification of levulinic acid with alcohols using sulfated zirconosilicates was conducted by Kuwahara et al. to produce ethyl levulinate and the influences of preparation method and structural properties on the catalyst performances were evaluated. Optimum catalyst composition was established and the process was extended for the direct conversion of cellulosic sugars into levulinate esters. Biodiesel from acid oil containing high free fatty acid (FFA) was synthesized by Maheria et al. using sulfonic acid functionalized mesostructured SBA-15 catalyst. The process parameters were optimized for 99% FFA and the reaction followed pseudo first order kinetic law. Glycerol to chemicals such as ketones, alcohols and carboxylic acid via glycerol carbonate formation were produced by Passos
http://dx.doi.org/10.1016/j.cattod.2014.08.004 0920-5861/© 2014 Elsevier B.V. All rights reserved.
et al. during its liquid phase reaction with carbon dioxide using Ni/␥-Al2 O3 . A novel catalyst method was developed for its use also for hydrocarbons and oxygenates of higher value in a batch reaction system. Also, glycerol carbonate from glycerol was produced by Yadav et al. using calcined hydrotalcite supported on hexagonal silica catalyst as a solid base catalyst. The catalyst was quite effective exhibiting a second order kinetics for glycerol carbonate formation. Glycerol conversion to synthesis gas via autothermal partial oxidation was performed by Lin and Liu using LaMnO3 and LaNiO3 perovskites. Hydrogen selectivity was improved by water addition especially for LaMnO3 . Also, Yadav et al. performed selective mono-isopropylation of 1,3-propanediols to 3-isopropyl1-propanol using cesium based catalyst and have optimized the process conditions, and developed reaction kinetics. In situ XANES studies of methanol decomposition and partial oxidation to synthesis gas over Pt/SrTiO3 nanotubes were conducted by Marshall et al. Extensive catalyst surface characterization indicated that CO adsorbed on the Pt sites was the only observed surface species which was oxidized to CO2 when O2 was present. Detailed experiments were performed by Pradhan et al. on the steam reforming of ethanol over alumina supported nano-NiO/SiO2 catalyst which was extensively characterized. A power-law model rate equation was derived for this process. Ethanol conversion to hydrocarbons, especially to aromatics and paraffin, on HZSM-5 with different Si/Al ratios was examined by Wang and Ramasamy at wide range of process conditions. Catalyst deactivation for this process was also examined. The effects of La2 O3 promoted Ni/␥-Al2 O3 fluidizable catalysts on steam gasification of a cellulose surrogate (glucose) and a lignin surrogate (2-methoxy-4-methylphenol) on the quality of synthesis gas was studied by de Lasa and Mazumdar in great detail. Ni dispersion was largely favored by the addition of 5 wt.% La2 O3 . The catalysts were characterized in great detail. Catalyst composition and process conditions were optimized for large conversion of feed stocks. Mahinpey and Mostafavi developed a mixed catalystsorbent for steam gasification of coal chars with in situ CO2 capture. During gasification process, catalyst enhanced the gasification and water-gas-shift reaction rates, whereas CO2 capture shifted the WGS equilibrium forward, favoring hydrogen production. Hydrodeoxygenation and selective acetalization of ethylene glycol using tungstated zirconia supported palladium and several cesium based solid acid catalysts were studied by Wang et al. and Yadav and Katole respectively. The catalysts were characterized and the reactions were correlated to metal particles and their
2
Preface for the special Issue: Sustainable Fuels and Chemicals / Catalysis Today 237 (2014) 1–2
sizes. Reaction mechanism and kinetic studies were performed by Yadav et al whereas Wang et al. correlated product selectivity with the Bronsted acid sites and electron deficient Pd particle species present in the catalyst. Hydrodeoxygenation of triglycerides and fatty acids over Ni–Al layered double hydroxide to fuel-like hydrocarbons was investigated by Santillan-Jimenez et al which indicated that this process is more effective on strong basic sites and the process produces intermediate fatty acids which then proceeds via aldehyde and/or fatty acid ester intermediates. Naik and Naik investigated on the enzymatic glycerolysis for conversion of sunflower oil to food based emulsifiers at mild reaction conditions and have recommended Fermase 10000 enzyme for such reaction in industrial scale. Abatzoglou and Blanchard experimented with iron carbide particles for Fischer–Tropsch synthesis and examined the role of iron loading and K, Cu promoters on the H2 + CO conversion, catalyst deactivation. Vohs et al. conducted fundamental studies of the glyceraldehyde and glucose reaction on Zn-modified Pt surfaces, and have demonstrated that the modification of catalyst properties through alloy formation affects the adsorption of these feeds thus influencing the formation and stability of adsorbed intermediates.
In summary, most of papers published in this special issue of Catalysis Today deal with materials synthesis, extensive physic-chemical characterizations, activity and reaction mechanism studies and development of reaction kinetics, especially for the sustainable fuels and chemicals production. Ajay K. Dalai ∗ Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical and Biological Engineering, College of Engineering, University of Saskatchewan, Saskatoon, SK, Canada S7N 5A9 Yong Wang Voiland School of Chemical Engineering and Bioengineering, Washington State University/Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, WA 99354, USA ∗ Corresponding
author. E-mail address: [email protected] (A.K. Dalai)