Transient behaviour of dense catalytic membranes based on Cu- and Co-doped Bi4V2O11 (BIMEVOX) in the oxidation of propene and propane

ME-doped γ-Bi₄V₂O₁₁ (BIMEVOX) oxides are highly oxide ion conducting materials and this property may be profitably used in selective oxidation of hydrocarbons. The catalytic properties of BICUVOX and BICOVOX when shaped as dense membranes displayed in catalytic dense membrane reactor are examined in the oxidation of propene and of propane. Mirror-polished BICUVOX and BICOVOX membranes studied previously were poorly active for propene oxidation because of a small number of active sites but showed an excellent stability and reproducibility (lasting more than 1 month) during which products of mild oxidation (acrolein, hexadiene) and CO were formed. Membranes with depolished surfaces exhibit high conversions of propene (up to 60 mol%), and also of propane (up to 20 mol%) but – contrary to mirror-polished membranes – a complex transient behaviour is observed during which syngas production occurs. The membrane polarisation followed by in situ solid electrolyte potentiometry shows that the oxygen reservoir is far higher than expected on the reaction side which is separated (by the membrane) from the oxidising side where (diluted) oxygen is reduced to O²⁻ specie. The influence of oxygen partial pressure on the catalytic performance suggests that the electronic conductivity of the material is limiting the oxygen flux through the membrane, and thus is determining the catalytic properties and transient behaviours of depolished membranes.     

Catalytic dense membranes of doped Bi4V2O11 (BIMEVOX) for selective partial oxidation: chemistry of defects versus catalysis

A catalytic dense membrane reactor (CDMR) is used to physically separate the reaction step from the reoxidation of the catalyst. By decoupling the redox mechanism prevailing in mild oxidation of hydrocarbons, the operating conditions may be optimized resulting in an increase of selectivity. The membranes are made up of BIMEVOX oxides, obtained by partial substitution of V in γ-Bi₄V₂O₁₁ by ME (Co, Cu, Ta). Experiments performed on BIMEVOX dense membranes using propene and propane are described in terms of, (i) active sites on polished or unpolished surfaces, (ii) operating conditions (T, pO₂ in the high oxygen partial pressure compartment), which determine the selectivity, either to mild oxidation products (acrolein, hexadiene, CO), or to partial oxidation products (CO, H₂), and, (iii) nature of ME cations and relative properties. The discussion deals with the respective role of electronic versus oxide ion conductivities which depend on defects in the structure as well as on the redox properties of cations.     

Oxidation state of palladium as a factor controlling catalytic activity of Pd/SiO2–Al2O3 in propane combustion

The oxidation state of palladium on SiO₂–Al₂O₃ used for propane combustion was examined by XPS and XRD, and the correlation of the catalytic activity with the oxidation state of palladium was systematically studied. The propane conversion over 5 wt% Pd/SiO₂–Al₂O₃ was measured in the range 1.0≤S≤7.2 (S is defined as [O₂]/5[C₃H₈] based on stoichiometric ratio). The propane conversion strongly depended on the S value and reached the maximum at S=5.5. The oxidation state of palladium also changed with the S value; palladium particles were more oxidized under the reaction mixture of higher S value. On the sample used for the reaction at S=5.5, both of metallic palladium and palladium oxide were found. It is concluded that partially oxidized palladium which has optimum ratio of metallic palladium to palladium oxide shows the highest catalytic activity in propane combustion.     

Oxidation behaviour and catalytic properties of Pd/Al2O3 catalysts in the total oxidation of methane

A series of Pd/Al₂O₃ catalysts with a wide range of mean Pd particle sizes (ca. 2–30 nm in diameter) was prepared by using various precursors (H₂PdCl₄, Pd(NO₃)₂ and Pd(AcAc)₂) and pre-treatments. The mean particle size of reduced samples was determined by H₂ chemisorption. The catalytic activity in methane oxidation under lean burn conditions was measured. The oxidation of reduced samples was studied at 300 °C. The extent of oxidation was found to decrease with increasing mean particle size. While small particles (<5 nm) oxidised very rapidly, the oxidation of large particles (ca. >15 nm) proceeded via a two-step process, being first fast and then slow. The decomposition of oxide species was studied by temperature-programmed experiments under vacuum. Two distinct oxidised species with different stability were evidenced depending on the particle size. Oxidised species in larger particles were found of lower stability than in smaller ones. A correlation between the existence of distinct types of oxide species and catalytic properties in methane oxidation was discussed.     

The promoting effect of Nb2O5 addition to Pd/Al2O3 catalysts on propane oxidation

Pd/Nb₂O₅/Al₂O₃ catalysts were investigated on propane oxidation. Diffuse reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS) analysis suggested that monolayer coverage was attained between 10 and 20 wt.% of Nb₂O₅. Temperature programmed reduction (TPR) evidenced the partial reduction of niobium oxide. The maximum propane conversion observed on the Pd/10% Nb₂O₅/Al₂O₃ corresponded to the maximum Nb/Al surface ratio. The presence of NbO_x polymeric structures near to the monolayer could favor the ideal Pd⁰/Pd²⁺ surface ratio to the propane oxidation which could explain the promoting effect of niobium oxide.     

Electrochemical synthesis of N2O5 by oxidation of N2O4 in nitric acid with PTFE membrane

Electrochemical synthesis of dinitrogen pentoxide (N₂O₅) by oxidation of dinitrogen tetroxide (N₂O₄) in a plate-and-frame electrolyzer was investigated. As the separator, different porous polytetrafluoroethylene (PTFE) membranes were tested in this process and the effects of hydrophilicity and of hydrophobicity on the electrolysis were discussed. The transport of N₂O₄ and water from catholyte to anolyte through membrane occurred in the electrolysis, especially at the end of the electrolysis. The water transport had a much more effect on the electrolysis than that of the N₂O₄ diffusion. The hydrophobic PTFE membranes had better performance on control of water transport from catholyte to anolyte than that of the hydrophilic ones. Hydrophobicity can increase the chemical yield of N₂O₅. The membranes with a low hydrophobic surface were preferred. All the hydrophobic PTFE membranes with low resistance have the specific energy of 1.1-1.5 kWh kg⁻¹ N₂O₅. The current efficiency of 67.3-80.2% and chemical yield of 58.9-60.9% were achieved in production of N₂O₅. The technique of replacing the catholyte with fresh nitric acid can minimize the transport of N₂O₄ and water to a great extent, it can further improve the chemical yield and reduce the specific energy.     

Modeling and simulation of non-isothermal catalytic packed bed membrane reactor for H2S decomposition

The recovery of H₂ from H₂S is an economical alternative to the Claus process in petroleum and minerals processing industries. Previous studies [React. Kinet. Catal. Lett. 62 (1997) 55; Catal. Lett. 37 (1996) 167] have demonstrated that catalytic decomposition of H₂S over bimetallic sulfide can proceed at relatively higher rates than over mono-metallic systems due to chemical synergism although conversions are still thermodynamically limited. In the present study, the performance of a catalytic membrane reactor containing a packed bed of Ru–Mo sulfide catalyst has been investigated with a view to improving H₂ yield beyond the equilibrium ceiling. A system of differential equations describing the non-isothermal reactor model has been solved to examine the effect of important hydrodynamic and transport properties on conversion. The results were obtained using a Pt-coated Nb membrane tube as the catalytic reactor enclosed in a quartz shell cylinder. Reynolds number for shell and tube side (Re^s and Re^t) as well as the modified wall Peclet number, Pe_m, dramatically affect H₂S conversions. Membrane reactor conversion rose monotonically with axial distance exceeding the equilibrium conversion by as much as eight times under some conditions.     

Oxidative dehydrogenation of propane over V2O5-MgO/TiO2 catalyst: Effect of reactants contact mode

The performance of the active catalyst 5%V₂O₅-1.9%MgO/TiO₂ in propane oxidative dehydrogenation is investigated under various reactant contact modes: co-feed and redox decoupling using fixed bed and co-feed using fluid bed. Using fixed bed reactor under co-feed conditions, propane is activated easily on the catalyst surface with selectivities ranging from 30 to 75% depending on the degree of conversion. Under varying oxygen partial pressures, especially for higher than the stoichiometric ratio O₂/C₃H₈ = 1/2, nor the propane conversion or the selectivities to propene and COx are affected. The performance of the catalyst in the absence of gas phase oxygen was tested at 400 °C. It was confirmed that the catalyst surface oxygen participates to the activation of propane forming propene and oxidation products with similar selectivities as those obtained under co-feed conditions. The ability of the catalyst to fully restore its activity by oxygen treatment was checked in repetitive reduction–oxidation cycles. Fluid bed reactor using premixed propane–oxygen mixtures was also employed in the study. The catalyst was proved to be very active in the temperature range 300–450 °C attaining selectivities comparable to those of fixed bed.     

Effects of the structural and cationic properties of AV2P2O10 solids on propane selective oxidation

The activity performances of five AV₂P₂O₁₀ compounds of either orthorhombic (A=Cd, Ca), or monoclinic (A=Cd, Ba, Pb) symmetry types, have been compared for propane partial oxidation. They present a rather good activity (9% of propane conversion at 460°C) and a high selectivity (60% of propene selectivity). Results are discussed as a function of the differences in the structural properties. Kínetic studies were also performed for propane and propene oxidation reaction.     

电镀法制备FeCrAl合金负载的Co_3O_4催化剂及对丙烷的电焦耳催化氧化

金属载体负载型催化剂的电焦耳催化氧化是挥发性有机物控制技术,其核心是向金属载体中通入电流,产生焦耳热来实现负载的催化剂活化。受制于催化剂涂层与金属载体之间较低的黏附力,催化剂在金属表面的负载是技术难点。将Co和Ce电镀到FeCrAl合金表面,焙烧形成氧化物催化剂,并用于丙烷的电焦耳催化氧化。结果表明,对合金载体表面进行阳极氧化预处理,可以有效促进催化剂组分的分散,而且催化剂涂层上有空穴结构,有利于反应过程的传质; CeO_2的存在显著提高Co_3O_4催化剂对丙烷的催化氧化性能。通过进一步优化,电镀法可成为制备金属负载型催化剂的有效方法。     

SO2 promoted oxidation of ethyl acetate, ethanol and propane

The effect of SO₂ addition on the oxidation of ethyl acetate, ethanol, propane and propene, over Pt/γ-Al₂O₃ and Pt/SiO₂ has been investigated. The reactants (300–800 vol. ppm) were mixed with air and led through the catalyst bed. The conversions below and above light-off were recorded both in the absence and in the presence of 1–100 vol. ppm SO₂. For the alumina-supported catalyst, the conversion of ethyl acetate, ethanol and propane was promoted by the addition of SO₂, while the conversion of propene was inhibited. The effect of SO₂ was reversible, i.e. the conversion of the reactants returned towards the initial values when SO₂ was turned off. However, this recovery was quite slow. The oxidation of propane was inhibited by water, both in absence and presence of SO₂. For the silica-supported catalyst no significant effect of SO₂ could be observed on the conversion of ethyl acetate, ethanol or propane, whereas the conversion of propene was inhibited by the presence of SO₂. In situ FTIR measurements revealed the presence of surface sulphates on the Pt/γ-Al₂O₃ catalyst with and after SO₂ addition. It is proposed that these sulphate groups enhance the oxidation of propane, ethyl acetate and ethanol by creating additional reaction pathways to Pt on the surface of the Pt/γ-Al₂O₃ catalyst.     

Synthesis of Mn3O4 nanoparticles and their catalytic applications in hydrocarbon oxidation

Monodispersed Mn₃O₄ nanoparticles with diameter of about 10 nm were synthesized via a simple low-temperature esterification process. It was found that the particle size could be tailored by varying the synthesis temperature. The materials showed catalytic activity in the oxidation of hydrocarbons with molecular oxygen under solvent- and additives-free conditions.     

Partial oxidation of methane in Ba0.5Sr0.5Co0.8Fe0.2O3−δ membrane reactor at high pressures

Oxygen permeation fluxes through dense disk-shaped Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCFO) membranes were investigated as a function of temperature (973–1123 K), pressure (2–10 atm), and membrane thickness (1–2 mm) under an air/helium gradient. A high oxygen permeation flux of 2.01 ml/cm² min was achieved at 1123 K and 10 atm under an air/He oxygen partial pressure gradient. Based on the dependence of the oxygen permeation flux on the oxygen partial pressure difference across the membrane and the membrane thickness, it is assumed that bulk diffusion of oxygen ions was the rate-controlling step in the oxygen transport across the BSCFO membrane disk under an air/He gradient. The partial oxidation of methane (POM) to syngas using LiLaNiO_x/γ-Al₂O₃ as catalyst in a BSCFO membrane reactor was successfully performed at high pressure (5 atm). Ninety-two percent methane conversion, 90% CO selectivity, and 15.5 ml/cm² min oxygen permeation flux were achieved in steady state at a temperature of 1123 K and a pressure of 5 atm. A syngas production rate of 79 ml/cm² min was obtained. Characterization of the membrane surface by SEM and XRD after reaction showed that the surface exposed to the air side preserved the Perovskite structure while the surface exposed to the reaction side was eroded.     

Investigation on the partial oxidation of methane to syngas in a tubular Ba0.5Sr0.5Co0.8Fe0.2O3−δ membrane reactor

A perovskite material of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF), with both electronic and ionic conductivity, was synthesized by a combined citrate–EDTA complexing method. The dense membrane tube made of BSCF was fabricated using the plastic extrusion method. The partial oxidation of methane (POM) to syngas was performed in the tubular BSCF membrane reactor packed with a LiLaNiO/γ–Al₂O₃ catalyst. The reaction performance of the membrane reactor was investigated as functions of temperature, air flow rate in the shell side and methane concentration in the tube side. The mechanism of POM in the membrane reactor was discussed in detail. It was found that in the tubular membrane reactor, combustion reaction of methane with permeated oxygen took place in the reaction zone close to the surface of the membrane, then followed by steam and CO₂ reforming of methane in the middle zone of the tube side. The membrane tube can be operated steadily for 500 h in pure methane with 94% methane conversion and higher than 95% CO selectivity, and higher than 8.0 ml/cm² min oxygen permeation flux.     

Lithium insertion in ultra-thin nanobelts of Ag2V4O11/Ag

In this study, ultra-thin nanobelts of Ag₂V₄O₁₁/Ag were successfully synthesized. The synthesized ultra-thin nanobelts of Ag₂V₄O₁₁/Ag are highly crystalline and the thickness is found to be about 5 nm. A lithium battery using ultra-thin nanobelts of Ag₂V₄O₁₁/Ag as the active materials of the positive electrode exhibits a high initial discharge capacity of 276 mAh g⁻¹, corresponding to the formation of Li_xAg₂V₄O₁₁ (x = 6). With increased cycling, the electrode made of ultra-thin nanobelts of Ag₂V₄O₁₁/Ag tends to loose electrochemical activity due to Ag⁺ ions in the ultra-thin nanobelts of Ag₂V₄O₁₁ were reduced and new phase was formed.     

Electrochemical oxidation of ammonia (NH4/NH3) on thermally and electrochemically prepared IrO2 electrodes

The electrochemical oxidation of ammonia (NH₄⁺/NH₃) in sodium perchlorate was investigated on IrO₂ electrodes prepared by two techniques: the thermal decomposition of H₂IrCl₆ precursor and the anodic oxidation of metallic iridium. The electrochemical behaviour of Ir(IV)/Ir(III) surface redox couple differs between the electrodes indicating that on the anodic iridium oxide film (AIROF) both, the surface and the interior of the electrode are electrochemically active whereas on the thermally decomposed iridium oxide films (TDIROF), mainly the electrode surface participates in the electrochemical processes.On both electrodes, ammonia is oxidized in the potential region of Ir(V)/Ir(IV) surface redox couple activity, thus, may involve Ir(V). During ammonia oxidation, TDIROF is deactivated, probably by adsorbed products of ammonia oxidation. To regenerate TDIROF, it is necessary to polarize the electrode in the hydrogen evolution region. On the contrary, AIROF seems not to be blocked during ammonia oxidation indicating its fast regeneration during the potential scan. The difference between both electrodes results from the difference in the activity of the iridium oxide surface redox couples.     

The effects of SO2 on the oxidation of CO and propane on supported Pt and Au catalysts

The catalytic activities of Pt and Au supported on TiO₂ were compared with respect to the oxidation of CO and propane. While the Au catalysts showed higher activities for CO oxidation, the Pt catalysts were more active for propane combustion. A strong de-activation of the CO oxidation activity by SO₂ was observed only over the TiO₂-supported Au catalyst, indicating that SO₂ can block the active sites for CO oxidation over Au catalysts. The results are consistent with a model in which the perimeter sites have a special role in the CO oxidation reaction over Au catalysts.     

Synthesis and catalytic properties of Ce0.6Zr0.4O2 solid solutions in the oxidation of soluble organic fraction from diesel engines

Ce_0.6Zr_0.4O₂ solid solutions were synthesized by co-precipitation, sol–gel like method, solution combustion and surfactant-assistant approaches, respectively. The catalytic properties of bulk and γ-Al₂O₃ supported Ce_0.6Zr_0.4O₂ solid solutions were studied for the oxidation of soluble organic fractions (SOF) from diesel engines by TG-DTA method. The physicochemical properties were characterized by XRD, BET surface area and pore distribution, SEM, TEM, and particle size distribution techniques. XRD and TEM results show that a Ce_0.6Zr_0.4O₂ solid solution was formed for samples as-prepared and heat-treated at 900 °C for 2 h in air. The co-precipitation derived Ce_0.6Zr_0.4O₂ has as high BET surface area as 153.71 m²/g by controlling preparation conditions. Notable is that the surface area and particle size for fresh Ce_0.6Zr_0.4O₂ ignited at 350 °C decreased little after a thermal treatment in air at 900 °C for 2 h. Furthermore, its bulk density is lowest. The commercial engine oil (SJ5W/40) for FAW-VOLKSWAGEN, which was used by Bora 1.9 TDI diesel cars in China market was substituted for SOF. The catalytic activity was evaluated by normalized peak areas and extrapolated onset temperatures of DTA curves. A computer program was developed by direct non-linear regression model for simulation of TG/DTG curves to determine the thermal processes and kinetic parameters. It is found that lube evaporation/decomposition and thermal decomposition (pyrolysis) were observed under a nitrogen atmosphere. Lube evaporation fractions were inhibited by Ce_0.6Zr_0.4O₂ and γ-Al₂O₃. While under an air atmosphere, namely, in the process of lube oxidation (combustion), evaporation/decomposition, low-temperature oxidation and high-temperature oxidation were distinguished. Ce_0.6Zr_0.4O₂ solid solutions are active catalysts for lube oxidation, in which the sample prepared by solution combustion has the highest activity, mainly due to the maintenance of the surface area and particle size upon sintering and its lowest bulk density. However, γ-Al₂O₃ is more like a support. There exists synergism between Ce_0.6Zr_0.4O₂ and γ-Al₂O₃: γ-Al₂O₃ adsorbs lube retaining it within its pore structure, whereas, Ce_0.6Zr_0.4O₂ solid solutions initiate oxidation reactions when light-off temperatures reach. The application of CeO₂-ZrO₂ solid solution prepared by solution combustion at lower temperature would be promising in diesel oxidation catalysts.     

An FT-IR and flow reactor study of the conversion of propane on γ-Al2O3 in oxygen-containing atmosphere

The conversion of propane in the presence of oxygen over alumina has been studied using a fixed bed flow reactor. The interaction of the same catalyst with propane, propene, isopropanol and acetone has also been investigated, with additional gas-phase monitoring, in an FT-IR cell. Alumina looks active in the catalytic conversion of propane to propene, with the production of CO₂, CO, ethylene, methane as the main by-products, depending on the reaction temperature. Higher hydrocarbons such as butenes, butadiene, benzene and toluene are also found.

This reactivity is mainly attributed to the weak but not negligible Brønsted acidity of the surface OH’s of alumina, possibly activating propane in the form of isopropoxides and allowing oligomerization of propene. This shows the detrimental effect of the uncovered alumina support in the case of alumina-supported catalysts for propane oxydehydrogenation and explains the positive role of doping with basic neutralizing agents such as potassium.     

Synthesis, characterization and performance of CuO/La2O3 composite catalyst for ammonia catalytic oxidation

This work considers the oxidation of ammonia (NH₃) by selective catalytic oxidation (SCO) over a CuO/La₂O₃ composite catalyst at temperatures between 150 and 400 °C. A CuO/La₂O₃ composite catalyst was prepared by co-precipitation of copper nitrate and lanthanum nitrate at various molar concentrations. This study also considers how the concentration of influent NH₃ (C₀ = 1000 ppm), the space velocity (GHSV = 92,000 l/h), the relative humidity (RH = 12%) and the concentration of oxygen (O₂ = 4%) affect the operational stability and the capacity for removing NH₃. The catalysts that were characterized using FTIR, XRD, UV-Vis, BET and PSA, have shown that the catalytic behavior is related to the copper (II) oxide, while lanthanum (III) oxide may serve only to provide active sites for the reaction during a catalyzed oxidation run. The experimental results show that the extent of conversion of ammonia by SCO in the presence of the CuO/La₂O₃ composite catalyst was a function of the molar ratio. The ammonia was removed by oxidation in the absence of CuO/La₂O₃ composite catalyst, and around 93.0% NH₃ reduction was achieved during catalytic oxidation over the CuO/La₂O₃ (8:2, molar/molar) catalyst at 400 °C with an oxygen content of 4.0%. Moreover, the effect of the reaction temperature on the removal of NH₃ in the gaseous phase was also monitored at a gas hourly space velocity of under 92,000 h^− 1.