Preparation and characterization of Al3+-doped TiO2 tight ultrafiltration membrane for efficient dye removal

Al³⁺-doped TiO₂ (AT) tight ultrafiltration membrane with stable anatase phase was prepared by a modified sol-gel process using butyl titanate and aluminum chloride as the precursor and aluminum source respectively. The removal of Alizarin red-S was investigated by filtration experiment. A dip-coating process on homemade flat Al₂O₃ intermediate layer by TiO₂ sol followed by heat treatment was adopted to obtain the desired AT membrane. The addition of Al³⁺ inhibits the phase transformation of nanosized TiO₂ from anatase to rutile and restrains the growth of crystallite, resulting in the pore size of the separation layer reducing to 3.5 nm. The prepared AT1-500 membrane exhibits enhanced hydrophilicity with no cracks or pinholes, and shows a water permeability of 9.6 L m^-2 h⁻¹ bar⁻¹ and cut-off molecular weight (MWCO) of 4650 Da. The membrane demonstrated a retention rate of 96.9% for Alizarin Red-S (250 ppm) and maintained almost constant under repeated using.     

Fabrication of Palladium Membranes Supported on a Silicalite‐1 Zeolite‐Modified Alumina Tube for Hydrogen Separation

Thin palladium membranes were fabricated on macroporous α‐Al₂O₃ tubes by electroless plating. The silicalite‐1 (Sil‐1) zeolite serving as intermediate and diffusion barrier layer was introduced to modify the surface roughness and pore size of the porous substrate and prevent the atomic interdiffusions of the metal elements between Pd layer and the support. The Pd composite membranes were studied by scanning electron microscopy (SEM), X‐ray diffraction (XRD), and electron probe microanalysis (EPMA), revealing that morphology and structure of the Sil‐1 layer significantly influence the Pd membrane preparation. Single‐gas permeation tests were carried out with gas H₂ and N₂ to determine the permeation performance of the membranes. The resulting membrane exhibited long‐term stability under hydrogen permeation.     

原位红外光谱法研究Pd-Ag/Al2O3和Pd/ Al2O3乙炔加氢催化剂

以一氧化碳和乙炔为探针分子,采用原位红外光谱技术研究了Pd-Ag/ Al₂O₃和Pd/ Al₂O₃催化剂上乙炔加氢反应以及催化剂本身的表面形态,动态考察了乙炔加氢的气相反应行为、CO吸附以及催化剂表面吸附物种的变化。结果表明,在Pd-Ag/ Al₂O₃催化体系中,由于Ag的加入而受到几何效应和电子效应的共同影响,引起了催化剂表面形态的改变从而改变了催化剂的性能。另外,乙炔加氢反应会导致钯催化剂表面形成由长分子链的饱和烃组成的碳氢化合物层,该碳氢化合物层有可能是加氢反应形成的绿油。     

Enhanced Conversion in the Direct Synthesis of Diethyl Carbonate from Ethanol and CO2 by Process Intensification

To overcome the low equilibrium conversion in the direct synthesis of diethyl carbonate from ethanol and CO₂ under moderate reaction conditions, the reaction was conducted in a membrane reactor packed with pelletized Cu‐Ni:3‐1 supported on activated carbon. A SiO₂/γ‐Al₂O₃ commercial membrane and zeolite A membranes synthesized on commercial Al₂O₃ supports were evaluated in the membrane reactor. Although characterization of the membranes by X‐ray diffraction confirmed the presence of a zeolite A layer on the supports, gas permeation and permselectivity tests of ethanol and water evidenced some defects of the synthesized membranes. An increase in conversion with respect to a conventional packed‐bed reactor was observed in the membrane reactors prepared on Al₂O₃, but equilibrium conversion was not attained. However, with the commercial membrane, the ethanol conversion was higher than the equilibrium conversion.     

Pd/Al2O3 composite hollow fibre membranes: Effect of substrate resistances on H2 permeation properties

Al₂O₃ hollow fibres with different asymmetric macrostructures, i.e. various thickness ratios between a finger-like layer and a sponge-like layer, have been prepared by a phase inversion/sintering technique. Such asymmetric hollow fibres are used as substrates on which Pd membrane is deposited directly by an electroless plating (ELP) technique without any pre-treatment on substrate surface. Influences of the substrate macrostructure on hydrogen permeation through the Pd/Al₂O₃ composite membranes have been investigated both experimentally and theoretically. The hydrogen permeation through the Pd/Al₂O₃ composite membranes was not only determined by the Pd membrane thickness, but also by the macrostructural parameters of the substrate, such as effective porosity, mean pore size and pore size distribution etc. The thinner the Pd membrane, the higher the effective porosity is required to alleviate the substrate effect on the hydrogen permeation. Also, the deviation of the pore size is suggested to be around 1.2 for the further improved hydrogen permeation through the composite hollow fibre membranes.     

Effect of metal‐support interface on hydrogen permeation through palladium membranes

Thin palladium membranes of different thicknesses were prepared on sol‐gel derived mesoporous γ‐alumina/α‐alumina and yttria‐stabilized zirconia/α‐alumina supports by a method combining sputter deposition and electroless plating. The effect of metal‐support interface on hydrogen transport permeation properties was investigated by comparing hydrogen permeation data for these membranes measured under different conditions. Hydrogen permeation fluxes for the Pd/γ‐Al₂O₃/α‐Al₂O₃ membranes are significantly smaller than those for the Pd/YSZ/α‐Al₂O₃ membranes under similar conditions. As the palladium membrane thickness increases, the difference in permeation fluxes between these two groups of membranes decreases and the pressure exponent for permeation flux approaches 0.5 from 1. Analysis of the permeation data with a permeation model shows that both groups of membranes have similar hydrogen permeability for bulk diffusion, but the Pd/γ‐Al₂O₃/α‐Al₂O₃ membranes exhibit a much lower surface reaction rate constant with higher activation energy, due possibly to the formation of Pd‐Al alloy, than the Pd/YSZ/α‐Al₂O₃ membranes. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Decomposition and oxidation of CH3 13CH2OH on A12O3, Pd/Al2O3, and PdO/Al2O3 catalysts

Temperature-programmed desorption (TPD) and oxidation (TPO) were used to investigate the decomposition and oxidation of ethanol on Al₂O₃, Pd/Al₂O₃, and PdO/Al₂O₃. Ethyl--¹³C alcohol (CH₃ ¹³CH₂OH) was adsorbed on the catalysts so that reaction pathways of the two carbons could be distinguished. Alumina was mainly a dehydration catalyst, but dehydrogenation was also observed and some carbon remained on the surface. In the presence of O₂, A1₂O₃ oxidized the decomposition products and the-carbon was oxidized faster. Ethanol, which was adsorbed on A1₂O₃, decomposed much faster on Pd/A1₂O₃ by diffusing to Pd and undergoing CO elimination to form CH₄,¹³CO, H₂, and surface carbon. On PdO/A1₂O₃, the decomposition was slower than on Pd/A1₂O₃ until lattice oxygen was extracted above 450 K; the decomposition products were oxidized by lattice oxygen. In the presence of gas phase O₂, Pd/Al₂O₃ was an active oxidation catalyst at low temperature, but lattice oxygen had to be extracted from PdO/A1₂O₃ before it had significant oxidation activity.     

The issue of selectivity in the direct synthesis of H2O2 from H2 and O2: the role of the catalyst in relation to the kinetics of reaction

The kinetic behavior in the direct synthesis of H₂O₂ with Pd–Me (Me = Ag, Pt) catalysts prepared by depositing the noble metals by electroless plating deposition (EPD) or deposition–precipitation (DP) methods on α-Al₂O₃ asymmetric ceramic membrane with or without a further surface coating by a carbon thin layer is reported. The effect of the second metal with respect to Pd-only catalysts considerably depends on the presence of the carbon layer on the membrane support. Several factors in the preparation of these membranes as well as the reaction conditions (temperature, concentration of Br⁻, pH) determine the selectivity in H₂O₂ formation, influencing the rate of the consecutive reduction of H₂O₂ (which is faster with respect to H₂O₂ decomposition on the metal surface) and/or of direct H₂ + O₂ conversion to H₂O. Defective Pd sites are indicated to be responsible for the two unselective reactions leading to water formation (parallel and consecutive to H₂O₂ formation), but the rate constants of the two reactions are differently influenced from the catalytic membrane characteristics. Increasing the noble metal loading on the membrane not only increases the productivity to H₂O₂, but also the selectivity, due to the formation of larger, less defective, Pd particles.     

Facile surface modification of porous stainless steel substrate with TiO2 intermediate layer for fabrication of H2-permeable composite palladium membranes

The increasing demand in compact hydrogen separators greatly stimulated the investigation and utilization of composite palladium membranes. Porous stainless steel (PSS) tubes were chosen as substrate material in this study, and a novel process of carbon-assisted solid-state sintering was introduced to modify the PSS surface with a TiO₂ layer. A Pd/TiO₂/PSS membrane with a Pd thickness of 6 µm was successfully fabricated via electroless plating. Scanning electron microscopy (SEM), metallographic microscopy, X-ray diffraction and pore-size analyses were performed for material characterizations. As measured by H₂/N₂ single-gas testing, the fabricated Pd/TiO₂/PSS membrane is permeable and selective to hydrogen, and it was stable during a time-on-stream of 100 h under 450°C.     

Mechanism of sulfur poisoning on supported noble metal catalyst — The adsorption and transformation of sulfur on palladium catalysts with different supports

A series of supported palladium catalysts (Pd/Al₂O₃, Pd/MgO and Pd/TiO₂) were prepared by the impregnating method and treated with H₂S, H₂ +O₂ or O₂, among which H₂S is used as a poison and H₂ +O₂ or O₂ are as purging atmospheres. The S^2– species in the supports was introduced by means of mechanically mixing Na₂S with the supports or catalysts. X-ray photoelectron spectroscopy (XPS) was employed to determine the changes in the chemical states of oxygen, palladium and sulfur in the catalysts before and after the treatment, while infrared (IR) spectroscopy was used to measure the SO^2– ₄ group produced in the catalysts and supports. The results show that on MgO and TiO₂ carriers whose acidities are weak, there exist two kinds of oxygen species, one is the lattice oxygen, the other one is the active species of oxygen. The latter can oxidize the S^2– into SO^2– ₄ even at room temperature in air. Because of the weak acidities and smaller specific surface area of MgO and TiO₂, the S^2– is liable to adsorb on the catalysts and to transform into SO^2– ₄. But for the case of Al₂O₃ support its acidity is rather strong, and its surface oxygen species under the experimental conditions is not so active as that in MgO and TiO₂ carries. The poison H₂S on the Al₂O₃ support only experiences a process of physical adsorption-desorption. In Pd/Al₂O₃ catalyst, the negatively charged sulfur ions are not so easily adsorbed and transformed as those in Pd/MgO and Pd/TiO₂. It is also implied that the properties of the carriers are related to the ability of self-regeneration of the corresponding catalysts. Pd/Al₂O₃ catalyst is more able to self-regenerate than Pd/MgO and Pd/TiO₂ catalyst.     

Spatially-Resolved Calorimetry: Using IR Thermography to Measure Temperature and Trapped NOX Distributions on a NOX Adsorber Catalyst

Palladium catalysts supported on CeO_2, Ce_0.75Zr_0.25O₂, ZrO_2, TiO₂, Nb₂O₅, Al₂O₃ were studied on the total oxidation of butyl carbitol. Several techniques were used to characterize the samples such as diffuse reflectance spectroscopy (DRS), temperature programmed reduction (TPR), cyclohexane dehydrogenation and CO temperature programmed desorption (TPD). DRS and TPR results revealed the presence of bulk PdO and PdO with strong interaction with the support. The catalytic tests showed the following order for decreasing activity: Pd/Ce_0.75Zr_0.25O₂ > Pd/CeO₂ > Pd/TiO₂ > Pd/Nb₂O₅ > Pd/Al₂O₃ > Pd/ZrO₂. However, when the turnover frequency (TOF) was calculated, all the samples had similar values.     

Design and processing of Al2O3–Al2TiO5 layered structures

Al₂O₃–Al₂TiO₅ layered composites were manufactured by a colloidal route from aqueous Al₂O₃ and TiO₂ suspensions with 50 vol.% solids. The mechanical behaviours of individual monolithic composite materials were combined and taken as basis for the design of the layered structures. Residual stresses which are likely to occur due to processing and thermally introduced misfits were calculated and considered for the manufacture of the laminates.Monoliths with 10, 30 and 40 vol.% of second phase showed that increasing proportions of aluminium titanate decrease strength and increase the non-linear behaviour.In order to obtain the desired combination of mechanical behaviours of the layers, two laminate designs with external and central layers of one composition and the alternating internal layer of the other composition were chosen taking into account chemical compatibility and development of residual stresses. In the system AA10, external and central layers of monophase Al₂O₃ with high strength were combined with intermediate layers of Al₂O₃ with 10 vol.% of Al₂TiO₅. The system A10A40 was selected to combine low strength and energy absorbing intermediate layers of Al₂O₃ with 40 vol.% of Al₂TiO₅ and sufficient strength provided by external layers of Al₂O₃ with 10 vol.% of Al₂TiO₅.The stress–strain behaviour of the laminates was linear up to their failure stresses, with apparent strain for zero load after fracture larger than that corresponding to the monoliths of the same composition as that of the external layers. Moreover, the stress drop of the laminate samples occurred in step-like form thus suggesting the occurrence of additional energy consuming processes during fracture.     

Palladium-Based Catalysts with Improved Sulphur Tolerance for Diesel-Engine Exhaust Systems

Palladium-based catalysts have been developed for the diesel exhaust system with an emphasis on their sulphur tolerance during the simultaneous oxidation of CO and HC. Promising materials include Au–Pd–Pt, Co–Pd–Pt and Ni–Pd–Pt supported on Al₂O₃ or TiO₂ and Pd–Pt/MoO₃–Al₂O₃ with the Al₂O₃ support modified with MoO₃ monolayer.     

Formation of TiO2 nano fibers on a micro-channeled Al2O3-ZrO2/TiO2 porous composite membrane for photocatalytic filtration

In this study, needle-shape TiO₂ fibers were successfully fabricated inside a micro-channeled Al₂O₃-ZrO₂ composite porous membrane system using sol-gel method. The micro-channeled Al₂O₃-ZrO₂ composite was fabricated using the fibrous monolithic (FM) process. Pure anatase phase TiO₂ was crystallized from the as-coated amorphous phase during calcination at 510 °C. The TiO₂ fibers grew on the surface frame of the micro-channeled Al₂O₃-ZrO₂ composite membrane and fully covered the inside of the micro-channeled pores. The specific surface area of the TiO₂ coated membrane system was dramatically increased by over 100 fold compared to that of the non-coated system. The photocatalytic activity of the membrane was also assessed and was shown to very effectively convert organic materials. Thus, this novel membrane holds promise for use as an advanced filtration system.     

In situ synthesis,mechanical and cyclic oxidation properties of Ti3AlC2/Al2O3 composites

ABSTRACT

Ti₃AlC₂/Al₂O₃ composite materials were successfully fabricated from TiO₂/TiC/Ti/Al powders by the in situ reactive hot pressed technique. The microstructure, mechanical and oxidation properties of the composites were investigated in the paper. Vickers hardness increased with the Al₂O₃ content. The relative density of Ti₃AlC₂/Al₂O₃ composites exhibits a declining tendency with Al₂O₃ content especially exceeds 10 vol.?%. The Ti₃AlC₂/Al₂O₃ composites show excellent electrical conductivity. The flexural strength and fracture toughness of Ti₃AlC₂/10 vol. % Al₂O₃ are 461 ± 20?MPa and 6.2?±?0.2?MPa m^1/2, respectively. The cyclic oxidation behaviour of resistance of Ti₃AlC₂/10 vol. % Al₂O₃ composites at 800–1000°C generally obeys a parabolic law. The oxide scale of sample consists of a mass of α-Al₂O₃ and TiO₂, forming a dense and adhesive protect layer. The result indicates that the Al₂O₃ can greatly improve the oxidation resistance of Ti₃AlC₂.     

Synthesis,characterization and performance evaluation of an optimized ceramic membrane with physical separation and photocatalytic degradation capabilities

The main goal of the present study is synthesis, characterization and performance evaluation of an optimized photocatalytic ceramic membrane for wastewater treatment. It consists of three layers including alumina (Al₂O₃) macroporous support, colloidal titania (TiO₂) mesoporous intermediate layer and polymeric TiO₂ mesoporous top layer in order to obtain a pore gradient from the support through the top layer of membrane. The colloidal and polymeric TiO₂ layers were prepared via the sol-gel method and coated using sol dip-coating approach. In order to optimize the membrane, physical separation and photocatalytic degradation capabilities of each colloidal and polymeric layer as a function of time were evaluated using Rhodamine B (RhB) aqueous solution. Thus, optimum coating number of intermediate layer and top layer were determined. Also, the performance of the optimized membrane was investigated via oily wastewater treatment using crude oil and water emulsion. Based on the performance results, two consequence colloidal layers and one polymeric layer were considered as the optimum layer number. Also, RhB photocatalytic degradation was 24.7% and RhB physical separation and permeation flux were 40.4% and 25.7?kg?m^?2 h^?1, respectively. Furthermore, based on the oily wastewater treatment experiments, permeation flux and chemical oxygen demand (COD) rejection at the best-operating conditions (pressure of 5?bar, the temperature of 30?°C and cross flow of 600?l?h^?1) were 29.1?kg?m^?2 h^?1 and 78.4%, respectively. The prepared membrane was found efficient and exhibited high industrial potential due to its multifunctional capability and thus can be employed as an advanced material for wastewater treatment applications.     

Support modification to improve the sulphur tolerance of Ag/Al2O3 for SCR of NOx with propene under lean-burn conditions

Ag/Al₂O₃ catalysts with 1 wt% SiO₂ or TiO₂ doping in alumina support have been prepared by wet impregnation method and tested for sulphur tolerance during the selective catalytic reduction (SCR) of NO_x using propene under lean conditions. Ag/Al₂O₃ showed 44% NO_x conversion at 623 K, which was drastically reduced to 21% when exposed to 20 ppm SO₂. When Al₂O₃ support in Ag/Al₂O₃ was doped with 1 wt% SiO₂ or TiO₂ the NO_x conversion remained constant in presence of SO₂ showing the improved sulphur tolerance of these catalysts. Subsequent water addition does not induce significant deactivation. On the contrary, a slight promotional effect on the activity of NO conversion to nitrogen is observed after Si and Ti incorporation. FTIR study showed the sulphation of silver and aluminum sites of Ag/Al₂O₃ catalysts resulting in the decrease in the formation of reactive intermediate species such as –NCO, which in turn decreases NO_x conversion to N₂. In the case of Ag/Al₂O₃ doped with SiO₂ or TiO₂, formation of silver sulphate and aluminum sulphate was drastically reduced, which was evident in FTIR resulting in remarkable improvement in the sulphur tolerance of Ag/Al₂O₃ catalyst. These catalysts before and after the reaction have been characterized with various techniques (XRD, BET surface area, transmittance FTIR and pyridine adsorption) for physico-chemical properties.     

An XPS evidence of the effect of the electronic state of Pd on CH4 oxidation on Pd/γ–Al2O3 catalysts

In this work, we investigated the catalytic activity of 2% Pd/γ–Al₂O₃ and 2% Pd–1% Sn/γ–Al₂O₃ for CH₄ oxidation in lean conditions in the presence and in the absence of SO₂ in the reaction feed. The catalysts were studied by the Pd3d_5/2 electron binding energy values determined by XPS analysis. Sulfates formation and/or tin addition to Pd/Al₂O₃ resulted in an increase of the Pd3d_5/2 electron binding energy. Results showed a direct relation between Pd activity for CH₄ oxidation and the degree of oxidation of Pd species.     

Effect of intermediate layer on gas separation performance of disk supported carbon membrane

Porous alumina disk ceramic was decorated with various types of intermediate layers via one-step spray coating-carbonization technique. P-84 (BTDA-TDI/MDI) polymeric solution was sprayed on the alumina disk with an incorporation of intermediate layer. The membrane was carbonized at 700°C under nitrogen (N₂) atmosphere with a heating rate of 3°C/min. The resultant carbon membrane was characterized in terms of its thermal stability, structural morphology, and gas permeation properties. A high-performance carbon membrane was obtained with the intermediate layer of the alumina powder, which exhibited the best selectivity of O₂/N₂, CO₂/N₂ and CO₂/CH₄ of 4.39, 19.89 and 58.43, respectively.     

Homogeneous/heterogeneous palladium based catalytic system for Heck reaction. The reversible transfer of palladium between solution and support

Pd(II)/Al₂O₃ and Pd(0)/Al₂O₃, containing 0.6% of palladium were characterized by EDX, SEM and XRD methods and used as catalysts of the Heck coupling of bromobenzene with butyl acrylate at 140 °C in molten [Bu₄N]Br salt. Monoarylated (trans-PhCH = CHC(O)OBu) (1) and diarylated (Ph₂C = CHC(O)OBu) (2) products were obtained in amounts dependent on kind of base present in the system (Scheme 1). During the reaction palladium was partially leached from the support forming [Bu₄N][PdBr₄] complex that catalyze Heck reaction or undergo readsorption on Al₂O₃. These soluble palladium complexes are partially reduced to Pd soluble nanoparticles which can also be anchored on Al₂O₃ giving active catalyst of Pd(0)/Al₂O₃ type. Reduction of Pd(II) to Pd(0) during catalytic process at the presence of bases (NaHCO₂, NaHCO₃, NaOAc, Cs₂CO₃) was studied by XPS method and the total reduction was observed in reactions of PdCl₂(PhCN)₂ with NaHCO₂ or with NaHCO₃ and [Bu₄N]Br. It was experimentally proved that heterogenized catalyst, Pd(0)/Al₂O₃, after oxidative addition of aryl halides, serve as a source of soluble palladium species and colloidal nanoparticles that are active as homogeneous catalysts.