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[EN] Nickel oxides supported on gamma-alumina (Ni-loading from 5 to 30 wt% NiO) have been synthesized and tested in the oxidative dehydrogenation (ODH) of ethane in order to determine the importance of the NiO-support interaction. The best performance was achieved by the catalyst with 15 wt% NiO; higher NiO-loadings lead to the formation of unselective bulk-like NiO and lower Ni-loadings present high proportion of free alumina surface sites. The presence of oxalic acid and/or niobium in the synthesis gel resulted in the formation of NiO particles with similar size, but higher crystallinity and reducibility than the standard 15 wt% NiO catalyst. The obtained results have revealed that, in addition to NiO crystal size, the nickel oxide-support interaction determines the catalytic performance of these catalysts.

[EN] Nickel oxides supported on gamma-alumina (Ni-loading from 5 to 30 wt% NiO) have been synthesized and tested in the oxidative dehydrogenation (ODH) of ethane in order to determine the importance of the NiO-support interaction. The best performance was achieved by the catalyst with 15 wt% NiO; higher NiO-loadings lead to the formation of unselective bulk-like NiO and lower Ni-loadings present high proportion of free alumina surface sites. The presence of oxalic acid and/or niobium in the synthesis gel resulted in the formation of NiO particles with similar size, but higher crystallinity and reducibility than the standard 15 wt% NiO catalyst. The obtained results have revealed that, in addition to NiO crystal size, the nickel oxide-support interaction determines the catalytic performance of these catalysts.

[EN] Catalysts consisting of NiO diluted in high surface area TiO2 can be as efficient in the oxidative dehydrogenation of ethane as the most selective NiO-promoted catalysts reported previously in the literature. By selecting the titania matrix and the NiO loading, yields to ethylene over 40% have been obtained. In the present article, three different titanium oxides (TiO2) have been employed as supports or diluters of nickel oxide and have been tested in the oxidative dehydrogenation of ethane to ethylene. All TiO2 used present anatase as the main crystalline phase and different surface areas of 11,55 and 85 m(2) g(-1). It has been observed that by selecting an appropriate nickel loading and the titanium oxide extremely high selectivity towards ethylene can be obtained. Thus, nickel oxide supported on TiO2 with high surface areas (i.e. 55 and 85 m(2) g(-1)) have resulted to give the best catalytic performance although the optimal nickel loading is different for each case. The optimal catalyst has been obtained for NiO-loadings up to 5-10 theoretical monolayers regardless of the TiO2 employed. Free TiO2 is inactive whereas unsupported NiO is active and unselective (forming mainly carbon dioxide) and, therefore, unmodified NiO particles have to be avoided in order to obtain the optimal catalytic performance. The use of low surface area titania (11 m(2) g(-1)) have led to the lowest selectivity to olefin due to the presence of an excess of free NiO particles. (C) 2017 Elsevier B.V. All rights reserved.

[EN] Bulk Ni-Sn-O catalysts have been synthesized, tested in the oxidative dehydrogenation of ethane and characterized by several physicochemical techniques. The catalysts have been prepared by evaporation of the corresponding salts using several additives in the synthesis gel, i.e. ammonium hydroxide, nitric acid, glyoxylic acid or oxalic acid, in the synthesis gel. The catalysts were finally calcined at 500 degrees C in air. Important changes in the catalytic behaviour have been observed depending on the additive. In fact, an important improvement in the catalytic performance is observed especially when some additives, such as glyoxylic or oxalic acid, are used. Thus the productivity to ethylene multiplies by 6 compared to the reference Ni-Sn-O catalyst if appropriate templates are used, and this is the result of an improvement in both the catalytic activity and the selectivity to ethylene. This improved performance has been explained in terms of the decrease of the crystallite size (and the increase in the surface area of catalyst) as well as the modification of the lattice parameter of nickel oxide.

[EN] Bulk Ni-Sn-O catalysts have been synthesized, tested in the oxidative dehydrogenation of ethane and characterized by several physicochemical techniques. The catalysts have been prepared by evaporation of the corresponding salts using several additives in the synthesis gel, i.e. ammonium hydroxide, nitric acid, glyoxylic acid or oxalic acid, in the synthesis gel. The catalysts were finally calcined at 500 degrees C in air. Important changes in the catalytic behaviour have been observed depending on the additive. In fact, an important improvement in the catalytic performance is observed especially when some additives, such as glyoxylic or oxalic acid, are used. Thus the productivity to ethylene multiplies by 6 compared to the reference Ni-Sn-O catalyst if appropriate templates are used, and this is the result of an improvement in both the catalytic activity and the selectivity to ethylene. This improved performance has been explained in terms of the decrease of the crystallite size (and the increase in the surface area of catalyst) as well as the modification of the lattice parameter of nickel oxide.

[EN] Porous clay heterostructures (PCH) have shown to be highly efficient supports for nickel oxide in the oxidative dehydrogenation of ethane. Thus NiO supported on silica with a PCH structure shows productivity towards ethylene three times higher than if NiO is supported on a conventional silica. This enhanced productivity is due to the increase in the catalytic activity and especially to the drastic increase in the selectivity to ethylene. Additionally, PCH silica partially modified with titanium in the columns (PCH-Ti) have also been synthesized and used as supports for NiO. An enhanced activity and selectivity to ethylene was found over NiO supported over PCH-Ti compared to the corresponding catalysts supported over the Ti-free PCH. The enhanced catalytic performance has been related to the high dispersion of nickel oxide particles on the support, which leads to a lower reducibility of the nickel oxide, hindering the oxidation of ethane into carbon oxides. More interestingly, the particle morphology plays an important role on the catalyst selectivity since a higher distortion of the NiO crystal lattice parameter meant an enhanced selectivity to ethylene.

[EN] The robustness of one selected Ni-W-O catalyst has been studied in the oxidative dehydrogenation of ethane. This catalyst initially deactivates for the first 10 h online decreasing 15% of its catalytic activity compared to its initial stable catalytic activity. However from 10 to 60 h online the catalytic activity keeps almost stable. On the other hand, it has been shown that the Ni-W-O catalyst cannot tolerate an oxygen-free atmosphere (C-2 and He) as nickel oxide is transformed into metallic nickel. Methane and hydrogen as well as abundant coke were formed on the surface of the catalyst in these O-free conditions. However a re-calcination in air leads to the removal of coke, the catalytic performance in the oxidative dehydrogenation of ethane being almost completely restored.

[EN] The robustness of one selected Ni-W-O catalyst has been studied in the oxidative dehydrogenation of ethane. This catalyst initially deactivates for the first 10 h online decreasing 15% of its catalytic activity compared to its initial stable catalytic activity. However from 10 to 60 h online the catalytic activity keeps almost stable. On the other hand, it has been shown that the Ni-W-O catalyst cannot tolerate an oxygen-free atmosphere (C-2 and He) as nickel oxide is transformed into metallic nickel. Methane and hydrogen as well as abundant coke were formed on the surface of the catalyst in these O-free conditions. However a re-calcination in air leads to the removal of coke, the catalytic performance in the oxidative dehydrogenation of ethane being almost completely restored.

[EN] In this paper we present the synthesis, characterization and catalytic behaviour in the oxidative dehydrogenation of ethane of NiO-CeO2 mixed oxides. The addition of cerium oxide to NiO strongly modifies its catalytic performance, although the changes in the catalytic behaviour depend on the catalyst composition. The incorporation of low amounts of cerium oxide to NiO multiplies the productivity to ethylene in the oxidative dehydrogenation of ethane by a factor of ca. 7, which is the result of an increase in both catalytic activity and selectivity to ethylene. The enhanced activity has been related to the remarkable increase of the surface area of catalyst and the low crystal sizes of NiO that takes place when a tiny amount of cerium oxide is incorporated to the NiO. The higher selectivity to ethylene has been related to the modification of the nature of Ni-O species, which implies a lower production of carbon oxides. On the other hand, high activity and selectivity is also observed over catalysts rich in cerium ( with Ni/ Ce ratios between 0.2 and 3). In this case, a different mechanism can be proposed in which the high capacity of CeO2 to bomb oxygen from bulk to surface and the partial formation of NiO and Ce1-xNixO2 facilitates a faster reoxidation of active Ni-sites by a synergic effect improving catalytic activity. (C) 2011 Elsevier B.V. All rights reserved.

[EN] In this paper we present the synthesis, characterization and catalytic behaviour in the oxidative dehydrogenation of ethane of NiO-CeO2 mixed oxides. The addition of cerium oxide to NiO strongly modifies its catalytic performance, although the changes in the catalytic behaviour depend on the catalyst composition. The incorporation of low amounts of cerium oxide to NiO multiplies the productivity to ethylene in the oxidative dehydrogenation of ethane by a factor of ca. 7, which is the result of an increase in both catalytic activity and selectivity to ethylene. The enhanced activity has been related to the remarkable increase of the surface area of catalyst and the low crystal sizes of NiO that takes place when a tiny amount of cerium oxide is incorporated to the NiO. The higher selectivity to ethylene has been related to the modification of the nature of Ni-O species, which implies a lower production of carbon oxides. On the other hand, high activity and selectivity is also observed over catalysts rich in cerium ( with Ni/ Ce ratios between 0.2 and 3). In this case, a different mechanism can be proposed in which the high capacity of CeO2 to bomb oxygen from bulk to surface and the partial formation of NiO and Ce1-xNixO2 facilitates a faster reoxidation of active Ni-sites by a synergic effect improving catalytic activity. (C) 2011 Elsevier B.V. All rights reserved.

[EN] An intensification process for the selective oxidation of hydrocarbons integrates a catalytic reactor and an oxygen separation membrane. This work presents the study of oxidative dehydrogenation of ethane at 1123 K in a catalytic membrane reactor based on mixed ionic-electronic conducting (MIEC) membranes. The surface of a membrane made of Ba0.5Sr0.5Co0.8Fe0.2O3-d has been activated using different porous catalytic layers based on rare earth-doped cerias (fluorite structure) and the porous catalytic coating was deposited by screen printing (coating around 15 mu m). The different catalyst formulations were developed by partial substitution of Ce and were synthesized by co-precipitation followed by cobalt impregnation when required. Specifically, seven different catalysts based on the system Ce1-xLnxO2-d (x=0.1 or 0.2; Ln=Tb, Pr, Er, Gd, and Tb+Er), including the effect of cobalt addition (2?% molar) in Ce0.8Tb0.2O2-d, were studied. The ceria catalysts were studied by XRD, SEM, DC-conductivity as a function of oxygen partial pressure, and the high-temperature stability in a CO2 environment was assessed using thermogravimetry. Then, the influence of the ceria catalytic coating on the oxygen permeation flux through the MIEC membrane was studied using argon and methane as the sweep gas in the permeate side. Finally, oxidative dehydrogenation of ethane reaction tests were performed at 1123 K, as a function of the ethane concentration in the feed. The use of a disk-shaped membrane in the reactor made it possible to prevent the direct contact of gaseous oxygen and hydrocarbons and thus to increase the ethylene yield. High ethylene yields (up to approximate to 84?%) were obtained using a catalytic coating based on 20?% Tb-doped ceria including macropores produced by the addition of graphite platelets in the screen printing ink. The high yields obtained in this kind of catalytic membrane are attributed to the combination of: the high catalytic activity; the control of th

[EN] Ni-Sn-O mixed oxides catalysts have been investigated for the oxidative dehydrogenation of ethane. The catalysts were prepared through the evaporation of aqueous solutions of nickel nitrate and tin oxalate and finally calcined in air at 500 degrees C for 2 h. These materials have been characterized by several techniques (N-2-adsorption, X-ray diffraction, High-Resolution Electron Microscopy, temperature programmed reduction, X-Ray Photoelectron Spectroscopy, Fourier Transformed Infrared Spectroscopy of adsorbed CO and O-18/O-16 isotope exchange). The addition of just a tiny amount of tin highly increases the selectivity to ethylene (from ca. 40% to 80-90%). Thus, high selectivity to ethylene (near to 90%) is observed on samples with high Ni/Sn atomic ratios (3 < Ni/Sn <50), in which no influence of ethane conversion on selectivity to ethylene is observed (suggesting high stability of ethylene on these catalysts). Additionally, for low Sn-loadings, an increase in the catalytic activity has also been observed. The enhanced catalytic properties have been explained in terms of changes in the nature of Ni species on the catalyst surface, which can be considered as the active sites. The nature of Ni species is related to changes in the crystal size of NiO particles (and surface area) of catalysts as well as to the presence of SnOx crystals. In addition, the role of the presence of acid sites on the catalyst surface on the selectivity to ethylene is also discussed. (C) 2012 Elsevier Inc. All rights reserved.

[EN] Ni-Sn-O mixed oxides catalysts have been investigated for the oxidative dehydrogenation of ethane. The catalysts were prepared through the evaporation of aqueous solutions of nickel nitrate and tin oxalate and finally calcined in air at 500 degrees C for 2 h. These materials have been characterized by several techniques (N-2-adsorption, X-ray diffraction, High-Resolution Electron Microscopy, temperature programmed reduction, X-Ray Photoelectron Spectroscopy, Fourier Transformed Infrared Spectroscopy of adsorbed CO and O-18/O-16 isotope exchange). The addition of just a tiny amount of tin highly increases the selectivity to ethylene (from ca. 40% to 80-90%). Thus, high selectivity to ethylene (near to 90%) is observed on samples with high Ni/Sn atomic ratios (3 < Ni/Sn <50), in which no influence of ethane conversion on selectivity to ethylene is observed (suggesting high stability of ethylene on these catalysts). Additionally, for low Sn-loadings, an increase in the catalytic activity has also been observed. The enhanced catalytic properties have been explained in terms of changes in the nature of Ni species on the catalyst surface, which can be considered as the active sites. The nature of Ni species is related to changes in the crystal size of NiO particles (and surface area) of catalysts as well as to the presence of SnOx crystals. In addition, the role of the presence of acid sites on the catalyst surface on the selectivity to ethylene is also discussed. (C) 2012 Elsevier Inc. All rights reserved.

[EN] An intensification process for the selective oxidation of hydrocarbons integrates a catalytic reactor and an oxygen separation membrane. This work presents the study of oxidative dehydrogenation of ethane at 1123 K in a catalytic membrane reactor based on mixed ionic-electronic conducting (MIEC) membranes. The surface of a membrane made of Ba0.5Sr0.5Co0.8Fe0.2O3-d has been activated using different porous catalytic layers based on rare earth-doped cerias (fluorite structure) and the porous catalytic coating was deposited by screen printing (coating around 15 mu m). The different catalyst formulations were developed by partial substitution of Ce and were synthesized by co-precipitation followed by cobalt impregnation when required. Specifically, seven different catalysts based on the system Ce1-xLnxO2-d (x=0.1 or 0.2; Ln=Tb, Pr, Er, Gd, and Tb+Er), including the effect of cobalt addition (2?% molar) in Ce0.8Tb0.2O2-d, were studied. The ceria catalysts were studied by XRD, SEM, DC-conductivity as a function of oxygen partial pressure, and the high-temperature stability in a CO2 environment was assessed using thermogravimetry. Then, the influence of the ceria catalytic coating on the oxygen permeation flux through the MIEC membrane was studied using argon and methane as the sweep gas in the permeate side. Finally, oxidative dehydrogenation of ethane reaction tests were performed at 1123 K, as a function of the ethane concentration in the feed. The use of a disk-shaped membrane in the reactor made it possible to prevent the direct contact of gaseous oxygen and hydrocarbons and thus to increase the ethylene yield. High ethylene yields (up to approximate to 84?%) were obtained using a catalytic coating based on 20?% Tb-doped ceria including macropores produced by the addition of graphite platelets in the screen printing ink. The high yields obtained in this kind of catalytic membrane are attributed to the combination of: the high catalytic activity; the control of th

[EN] An intensification process for the selective oxidation of hydrocarbons integrates a catalytic reactor and an oxygen separation membrane. This work presents the study of oxidative dehydrogenation of ethane at 1123 K in a catalytic membrane reactor based on mixed ionic-electronic conducting (MIEC) membranes. The surface of a membrane made of Ba0.5Sr0.5Co0.8Fe0.2O3-d has been activated using different porous catalytic layers based on rare earth-doped cerias (fluorite structure) and the porous catalytic coating was deposited by screen printing (coating around 15 mu m). The different catalyst formulations were developed by partial substitution of Ce and were synthesized by co-precipitation followed by cobalt impregnation when required. Specifically, seven different catalysts based on the system Ce1-xLnxO2-d (x=0.1 or 0.2; Ln=Tb, Pr, Er, Gd, and Tb+Er), including the effect of cobalt addition (2?% molar) in Ce0.8Tb0.2O2-d, were studied. The ceria catalysts were studied by XRD, SEM, DC-conductivity as a function of oxygen partial pressure, and the high-temperature stability in a CO2 environment was assessed using thermogravimetry. Then, the influence of the ceria catalytic coating on the oxygen permeation flux through the MIEC membrane was studied using argon and methane as the sweep gas in the permeate side. Finally, oxidative dehydrogenation of ethane reaction tests were performed at 1123 K, as a function of the ethane concentration in the feed. The use of a disk-shaped membrane in the reactor made it possible to prevent the direct contact of gaseous oxygen and hydrocarbons and thus to increase the ethylene yield. High ethylene yields (up to approximate to 84?%) were obtained using a catalytic coating based on 20?% Tb-doped ceria including macropores produced by the addition of graphite platelets in the screen printing ink. The high yields obtained in this kind of catalytic membrane are attributed to the combination of: the high catalytic activity; the control of th

Ni-W-O mixed oxides were prepared through the evaporation of aqueous solutions of nickel nitrate and ammonium tungstate and calcined in air at 500 degrees C for 2 h. The catalysts were characterized by several techniques (N(2) adsorption, X-ray diffraction, temperature-programmed reduction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy of adsorbed CO, and (18)O/(16)O isotope exchange) and tested in the oxidative dehydrogenation of ethane. The catalytic activity and catalyst reducibility decrease when the W content increases. Thus, nickel sites seem to be the active centers for ethane activation in these catalysts. However, the selectivity to ethylene strongly changes depending on the Ni/W ratio. In W-rich catalysts, in which NiWO(4) and WO(3) are mainly observed, a strong influence of ethane conversion on the selectivity to ethylene is observed. However, in Ni-rich catalysts, in which NiO crystallites and WO(x) nanoparticles are mainly observed, ethane conversion hardly influences the selectivity to ethylene. It has been demonstrated that the nature of the Ni sites and the characteristics and number of the acid sites determine the catalytic behavior of these catalysts. The presence of Lewis acid sites with high acid strength in W-rich catalysts facilitates the decomposition of ethylene during ethane oxidation. (C) 2011 Elsevier Inc. All rights reserved.

Ni-W-O mixed oxides were prepared through the evaporation of aqueous solutions of nickel nitrate and ammonium tungstate and calcined in air at 500 degrees C for 2 h. The catalysts were characterized by several techniques (N(2) adsorption, X-ray diffraction, temperature-programmed reduction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy of adsorbed CO, and (18)O/(16)O isotope exchange) and tested in the oxidative dehydrogenation of ethane. The catalytic activity and catalyst reducibility decrease when the W content increases. Thus, nickel sites seem to be the active centers for ethane activation in these catalysts. However, the selectivity to ethylene strongly changes depending on the Ni/W ratio. In W-rich catalysts, in which NiWO(4) and WO(3) are mainly observed, a strong influence of ethane conversion on the selectivity to ethylene is observed. However, in Ni-rich catalysts, in which NiO crystallites and WO(x) nanoparticles are mainly observed, ethane conversion hardly influences the selectivity to ethylene. It has been demonstrated that the nature of the Ni sites and the characteristics and number of the acid sites determine the catalytic behavior of these catalysts. The presence of Lewis acid sites with high acid strength in W-rich catalysts facilitates the decomposition of ethylene during ethane oxidation. (C) 2011 Elsevier Inc. All rights reserved.