Nickel oxide-based catalysts for ethane oxidative dehydrogenation: a review

NiO-based catalysts are among the most active and selective catalytic systems for low-temperature oxidative dehydrogenation (ODH) of ethane into ethylene and, therefore, they have been extensively studied in the last twenty-five years. This paper reviews the most relevant works focusing on NiO-based catalysts for ethane ODH, including promoted and unpromoted, bulk and supported NiO. The effects of the nature of the promoter and of the support together with the influence of the method of preparation used on their activity in ethane ODH are discussed in detail as they were shown to be key factors controlling the catalytic performance, including the catalyst stability. The reaction mechanism involved in ethane ODH reaction over NiO-based catalysts is also presented and discussed

Nickel oxide-based catalysts for ethane oxidative dehydrogenation: a review

NiO-based catalysts are among the most active and selective catalytic systems for low-temperature oxidative dehydrogenation (ODH) of ethane into ethylene and, therefore, they have been extensively studied in the last twenty-five years. This paper reviews the most relevant works focusing on NiO-based catalysts for ethane ODH, including promoted and unpromoted, bulk and supported NiO. The effects of the nature of the promoter and of the support together with the influence of the method of preparation used on their activity in ethane ODH are discussed in detail as they were shown to be key factors controlling the catalytic performance, including the catalyst stability. The reaction mechanism involved in ethane ODH reaction over NiO-based catalysts is also presented and discussed

CuxCeMgAlO mixed oxide catalysts derived from multicationic LDH precursors for methane total oxidation

International audienc

Catalyse par les oxydes: conversion des molecules organiques legeres

Date de redaction: 31 janvier 2013.In this thesis I present my most relevant research work I performed as a main author from 2002 until these days in the field of Catalysis by Oxides by grouping it on a thematic basis. Consequently, each chapter in Section A presents a research direction which corresponds to several papers. I tried to avoid technical details in the text and illustrate the main ideas using results and their discussion. It is worth noting that the results presented here were mainly obtained in the Laboratory of Chemical Technology and Catalysis from the University of Bucharest but also in laboratories abroad where I worked or we are collaborating with. Chapter I presents the most relevant of my results on the subject of the oxidative dehydrogenation (ODH) of light alkanes following two main directions: i) enhancing the ODH selectivity of highly active catalysts and ii) developing new effective catalysts for ODH of light alkanes. Thus, we have shown that the ODH reaction of n-butane over highly active and selective TiP2O7 catalysts can be further improved by addition of CO2 in the feed and that phosphating ceria produces an increase in ODH selectivity mainly at the expense of total oxidation products. We studied new rare earth and transition metal-containing mixed-oxides obtained from layered double hydroxides (LDH) precursors as ODH catalysts. We have shown first that the use of the LDH-derived Mg-containing mixed oxides as catalysts in the ODH reaction favored the desorption of alkenes, and, consequently, improved the ODH selectivity. Among them the Co-containing system was the most active and selective for propane ODH. In this case we have shown that the well-dispersed cobalt species with tetrahedral coordination played a main role in the ODH reaction of propane into propene, the highest propene yields being obtained with the catalysts containing 7.5-9 at % Co with respect to cations. Chapter II is dedicated to the study of total oxidation of short-chain alkanes over different novel oxide-based catalysts with the aim of finding highly active catalysts for volatile organic compounds (VOCs) destruction, capable to replace the precious metal catalysts presently used. Thus, we have studied Pb and Ba titanates, LDH-derived transition metal-containing mixed oxides and Ni and Co ferrospinels. The most active and stable catalyst in the total oxidation of methane was the LDH-derived Cu-containing system. In this case we have shown that the active sites were the highly reducible copper species, their optimum dispersion being observed for the catalyst containing ~ 12 at % Cu with respect to cations. We have also shown for the first time that Co ferrite was highly active and stable in the total oxidation of propane as a VOC model. Chapter III is focussed on the study of oxidation catalysts by electrical conductivity measurements, a powerful technique for catalysts characterization that can provide information on the nature of surface oxidizing species, of structure defects and of the oxidic phase involved in the catalytic reaction which allows us to explain the catalytic behavior of the catalysts studied and to propose a reaction mechanism. Thus, we studied by electrical conductivity measurements ceria and phosphated ceria, catalysts for isobutane ODH, Pb and Ba titanates, catalysts for methane total oxidation, and vanadium antimonate and mixed vanadium and iron antimonate, catalysts for propane ammoxidation, the relationship existing between their redox and catalytic properties being evidenced and their catalytic behavior explained. Chapter IV is devoted to the study of catalytic processes involving the acid-base properties of the catalyst, such as conversion of ethanol into higher added value products over LDH-derived mixed oxides, cyanoethylation of methanol over transition-metal containing Mg-Al hydrotalcites and their corresponding mixed oxides and esterification of n-butanol with acetic acid over almina-supported molibdena and vanadia catalysts. Thus, we have shown that the Pd-containing LDH-derived mixed oxide was active for ethanol conversion into n-butanol while the Cu-based catalyst oriented the transformation towards n-butanol or 1,1-diethoxyethane depending on the reaction conditions and on the copper content. In the cyanoethylation reaction of methanol MgAlO system showed the best catalytic performances which diminished after introduction of the transition metal cations, the equilibrium between basic and acid sites being a key factor. Finally, we have shown that molybdena supported on γ-alumina acts as an efficient stable solid acid catalyst for the esterification of acetic acid with n-butanol, while vanadia supported on γ-alumina loose its activity because of the leaching of the active component. In Section B a plan for my research and academic career development is emphasized, different research topics in the field of Catalysis by Oxides that I intend to tackle in the future being described and justified based on a literature survey

Déshydrogénation oxydante du n-butane sur des catalyseurs à base de pyrophosphates métalliques

JURY: Mme. E. Bordes-Richard (Rapporteur), M. M. Che (Rapporteur), M. J.M. Herrmann (Président), M. J.M.M. Millet (Directeur de thèse), M. Ioan Sandulescu (Directeur de thèse)Oxidative dehydrogenation of n-butane over Ti, Zr, Ce and Sn pyrophosphates based catalysts was studied. The catalysts were characterized by several physical techniques and the catalytic properties evaluated in the temperature range of 410-570°C. TiP2O7 led to the best yield with butenes and butadiene selectivities of 42% and 14%, respectively, for 25% conversion at 530°C. The addition of water to the gas feed has a negative effect on both the conversion and selectivity to butenes and butadiene. Except CeP2O7 which was totally decomposed after catalytic test leading to a mixture of Ce(III) phosphates, the catalysts remain unchanged and can be classified into two groups depending upon the reaction mechanism involved. The first one is composed of ZrP2O7, SnP2O7 and TiP2O7 at low temperature and the second of TiP2O7 at high temperature. The reaction mechanism was studied using electrical conductivity measurements, ESR, Raman spectroscopy and TAP experiments. On both types of catalysts the initial step of activation of alkane would correspond to the attack of the alkane by the O– species giving a radical. But whereas the radical formed rapidly undergo a second hydrogen abstraction according to a similar mechanism leading to butene on the first type, it would either be trapped into an anionic vacancy or on a Ti4+ Lewis acid site to be transformed into an alkoxide intermediate or directly into butene with the abstraction of a proton, on the second type. In the first mechanism the rate limiting step is the attack of the alkane by the O– species but in the second, the reoxidation of the catalytic site by diffusion of the lattice oxygen or directly by gas phase oxygen. For TiP2O7 between 400 et 450°C we observe a special behavior : the rate limiting step is still the attack of the alkane by the O– species but the formed intermediate may also be trapped on the catalyst.La déshydrogénation oxydante du n-butane a été étudiée sur des catalyseurs à base de pyrophosphates de Ti, Zr, Ce et Sn. Leurs propriétés physico-chimiques (morphologie, structure, composition) ont été suivies par une série de techniques physiques et leurs propriétés catalytiques évaluées entre 410 et 570°C. TiP2O7 présente, à 530°C, le meilleur rendement : les sélectivités en butènes et butadiène atteignent respectivement 42% et 14% pour une conversion de 25%. L'ajout d'eau a un effet négatif sur les performances catalytiques. Mis à part CeP2O7, qui se transforme en deux phases phosphate de Ce(III) durant la réaction, les catalyseurs restent inchangés et peuvent être classifiés en deux groupes en fonction de mécanisme réactionnel impliqué : le premier avec ZrP2O7, SnP2O7 et TiP2O7 à basse température et le deuxième avec TiP2O7 à haute température. Des mesures de conductivité électrique et des caractérisations par RPE, spectroscopie Raman et TAP ont été mises en œuvre pour étudier le mécanisme réactionnel. Sur les deux types de catalyseur l'étape initiale d'activation de l'alcane correspond à l'attaque de l'alcane par une espèce O– menant à un radical, mais tandis que le radical formé est rapidement transformé en butène suite à une deuxième abstraction d'hydrogène par un mécanisme similaire sur le premier type de catalyseur, il est piégé dans une lacune anionique ou sur un site acide de Lewis Ti4+, étant transformé en une espèce alcoxyde ou directement en butènes par l'abstraction d'un proton, sur le deuxième type. Dans le premier mécanisme l'étape limitante est l'attaque de l'alcane par une espèce O– alors que dans le second c'est la réoxydation du site par diffusion de l'oxygène réticulaire ou directement par l'oxygène de la phase gaz. On observe pour TiP2O7 entre 400 et 450°C une situation particulière dont l'étape limitante est toujours l'attaque de l'alcane par une espèce O– mais l'intermédiaire réactionnel peut également être piégé sur le catalyseur

Study of sulfur dioxide adsorption on Y zeolite

Sulfur dioxide adsorptive properties of Y zeolite, the structure of which was confirmed by XRD, were investigated at temperatures within the 25200 ºC range and sulfur dioxide concentrations between 0.9 to 6 % (vol./vol.). It was found that this sorbent possesses a relatively high adsorption capacity. The Y zeolite did not lose its activity during 20 adsorption-desorption-regeneration cycles. The manner in which sulfur dioxide is adsorbed on Y type zeolite was also investigated by analyzing the sample with and without adsorbed SO2, using IR spectroscopy, as well as total and Lewis acidity measurements. The sulfur dioxide molecule is probably adsorbed by hydrogen bonding to one or two conveniently positioned surface hydroxyl groups