Influence of pretreatment methods on adsorption and catalytic characteristics of toluene over heterogeneous palladium based catalysts

The adsorption and catalytic characteristics of heterogeneous palladium based catalyst and its modified catalysts with gases (air and hydrogen) and acidic aqueous solution (HCl) were studied for evaluating the influence of pretreatment methods for toluene. The structural and energetic adsorption properties of the parent and pretreated catalysts were analyzed by means of nitrogen adsorption isotherms and gravimetric methods. The light-off curve and the XPS investigation were used for analyzing the catalytic activity and the surface state of palladium. It was clearly shown from the experimental results that hydrogen pretreated catalysts having metallic surface state exhibited the highest adsorption capacity and catalytic activity compared to that of parent and modified catalysts. The adsorption equilibrium data for toluene were obtained at three different temperatures and correlated successfully with the two-site Langmuir molecular isotherm model (L2m). It was also found that the palladium phase has more adsorption affinity for toluene molecules than the alumina support. The isosteric heat of adsorption calculated by using the Clausius-Clapeyron equation significantly changed with the coverage and the lateral interactions between the adsorbate-adsorbate molecules control the system. Furthermore, comparative analysis of the adsorption energy distribution revealed that the parent and its modified catalysts have different types of surface energetic heterogeneities.     

Hydrogen assisted self-ignition of propane/air mixtures in catalytic microburners

A catalytic Pt-based microdevice is evaluated for the combustion of hydrogen and/or propane. It is found that in confined ceramic microchannels hydrogen/air mixtures self-ignite over a wide range of compositions. This discovery is capitalized to self-ignite propane/air mixtures with the assistance of hydrogen addition. It is shown that propane kinetically inhibits hydrogen catalytic combustion at low hydrogen fractions. The minimum hydrogen composition for self-ignition of propane/air mixture compositions is found to be relatively constant, irrespective of propane composition. The transient and steady state behavior of these systems is described, and the minimization of hydrogen usage and startup time are discussed.     

ZnO/MoO3 mixed oxide nanotube: A highly efficient and stable catalyst for degradation of dye by air under room conditions

As a continuation of our work to develop catalysts with high activity for catalytic air wet oxidation process under mild conditions, degradation of wastewater containing 0.3 g/L Safranin-T (ST) by air oxidation over ZnO/MoO₃ nanotube catalyst was studied. It was found the decolorization efficiency and the chemical oxygen demand (COD) removal of ST reached above 98% and 95%, respectively, within 18 min at room temperature and atmospheric pressure. And the organic pollutants were totally mineralized to simple inorganic species such as HCO₃⁻, Cl⁻ and NO₃⁻, while the total organic carbon (TOC) decreased 99.3%. The structure and morphology of the catalyst after ten cycling runs showed that the catalyst was stable under such operating condition and the leaching test showed negligible leaching effect. This ZnO/MoO₃ nanotube is proved to be an active and stable heterogeneous catalyst in CWAO of ST under extremely mild conditions.     

高真空多层绝热结构中一氧化钯吸氢特性研究

对高真空下的一氧化钯吸附氢气的特性进行了分析和研究,实验测定了一氧化钯吸附氢气的机理,不同条件下一氧化钯对氢气的吸附特性,以及设置一氧化钯对夹层漏放气的影响。实验证明,在夹层中使用恰当的混合吸附剂,可以有效减小夹层的漏放气量,提高低温储罐的寿命。     

Surface and catalytic properties of doped tin oxide nanoparticles

Mixed oxides composed of Zn-Sn, Ti-Sn and V-Sn were prepared by a co-precipitation method and evaluated as catalysts for methanol oxidation in an ambient fixed-bed reactor. Surface analysis by X-ray photoelectron spectroscopy (XPS) revealed an electronic interaction between dopant and Sn atoms in the oxide structure and showed the formation of surface states associated with the dopants. Oxygen vacancies were present on the Zn-doped oxide, and the oxidation of methanol to carbon oxides was favored. The Ti-doped oxide exhibited a favorable selectivity to dimethyl ether, related to the oxygen anions near Ti centers. Vanadium dopants not only dramatically increased the catalytic activity but also promoted the partial oxidation of methanol to formaldehyde. Results demonstrate that the bridging dopant-O-Sn bond acts as active sites and influences product distribution.     

Al-pillared clays supported rare earths and palladium catalysts for deep oxidation of low concentration of benzene

Al-pillared clays supported rare earths (RE/Al-PILC) are prepared and used as supports of palladium catalysts for deep oxidation of low concentrations of benzene (130-160 ppm). The supports and catalysts are characterized by X-ray powder diffraction (XRD), FT-IR, BET, transmission electron microscopy (TEM) and temperature-programmed reduction (H₂-TPR). The results show that Al-pillaring results in a strong increase in the basal spacing (d_0 0 1) from about 1.2 to 1.8 nm, and an increase in the BET surface area from 63.6 (±3.2) to 238.8 (±11.9) m²/g. Activity tests of deep oxidation of low concentration benzene show catalysts supported on Al-PILC and RE/Al-PILC are obviously more active than that on raw clay. Pd/6% Ce/Al-PILC, in particular, can catalyze the complete oxidation of low concentration benzene at a temperature as low as about 290 °C.     

Electrochemical performance of mixed ionic–electronic conducting oxides as anodes for solid oxide fuel cell

Mixed ionic–electronic conducting (MIEC) oxides, SrFeCo_0.5O_x, SrCo_0.8Fe_0.2O_3−δ and La_0.6Sr_0.4Fe_0.8Co_0.2O_3−δ have been synthesized and prepared on yttria-stabilized zirconia as anodes for solid oxide fuel cells. Power output measurements show that the anodes composed of such kinds of oxides exhibit modest electrochemical activities to both H₂ and CH₄ fuels, giving maximum power densities of around 0.1 W/cm² at 950°C. Polarization and AC impedance measurements found that large activation overpotentials and ohmic resistance drops were the main causes for the relative inferior performance to the Ni-YSZ anode. While interlayered with an Ni-YSZ anode, a significant improvement in the electrochemical performance was observed. In particular, for the SrFeCo_0.5O_x oxide interlayered Ni-YSZ anode, the maximum power output reaches 0.25 W/cm² on CH₄, exceeding those of both SrFeCo_0.5O_x and the Ni-YSZ, as anodes alone. A synergetic effect of SrFeCo_0.5O_x and the Ni-YSZ has been observed. Future work is needed to examine the long-term stability of MIEC oxide electrodes under a very reducing environment.     

Shock-tube study of the ignition of methane/ethane/hydrogen mixtures with hydrogen contents from 0% to 100% at different pressures

The ignition delay times of diluted hydrogen/reference gas (92% methane, 8% ethane)/O₂/Ar mixtures with hydrogen contents of 0%, 40%, 80% and 100% were determined in a high-pressure shock tube at equivalence ratios ? = 0.5 and 1.0 (dilution 1:5). The temperature range was 900 K ? T ? 1800 K at pressures of about 1, 4 and 16 bar.The reference gas and the 40% hydrogen/60% reference gas data showed typical characteristics of hydrocarbon systems and can be represented by:

     

Characterization of the effects of pressure and hydrogen concentration on laminar burning velocities of methane–hydrogen–air mixtures

The aim of the present work was to characterize both the effects of pressure and of hydrogen addition on methane/air premixed laminar flames. The experimental setup consists of a spherical combustion chamber coupled to a classical shadowgraphy system. Flame pictures are recorded by a high speed camera. Global equivalence ratios were varied from 0.7 to 1.2 for the initial pressure range from 0.1 to 0.5 MPa. The mole fraction of hydrogen in the methane + hydrogen mixture was varied from 0 to 0.2. Experimental results were compared to calculations using a detailed chemical kinetic scheme (GRIMECH 3.0). First, the results for atmospheric laminar CH₄/air flames were compared to the literature. Very good agreements were obtained both for laminar burning velocities and for burned gas Markstein length. Then, increasing the hydrogen content in the mixture was found to be responsible for an increase in the laminar burning velocity and for a reduction of the flame dependence on stretch. Transport effects, through the reduction of the fuel Lewis number, play a role in reducing the sensitivity of the fundamental flame velocity to the stretch. Finally, when the pressure was increased, the laminar burning velocity decreased for all mixtures. The pressure domain was limited to 0.5 MPa due to the onset of instabilities at pressures above this value.     

The surface properties and the activities in catalytic wet air oxidation over CeO2-TiO2 catalysts

No-noble metal CeO₂-TiO₂ catalysts prepared by sol-gel method were developed and examined for catalytic wet air oxidation (CWAO) of acetic acid. The structure of the catalysts was measured by BET, SEM, XRD, XPS and DTA-TG. We investigated the effect of the interactions of Ce and Ti on the structure of CeO₂-TiO₂ catalysts. The mechanisms of the relationships between the different content of Ti and the activity of CeO₂-TiO₂ catalysts were discussed. The results showed that the average crystal size of CeO₂ decreased and the surface areas increased; the low valence of Ce³⁺ increase, and the chemisorbed oxygen slightly decreased with the increase of Ti content on the surface of CeO₂-TiO₂ catalysts. The order of the activity in CWAO of acetic acid followed: Ce/Ti 1/1 > Ce/Ti 3/1 > Ce/Ti 1/3 > Ce/Ti 5/1 > CeO₂ > TiO₂ > no catalyst. In CWAO of acetic acid, the optimal atomic ratio of Ce and Ti was 1, and the highest COD removal was over 64% at 230 °C, 5 MPa and 180 min reaction time over Ce/Ti 1/1 catalyst. The excellent activity and stability of CeO₂-TiO₂ catalysts was observed in our study.     

Heterogeneous adsorption and catalytic oxidation of benzene, toluene and xylene over spent and chemically regenerated platinum catalyst supported on activated carbon

The heterogeneous adsorption and catalytic oxidation of benzene, toluene and o-xylene (BTX) over the spent platinum catalyst supported on activated carbon (Pt/AC) as well as the chemically treated spent catalysts were studied to understand their catalytic and adsorption activities. Sulfuric aqueous acid solution (0.1N, H₂SO₄) was used to regenerate the spent Pt/AC catalyst. The physico-chemical properties of the catalysts in the spent and chemically treated states were analyzed by using nitrogen adsorption-desorption isotherm and elemental analysis (EDX). The gravimetric adsorption and the light-off curve analysis were employed to study the BTX adsorption and oxidation on the spent catalyst and its modified Pt/AC catalysts. The experimental results indicate that the spent Pt/AC catalyst treated with the H₂SO₄ aqueous solution has a higher toluene adsorption and conversion ability than that of the spent Pt/AC catalyst. A further studies of H₂SO₄ treated Pt/AC catalyst on their catalytic and heterogeneous adsorption behaviours for BTX revealed that the activity of the H₂SO₄ treated Pt/AC catalyst follows the sequence of benzene > toluene > o-xylene. The adsorption equilibrium isotherms of BTX on the H₂SO₄ treated Pt/AC were measured at different temperatures ranging from 120 to 180 °C. To correlate the equilibrium data and evaluate their adsorption affinity for BTX, the two sites localized Langmuir (L2m) isotherm model was employed. The heterogeneous surface feature of the H₂SO₄ treated Pt/AC was described in detail with the information obtained from the results of isosteric enthalpy of adsorption and adsorption energy distributions. Furthermore, the activity of H₂SO₄ treated Pt/AC about BTX was found to be directly related to the Henry's constant, isosteric enthalpy of adsorption and adsorption energy distribution functions.     

Experimental and numerical investigation of the hetero-/homogeneous combustion of lean propane/air mixtures over platinum

The pure heterogeneous and the coupled hetero-/homogeneous combustion of fuel-lean propane/air mixtures over platinum have been investigated at pressures 1 bar  p  7 bar, fuel-to-air equivalence ratios 0.23  φ  0.43, and catalytic wall temperatures 723 K  T_w  1286 K. Experiments were performed in an optically accessible catalytic channel-flow reactor and involved 1-D Raman measurements of major gas-phase species concentrations across the reactor boundary layer for the assessment of catalytic fuel conversion and planar laser induced fluorescence (LIF) of the OH radical for the determination of homogeneous ignition. Numerical predictions were carried out with a 2-D elliptic CFD code that included a one-step catalytic reaction for the total oxidation of propane on Pt, an elementary C₃ gas-phase chemical reaction mechanism, and detailed transport. A global catalytic reaction step valid over the entire pressure–temperature-equivalence ratio parameter range has been established, which revealed a p^0.75 dependence of the catalytic reactivity on pressure. The aforementioned global catalytic step was further coupled to a detailed gas-phase reaction mechanism in order to simulate homogeneous ignition characteristics in the channel-flow reactor. The predictions reproduced within 10% the measured homogeneous ignition distances at pressures p  5 bar, while at p = 7 bar the simulations overpredicted the measurements by 19%. The overall model performance suggests that the employed hetero-/homogeneous chemical reaction schemes are suitable for the design of propane-fueled catalytic microreactors.     

A study of ignition and combustion of liquid hydrocarbon droplets in premixed fuel/air mixtures in a rapid compression machine

The combustion of two fuels with disparate reactivity such as natural gas and diesel in internal combustion engines has been demonstrated as a means to increase efficiency, reduce fuel costs and reduce pollutant formation in comparison to traditional diesel or spark-ignited engines. However, dual fuel engines are constrained by the onset of uncontrolled fast combustion (i.e., engine knock) as well as incomplete combustion, which can result in high unburned hydrocarbon emissions. To study the fundamental combustion processes of ignition and flame propagation in dual fuel engines, a new method has been developed to inject single isolated liquid hydrocarbon droplets into premixed methane/air mixtures at elevated temperatures and pressures. An opposed-piston rapid compression machine was used in combination with a newly developed piezoelectric droplet injection system that is capable of injecting single liquid hydrocarbon droplets along the stagnation plane of the combustion chamber. A high-speed Schlieren optical system was used for imaging the combustion process in the chamber. Experiments were conducted by injecting diesel droplet of various diameters (50 µm < d_o < 400 µm), into methane/air mixtures with varying equivalence ratios (0 < ϕ < 1.2) over a range of compressed temperatures (700 K < T_c < 940 K). Multiple autoignition modes was observed in the vicinity of the liquid droplets, which were followed by transition to propagating premixed flames. A computational model was developed with CONVERGE™, which uses a 141 species dual-fuel chemical kinetic mechanism for the gas phase along with a transient, analytical droplet evaporation model to define the boundary conditions at the droplet surface. The simulations capture each of the different ignition modes in the vicinity of the injected spherical diesel droplet, along with bifurcation of the ignition event into a propagating, premixed methane/air flame and a stationary diesel/air diffusion flame.     

Nitrous oxide conversion in laminar premixed flames of CH4 + O2 + Ar

Experimental measurements of the adiabatic burning velocity in neat and NO formation in CH₄ + O₂ + Ar flames doped with small amounts of N₂O are presented. The oxygen content in the oxidizer was varied from 15 to 17%. Non-stretched flames were stabilized on a perforated plate burner at 1 atm. The Heat Flux method was used to determine burning velocities under conditions when the net heat loss of the flame is zero. Adiabatic burning velocities of methane + oxygen + argon mixtures were found in satisfactory agreement with the modeling. The NO concentrations in the flames doped with N₂O (100 ppm in the argon stream before mixing) were measured in the burnt gases at a fixed distance from the burner using probe sampling. Axial profiles of [NO] were found insensitive to the downstream heat losses. Experimental dependencies of [NO] versus equivalence ratio had a maximum between φ = 1.1 and 1.2. Calculated concentrations of NO were in good agreement with the measurements. In lean flames calculated concentrations of NO strongly depends on the rate constant of reaction N₂O + O=NO + NO if too high values proposed in the literature are employed. These new experimental data thus allowed for validation of the key reactions of the nitrous oxide mechanism of NO formation in flames.     

A mechanistic study on kinetic compensation effect during low-temperature oxidation of coal chars

This paper provides mechanistic insights into the low-temperature oxidation of a range of carbon materials (graphite, a sub-bituminous coal char, and a brown coal char). Kinetic analysis was carried out on oxidation of the chars, prepared from fast-heating pyrolysis, under chemical-reaction-controlled regime. FT-Raman spectroscopic analysis was adopted to provide direct structural information on the carbon structure of reacting carbon materials throughout oxidation. The results demonstrate the significance of selective oxidation under the conditions, and parallel to this, the kinetic compensation effect of carbon oxidation reaction throughout conversion for all samples. Supported by the results from FT-Raman spectroscopy, the kinetic compensation effect seems to be a result of the selective oxidation of these carbon materials with heterogeneous carbon structures. Oxidation of all samples, with or without catalysts, appears to be similar in terms of the ‘nature’ of carbon structural condensation during low-temperature oxidation, suggesting a similar increase in apparent active sites population with respect to increase of apparent energy barrier. Under the current experimental conditions, a general kinetic compensation effect correlation has been deduced for various materials, requiring only the initial char kinetic parameters. The inherent inorganic species in chars also seem to alter the ‘degree/extent’ of carbon structural condensation as results of selective oxidation. In this case, the use of the compensation effect correlation will require more information on the catalysis during oxidation, apart from the initial char kinetic parameters.     

Influence of the ignition delay time on the explosion parameters of hydrocarbon–air–oxygen mixtures at elevated pressure and temperature

Combustion phenomena change as the conditions in which they are occurring change. Proper understanding and reliable prediction of these phenomena, including important explosion indexes (e.g., flammability limits, explosion pressures), are required for achieving safe and optimal performance of industrial processes and creating new applications. To this end, we investigated the influence of the residence time on aforementioned parameters of n-butane–oxygen mixture and a typical mixture for ethylene oxide production: methane–ethylene–oxygen, focusing on how elevated conditions affect the upper explosion limit and the explosion pressure. Elevated initial conditions (T = 230 °C, P = 4–16 bar) cause pre-ignition reactions to occur in the regime of the low temperature oxidation mechanism (LTOM). These reactions change the mixture composition prior to ignition. For both mixtures investigated, these changes in the initial mixture composition, due to pre-ignition reactions, result in a different explosion pressure. This is significant, because pressure rise is used as the ignition criterion. Consequently, a different classification of the investigated mixtures, as flammable or non-flammable, is possible, depending on the residence time prior to ignition. The experimental results are compared with theoretical calculations performed using detailed reaction kinetic models.     

A resonant photoemission study of the Ce and Ce-oxide/Pd(1 1 1) interfaces

We have investigated the Ce 4f electronic states in the Ce/Pd(1 1 1) and Ce-oxide/Pd(1 1 1) systems, using resonant photoemission (Ce 4d → 4f transitions), and XPS to understand Pd-Ce interactions in ultra thin layers of cerium and ceria deposited on Pd(1 1 1). Cerium deposited on Pd(1 1 1) at room temperature forms surface Ce-Pd alloys with Ce rich character, while a Pd rich Ce-Pd alloy is formed by heating to 700 °C. A modification of the chemical state of Ce can also be seen after oxygen exposure. RPES provides evidence that Ce-oxide layers deposited on Pd(1 1 1) have a CeO₂ (Ce⁴⁺) character, however a net contribution of the Ce³⁺ states is also revealed. The Ce³⁺ states have surface character and are accompanied by oxygen vacancies. Heating to 600 °C causes Ce-oxide reduction. A significant shift of Pd 4d-derived states, induced by Pd 4d and Ce 4f hybridization, was observed. The resonant features in the valence band corresponding to Ce⁴⁺, Ce³⁺ and Ce⁰ states have been investigated for various Pd−Ce(CeO_x) coverages.     

X‐ray absorption study of the local structure at the NiO/oxide interfaces

This work reports an X‐ray absorption near‐edge structure (XANES) spectroscopy study at the Ni K‐edge in the early stages of growth of NiO on non‐ordered SiO₂, Al₂O₃ and MgO thin films substrates. Two different coverages of NiO on the substrates have been studied. The analysis of the XANES region shows that for high coverages (80 Eq‐ML) the spectra are similar to that of bulk NiO, being identical for all substrates. In contrast, for low coverages (1 Eq‐ML) the spectra differ from that of large coverages indicating that the local order around Ni is limited to the first two coordination shells. In addition, the results also suggest the formation of cross‐linking bonds Ni—O—M (M = Si, Al, Mg) at the interface.