Relationship between surface acidity and activity of solid-acid catalysts in vapour phase dehydration of methanol

A series of solid-acid catalysts comprised of γ-alumina and modified γ-alumina with different of silica were prepared by co-precipitation method. The catalysts were characterized using XRD, TGA, NH₃-TPD and BET techniques. Dehydration of methanol to dimethyl ether (DME) on solid-acid catalysts was studied in a fixed-bed reactor at the same operating conditions (T = 300 °C, P = 16 bar, WHSV = 26.07 h^− 1). According to the experimental results, silica-modified catalysts have shown better performance compared to the pure γ-alumina. It was found that surface areas increase with increasing silica loading. The results of NH₃-TPD analysis showed that the surface acidity of aluminosilicate catalysts increases with increase in SiO₂/Al₂O₃ molar ratio. Also, it was found that the catalysts with highest portion of weak and/or moderate acid sites exhibit the best catalytic performance and stability. The sample with 3 wt.% silica loading has exhibited the best activity for methanol conversion.     

Hydrogenation of aromatic compounds during gas oil hydrodewaxing: I. Effect of ruthenium content and method of nickel catalyst preparation

Ni-based (8 wt.% NiO) dewaxing catalysts for the hydroconversion of the hydroraffinate of oil fraction (d_20 °C = 0.845 g/cm³; cloud point (CP) = −2 °C; aromatics = 25.8 wt.%; S = 25 ppm) were modified with Ru. The effect of Ru content (0.6, 0.75 and 0.9 wt.% of RuO₂) and the methods of Ni catalyst preparation were examined. The catalysts were characterised by N₂ sorption, TPR, ICP, XRD, SEM, XPS, H₂ chemisorption. Activity was tested in a continuous-flow system at 6 MPa (LHSV, 2.5 h⁻¹; H₂:CH, 350 N m³/m³). NiO and RuO₂ were found to exert a synergic effect on catalytic activity. The rise in RuO₂ content from 0.6 to 0.9 wt.% increased the HDA of HON from 23 to 65% at 240 °C and was parallelled by a drop in CP (by about 15 °C). The effect of Ru was found to depend on the method of Ni catalyst preparation.     

Deactivation phenomena during catalytic wet air oxidation (CWAO) of phenol over platinum catalysts supported on ceria and ceria–zirconia mixed oxides

Catalytic wet air oxidation (CWAO) of aqueous solution of phenol was carried out with pure oxygen at 160 °C in a stirred batch reactor on platinum supported oxide catalysts (Pt/CeO₂^c calcined at 650 and 800 °C and Pt/Ce_xZr_1 − xO₂ with x = 0.90, 0.75 and 0.50). The catalysts were characterized before (BET, FT-IR spectroscopy, hydrogen chemisorptions, oxygen storage capacity (OSC)) and after reaction (TPO, elementary analysis, GC–MS and DTA–TGA). The results demonstrate a poisoning of the catalysts during CWAO reaction due to the formation of different forms of carbon deposit on the materials: carbonates and polymeric carbon species. This poisoning phenomenon is limited by the introduction of 50% of zirconium into ceria lattice for the catalysts presenting the lowest surface area. Polymeric deposits play a major role in the catalyst deactivation.     

Bimetallic catalysts for the catalytic combustion of methane using microreactor technology

Pt–W and Pt–Mo based catalysts were evaluated for methane combustion using a sandwich-type microreactor. Alumina washcoated microchannels were impregnated with platinum in combination with and promoted with tungsten and molybdenum and compared with commercially available Pt/Al₂O₃ catalysts. Catalysts were tested in the range of 300–700 °C with flow rates adjusted to GHSV of 74,000 h⁻¹ and WHSV of 316 L h⁻¹ g⁻¹. Catalysts containing tungsten were found to be the most active and the most stable possibly due to a metal interaction effect. A Pt–W/γ-Al₂O₃ containing 4.6 wt% Pt and 9 wt% W displayed the highest activity with full conversion at 600 °C and a selectivity to CO₂ of 99%.     

Gasification of charcoal using supercritical CO2 at high pressures

A novel one-shell high temperature and high pressure semi-continuous reactor has been developed for the study of the Boudouard reaction at temperatures up to 820 °C and pressures up to 32.5 MPa. Semicontinuous gasification of charcoal using supercritical CO₂ has been achieved at conversions up to 90.8% (w/w) at LSHV between 20 and 30 h⁻¹ after 5–9 h. A gasification model is proposed and validated. Effective rates of gasification (1.32 ± 0.12) × 10⁻⁶ to (6.10 ± 2.03) × 10⁻⁵ s⁻¹ were obtained. The results indicated that this method is technically feasible for the on-line production of high pressures streams of CO/CO₂ in the lab for carrying out further chemistries, avoiding the use of CO high pressure bottles.     

Uptake of heavy metal ions from aqueous solution using Mg–Al layered double hydroxides intercalated with citrate, malate, and tartrate

Mg–Al layered double hydroxide (Mg–Al LDH) was modified with organic acid anions using a coprecipitation technique, and the uptake of heavy metal ions from aqueous solution by the Mg–Al LDH was studied. Citrate·Mg–Al LDH, malate·Mg–Al LDH, or tartrate·Mg–Al LDH, which had citrate³⁻ (C₆H₅O₇³⁻), malate²⁻ (C₄H₄O₅²⁻), or tartrate²⁻ (C₄H₄O₆²⁻) anions intercalated in the interlayer, was prepared by dropwise addition of a mixed aqueous solution of Mg(NO₃)₂ and Al(NO₃)₃ to a citrate, malate, or tartrate solution at a constant pH of 10.5. These Mg–Al LDHs were found to take up Cu²⁺ and Cd²⁺ rapidly from an aqueous solution at a constant pH of 5.0. This capacity was mainly attributable to the formation of the citrate–metal, malate–metal, and tartrate–metal complexes in the interlayers of the Mg–Al LDHs. The uptake of Cu²⁺ increased in the order malate·Mg–Al LDH < tartrate·Mg–Al LDH < citrate·Mg–Al LDH. The uptake of Cd²⁺ increased in the order malate·Mg–Al LDH < tartrate·Mg–Al LDH = citrate·Mg–Al LDH. These differences in Cu²⁺ and Cd²⁺ uptake were attributable to differences in the stabilities of the citrate–metal, malate–metal, and tartrate–metal complexes. These results indicate that citrate³⁻, malate²⁻, and tartrate²⁻ were adequately active as chelating agents in the interlayers of Mg–Al LDHs.     

Thermal and mechanical properties of LaNbO4-based ceramics

Thermal and mechanical properties of polycrystalline La_1−xA_xNbO₄ (x = 0, 0.005, 0.02 and A = Ca, Sr and Ba) are reported. The materials possess a ferroelastic to paraelastic phase transition close to 500 °C, and the linear thermal expansion is significantly lower (8.6 ± 0.5 × 10⁻⁶ °C⁻¹) for the paraelastic phase compared to the ferroelastic phase (15 ± 3 × 10⁻⁶ °C⁻¹). The hardness was significantly higher for acceptor doped materials (6 GPa) compared to pure LaNbO₄ (3 GPa) due to a significantly smaller average grain size. The fracture toughness of La_0.98Sr_0.02NbO₄, measured by single edge V-notched beam method, was 1.7 ± 0.2 MPa m^1/2 independent of temperature up to 600 °C. The ferroelastic properties of the materials were confirmed by non-linear relationships between stress and strain during compression/decompression, a remnant strain after decompression and the presence of ferroelastic domains. The mechanical properties of LaNbO₄-based materials are discussed with focus on ferroelasticity, microcracking due to crystallographic anisotropy and pinning of ferroelastic domain boundaries.     

Effect of Pd additive on the activity of monolithic LaMnO3-based catalysts for methane combustion

When the perovskites are calcined at 750 °C, the incorporation of Pd into LaMnO₃ enhances the activity of the catalyst in methane combustion at temperatures below 750 °C upon substitution of 0.1 mol La with Pd, and at temperatures below 600 °C when Pd is substituted for 0.1–0.15 mol Mn. Monolith catalysts based on La_1−xPd_xMnO₃ (x = 0.1, 0.15) display a higher activity in methane combustion than do LaMn_1−xPd_xO₃-based catalysts, which is due to the higher Pd/(Pd + Mn + La) ratio. The activities of the two perovskite types increase when calcination temperature is raised from 650 to 800 °C. With the increase in calcination temperature, an increase in the Pd content and a decrease in the La content is observed on the surfaces (X-ray photoelectron spectroscopy (XPS)). The rise in the temperature of perovskite calcination to 850 °C produces sintering which leads to the lowering in both the Pd content on the surfaces and the specific surface areas (SSAs) of the perovskites and, consequently, decreases catalytic activity.     

Sintering of aluminum nitride by using alumina crucible and MoSi2 heating element at temperatures of 1650 °C and 1700 °C

Aluminum nitride (AlN) ceramics, prepared with Y₂O₃ and CaO sintering additives, have been densified in an Al₂O₃ crucible at temperatures of up to 1650 °C and 1700 °C using a conventional MoSi₂ heating element furnace. The results of this study show that relative densities in excess of 99% of theoretical and a relatively high-thermal conductivity of 147 W m⁻¹ K⁻¹ have been achieved for feedstock materials prepared with combined addition of 1 wt.% Y₂O₃ and 1 wt.% CaO. All of the phases in sintered samples have been shown to be crystalline AlN and minor amount of secondary phases, were detected such as enriched Y- and Ca-aluminates by the XRD patterns, back-scattered imagery and microprobe analysis. The advantage of using the particular experimental system and sintering condition is considered to be amenable to lower production cost and enhance the feasibility of mass production. Critical temperature for AlN densification to obtain the highest density is about 1650 °C.     

钙钛矿型混合导体透氧膜SrFe0.6Cu0.3Ti0.1O3－δ的制备与表征

Dense membrane with the composition of SrFe0.6Cu0.3Ti0.1O3-δ （SFCTO） was prepared by solid state reaction method. Oxygen permeation flux through this membrane was investigated at operating temperature ranging from 750℃ to 950℃ and different oxygen partial pressure. XRD measurements indicated that the compound was able to form single-phased perovskite structure in which part of Fe was replaced by Cu and Ti. The oxygen desorption and the reducibility of SFCTO powder were characterized by thermogravimetric analysis and temperature programmed reduction analysis, respectively. It was found that SFCTO had good structure stability under low oxygen pressure at high temperature. The addition of Ti increased the reduction temperature of Cu and Fe. Performance tests showed that the oxygen permeation flux through a 1.5 mm thick SFCTO membrane was 0.35-0.96 ml·min ^-1·cm^-2 under air/helium oxygen partial pressure gradient with activation energy of 53.2 kJ·mol^-1. The methane conversion of 85%, CO selectivity of 90% and comparatively higher oxygen permeation flux of 5 ml·min^-1·cm^- 2 were achieved at 850℃, when a SFCTO membrane reactor loaded with Ni-Ce/Al2O3 catalyst was applied for the partial oxidation of methane to syngas.     

Nano-gold supported on Fe2O3: A highly active catalyst for low temperature oxidative destruction of methane green house gas from exhaust/waste gases

A number of nano-gold catalysts were prepared by depositing gold on different metal oxides (viz. Fe₂O₃, Al₂O₃, Co₃O₄, MnO₂, CeO₂, MgO, Ga₂O₃ and TiO₂), using the homogeneous deposition precipitation (HDP) technique. The catalysts were evaluated for their performance in the combustion of methane (1 mol% in air) at different temperatures (300–600 °C) for a GHSV of 51,000 h⁻¹. The supported nano-gold catalysts have been characterized for their gold loading (by ICP) and gold particle size (by TEM/HRTEM or XRD peak broadening). Among these nano-gold catalysts, the Au/Fe₂O₃ (Au loading = 6.1% and Au particle size = 8.5 nm) showed excellent performance. For this catalyst, temperature required for half the methane combustion was 387 °C, which is lower than that required for Pd(1%)/Al₂O₃ (400 °C) and Pt(1%)/Al₂O₃ (500 °C) under identical conditions. A detailed investigation on the influence of space velocity (GHSV = 10,000–100,000 cm³ g⁻¹ h⁻¹) at different temperatures (200–600 °C) on the oxidative destruction of methane over the Au/Fe₂O₃ catalyst has also been carried out. The Au/Fe₂O₃ catalyst prepared by the HDP method showed much higher methane combustion activity than that prepared by the conventional deposition precipitation (DP) method. The XPS analysis showed the presence of Au in the different oxidation states (Au⁰, Au¹⁺ and Au³⁺) in the catalyst.     

Thin-film CoB catalyst templates for the hydrolysis of NaBH4 solution for hydrogen generation

Thin-film CoB alloy catalysts were prepared on Ni-foam substrates using electroless as well as electroplating techniques. Electroless plating was carried out using cobalt (II) sulfate as the source of Co²⁺, sodium succinate as the complexing agent, and dimethyamine borane as the source of boron as well as the reducing agent. Electroplating was carried out using cobalt (II) sulfate and cobalt (II) chloride as the sources of cobalt, and boric acid as the source of boron. The thin-film CoB/Ni-foam templates were characterized using ICP, XRD and SEM techniques. The normalized B content was in the range of 1.0–1.30 and 0.20–0.60 wt.% for electroless and electroplated templates, respectively. The B content is less than that required for stoichiometric alloy formation, which indicates the simultaneous deposition of the Co metal along with CoB alloy. An optimum condition of 0.100 M L⁻¹ each of cobalt (II) sulfate heptahydrate Co(SO₄)·7H₂O, sodium succinate (Na₂C₄H₄O₄) and dimethylamine borane (CH₃)₂NHBH₃, at 60 °C with the pH value of 4–5 and a plating time of 1 h was identified for the preparation of the catalyst templates by electroless plating. Where as, 0.125 M L⁻¹ each of cobalt (II) chloride hexahydrate (CoCl₂·6H₂O), Co(SO₄)·7H₂O, 0.125 M L⁻¹ of boric acid at the current density range of 160–320 mA cm⁻² and a temperature of 60 °C was identified as the optimum condition for the electroplating method. Maximum H₂ generation rates of 1.64 and 0.30 L min⁻¹ g⁻¹ of catalyst were obtained with electroless and electroplated thin-film CoB/Ni-foam templates, respectively. The suitability of the electroless plated CoB/Ni-foam catalyst template for extended duration of hydrogen generation from NaBH₄ was studied up to 60 h. Activation energies of 44.47 and 54.89 kJ mol⁻¹ were calculated for electroless and electroplated CoB/Ni-foam catalyst templates, respectively.     

Plasma catalytic methane conversion over sol–gel derived Ru/TiO2 catalyst in a dielectric-barrier discharge reactor

Plasma catalytic methane conversion was carried out in the presence of sol–gel derived Ru/TiO₂ catalysts within a dielectric-barrier discharge (DBD) reactor. Plasma-assisted reduction (PAR) was applied to reduce the prepared Ru/TiO₂ catalysts in DBD reactor, and most of the catalysts were successively reduced by PAR within 15 min. The highest methane conversion was obtained when 5 wt% Ru/TiO₂ catalysts were used after calcination at 400 °C. The selectivities of light alkanes (C₂H₆, C₃H₈, C₄H₁₀) were highly increased when Ru/TiO₂ catalysts were used in DBD reactor.     

C9-aldehyde hydrogenation over nickel/kieselguhr catalysts in trickle bed reactor

The objective of the present study was to select the optimal catalyst and operating conditions for the manufacture of C₉-alcohol, using C₉-aldehyde and hydrogen, in a trickle bed reactor. When CaO, Ce₂O₃ or MgO was added as a promoter to the Ni/kieselguhr catalyst, the BET and Ni surface areas were increased. In the reaction for the manufacture of C₉-alcohol, using C₉-aldehyde and hydrogen in a batch reactor, a Ni–MgO/kieselguhr catalyst showed the highest activity. In addition, the catalyst using Na₂CO₃ as a precipitant showed the highest activity. According to the result of an experiment to find the optimal reaction conditions for C₉-alcohol synthesis, using C₉-aldehyde and hydrogen in a trickle bed reactor loaded with Ni–MgO/kieselguhr catalyst, the highest yield of C₉-alcohol was 91.5 wt% at 130 °C, 400 psi and WHSV = 3. The C₉-aldehyde hydrogenation performance of the Ni–MgO/kieselguhr catalyst was similar to that of a Cu/ZnO/Al₂O₃ catalyst, but superior to that of Cu–Ni–Cr–Na/Al₂O₃ and Ni–Mo/Al₂O₃ catalysts. In a long-term catalysis test, the Ni–MgO/kieselguhr catalyst showed higher stability than the Cu/ZnO/Al₂O₃ catalyst.     

Dimethyl ether synthesis via methanol and syngas over rare earth metals modified zeolite Y and dual Cu–Mn–Zn catalysts

A series of zeolite Y modified with La, Ce, Pr, Nd, Sm and Eu were prepared via ion-exchange, and characterized by XRD, FT-IR and NH₃-TPD. It was found that these rare earth metals were encapsulated in the supercage of zeolite Y and resulted in its enhanced acidity. Among them, La-, Ce-, Pr- and Nd-modified zeolite Y exhibited higher activity and stability (than pure HY) for methanol dehydration to dimethyl ether (DME). For DME synthesis directly from CO hydrogenation using the dual Cu–Mn–Zn/modified-Y catalysts, it was found that Cu–Mn–Zn/La–Y and Cu–Mn–Zn/Ce–Y were more active than Cu–Mn–Zn/pure-HY. The conversion of CO on Cu–Mn–Zn/Ce–HY achieved 77.1% in an isothermal fixed bed reactor at 245 °C, 2.0 MPa, H₂/CO = 3/2 and 1500 h⁻¹.     

Effect of strontium and cerium doping on the structural characteristics and catalytic activity for C3H6 combustion of perovskite LaCrO3prepared by sol–gel

Two series of Sr- or Ce-doped La_1−xM_xCrO₃ (x = 0.0, 0.1, 0.2 and 0.3) catalysts were prepared by thermal decomposition of amorphous citrate precursors followed by annealing at 800 °C in air atmosphere. The effect of Ce and Sr on the morphological/structural properties of LaCrO₃ was investigated by means of thermogravimetric/differential thermal analysis (TG/DTA) of the precursors decomposition under air, X-ray diffraction (XRD), electron paramagnetic resonance (EPR), transmission electron microscopy–X-ray energy dispersive spectroscopy (TEM–XEDS), S_BET determination, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) techniques. The characterization results are employed to explain catalytic activity results for C₃H₆ combustion. It is shown that the lanthanum chromite perovskite structure is obtained upon thermal treatment of the sol–gel derived precursors at T > ca. 800 °C. The presence of the dopant generally induces the formation of segregated oxide phases in the samples calcined at 800 °C although some introduction of the Sr in the perovskite structure is inferred from EPR measurements. The oxidation activity becomes maximised upon formation of such doped perovskite structure.     

ZnBO-doped (Ba, Sr)TiO3 ceramics for the low-temperature sintering process

ZnBO-doped (Ba, Sr)TiO₃ ceramics were investigated for low-temperature co-fired ceramics (LTCCs) applications. Until now, B₂O₃ and Li₂CO₃ dopants have been commonly employed as the low-temperature sintering aids. In this paper, we suggest ZnBO as an alternative dopant to the B₂O₃ and Li₂CO₃. To reduce the sintering temperature of (Ba, Sr)TiO₃, we have added 1–5 wt.% of ZnBO to (Ba, Sr)TiO₃. ZnBO-doped (Ba, Sr)TiO₃ ceramics were respectively sintered from 750 to 1350 °C by 50 °C to confirm the sintering temperature with different dopant contents. By adding 5 wt.% of ZnBO to the (Ba, Sr)TiO₃ ceramics, the sintering temperature of (Ba, Sr)TiO₃ ceramics can be reduced to 1100 °C. From the XRD analysis, ZnBO-doped (Ba, Sr)TiO₃ has no pyro phase. By adding ZnBO dopants to (Ba, Sr)TiO₃ ceramics, both of relative dielectric permittivity and loss tangent were decreased. From the frequency dispersion of dielectric properties, the relative dielectric permittivity and loss tangent of 5 wt.% ZnBO-doped (Ba, Sr)TiO₃ were 1180 and 3.3 × 10⁻³, while those of BST were 1585 and 4.8 × 10⁻³, respectively.     

Effect of ethyleneglycol addition on the properties of P-doped NiMo/Al2O3 HDS catalysts: Part I. Materials preparation and characterization

Phosphorous-doped NiMo/Al₂O₃ hydrodesulfurization (HDS) catalysts (nominal Mo, Ni and P loadings of 12, 3, and 1.6 wt%, respectively) were prepared using ethyleneglycol (EG) as additive. The organic agent was diluted in aqueous impregnating solutions obtained by MoO₃ digestion in presence of H₃PO₄, followed by 2NiCO₃·3Ni(OH)₂·4H₂O addition. EG/Ni molar ratio was varied (1, 2.5 and 7) to determine the influence of this parameter on the surface and structural properties of synthesized materials. As determined by temperature-programmed reduction, ethyleneglycol addition during impregnation resulted in decreased interaction between deposited phases (Mo and Ni) and the alumina carrier. Dispersion and sulfidability (as observed by X-ray photoelectron microscopy) of molybdenum and nickel showed opposite trends when incremental amounts of the organic were added during catalysts preparation. Meanwhile Mo sulfidation was progressively decreased by augmenting EG concentration in the impregnating solution, more dispersed sulfidic nickel was evidenced in materials synthesized at higher EG/Ni ratios. Also, enhanced formation of the so-called “NiMoS phase” was registered by increasing the amount of added ethyleneglycol during simultaneous Ni–Mo–P–EG deposition over the alumina carrier. That fact was reflected in enhanced activity in liquid-phase dibenzothiophene HDS (batch reactor, T = 320 °C, P = 70 kg/cm²) and straight-run gas oil desulfurization (steady-state flow reactor), the latter test carried out at conditions similar to those used in industrial hydrotreaters for the production of ultra-low sulfur diesel (T = 350 °C, P = 70 kg/cm², LHSV = 1.5 h⁻¹ and H₂/oil = 2500 ft³/bbl).     

The Electro-Reduction of Carbon Dioxide in a Continuous Reactor

This paper reports an investigation into the electro-reduction of CO₂ in a laboratory bench-scale continuous reactor with co-current flow of reactant gas and catholyte liquid through a flow-by 3D cathode of 30^# mesh tinned-copper. Factorial and parametric experiments were carried out in this apparatus with the variables: current (1–8 A), gas phase CO₂ concentration (16–100 vol%) and operating time (10–180 min), using a cathode feed of [CO₂ + N₂] gas and 0.45 m KHCO₃(aq) with an anolyte feed of 1 m KOH(aq), in operation near ambient conditions (ca. 115 kPa(abs), 300 K). The primary and secondary reactions here were respectively the reduction of CO₂ to formate (HCOO⁻) and of water to hydrogen, while up to ca. 5% of the current went to production of CO, CH₄ and C₂H₄. The current efficiency for formate depended on the current density and CO₂ pressure, coupled with the hydrogen over-potential plus mass transfer capacity of the cathode, and decreased with operating time, as tin was lost from the cathode surface. For superficial current densities ranging from 0.22 to 1.78 kA m⁻², the measured values of the performance indicators are: current efficiency for HCOO⁻ = 86–13%, reactor voltage = 3–6 Volt, specific energy for HCOO⁻ = 300–1300 kWh kmol⁻¹, space-time yield of HCOO⁻ = 2 × 10⁻⁴–6 × 10⁻⁴ kmol m⁻³ s⁻¹, conversion of CO₂ = 20–80% and yield of organic products from CO₂ = 6–17%.     

Preparation and electrochemical performance of micro-nanostructured nickel

Micro-nanostructured nickel has been prepared as anode materials for Li ion batteries, via a rheological phase reaction method. Ni₂C₂O₄·xH₂O (x = 2 or 2.5) as precursors are obtained from the solid–liquid rheological mixture of (NH4)₂C₂O₄·H₂O and Ni(NO₃)₂. The nickel powders are prepared by thermal decomposition of the precursors. The structural, morphological and electrochemical performance are investigated by means of thermogravimetry (TG), differential scanning calorimetry (DSC), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM) and typical electrochemical tests. The micro-nanostructured nickel displays an initial discharge capacity of 457 mAh g⁻¹. It also has a remarkable cycling stability with an average capacity fade of 0.17% per cycle from 13th to 50th cycle in 0.01–3.00 V versus Li at a constant current density of 100 mA g⁻¹.