Milliseconds steam reforming of methane using Rh/MgO/γ-Al2O3 catalyst

采用负载型Rh/MgO/γ-Al₂O₃催化剂研究了毫秒级甲烷蒸汽重整过程,在水碳比为1和3的条件下,详细考察了反应温度、空速和催化剂Rh含量对反应转化率和选择性的影响。研究结果表明,Rh/MgO/γ-Al₂O₃催化剂在毫秒级操作条件下具有良好的催化性能,使用5%（质量分数）Rh催化剂,在水碳比3、反应温度1150 K、空速641.11 L•（g cat）^-1•h^-1时,CH₄转化率约90%,CO₂选择性约20%,毫秒级接触时间反应行为即可接近热力学平衡。高温有利于毫秒级甲烷蒸汽重整过程。     

Effect of steam on the acid strength of H3PW12O40/SiO2 · nH2O and its application in skeletal isomerization of n-butane

The effect of steam on the acid strength of H₃PW₁₂O₄₀ (HPW)/SiO₂ · nH₂O was determined by the Hammett indicators. When the steam content in N₂ was 1.6%, the acidity (H₀ > −13.7) of HPW/SiO₂ · nH₂O could be kept for over 10 h at 300 °C, but for only 2 h when steam was lacking. When it was used as a catalyst for skeletal isomerization of n-butane to isobutane at 300 °C, the HPW/SiO₂ · nH₂O showed stability in the presence of steam (1.6% in feed) better than that without steam, due to a suppression of the loss of crystalline water.     

Parallel screening of Cu/CeO2/γ-Al2O3 catalysts for steam reforming of methanol in a 10-channel micro-structured reactor

Steam reforming of methanol (SRM) was investigated over Cu/CeO₂/γ-Al₂O₃ catalysts with different compositions in a parallelized 10-channel micro-structured reactor. The catalytic activity was found to be strongly dependent on the copper loading. The parallel screening result was tentatively discussed with surface analysis characterization results and previous proposals. A reaction mechanism is proposed to rationalize the catalytic activity data and characteristics of the catalysts, which supposes that the copper/ceria interfacial area (partially oxidized copper nanoparticle and defective ceria) is the active site for SRM. The oxygen reverse spillover from ceria to copper is suggested to be involved in the catalysis cycle.     

Thermal cycle test performances of environmental barrier coatings of HfO2-SiO2/Yb2Si2O7 in the steam environment at 1475 °C

The novel bi-layer environmental barrier coatings (EBCs) with HfO₂-SiO₂/Yb₂Si₂O₇ structure (70HfO₂-30SiO₂/Yb₂Si₂O₇: 70HS/YbDS, 50HfO₂-50SiO₂/Yb₂Si₂O₇: 50HS/YbDS, molar ratios) was tested in 90%H₂O–10%O₂ conditions between room temperature and 1475 °C in an Al₂O₃ tube furnace, then its performance was evaluated. The YbDS layer was contaminated by alumina impurities under steam conditions. After 22 cycles, the 70HS/YbDS completely separated from the SiC substrate, while the 50HS/YbDS and SiC did not separate, even though cracks formed at the 50HS/SiC interface and the TGO layer. Furthermore, the thermally grown oxide (TGO) layer formed at the HfO₂-SiO₂/SiC interface. Formation and growth of the TGO led to the formation and propagation of cracks at the HfO₂-SiO₂/TGO interface and TGO interior, which was the culprit leading to the failure of EBCs. These results demonstrated that the 50HS/YbDS EBCs have the potential to protect SiC in steam conditions at 1475 °C.     

Production of hydrogen via combined steam reforming of methanol over CuO–CeO2 catalysts

Hydrogen production by (combined) steam reforming of methanol (CSRM) was investigated over CuO–CeO₂ catalysts prepared via the urea-combustion method. The characteristics of the resulting oxides were strongly influenced by the autoignition time during synthesis and the sample prepared with near stoichiometric quantity of urea had less favorable catalytic properties. Catalysts prepared from urea-rich or lean mixtures were more active and selective and an optimum behavior was obtained with 75% excess of urea and Cu/(Cu + Ce) ratio equal to 0.15. The higher methanol conversion in the CSRM process may be attributed to more efficient heat transfer in the bed due to combustion of part of methanol.     

Catalytic steam reforming of biomass-derived tar for hydrogen production with K2CO3/NiO/γ-Al2O3 catalyst

A major problem of using Ni-based catalysts is deactivation during catalytic cracking and reforming, lowering catalytic performance of the catalysts. Modification of catalyst with alkali-loading was expected to help reduce coke formation, which is a cause of the deactivation. This paper investigated the effects of alkali-loading to aluminasupported Ni catalyst on catalytic performance in steam reforming of biomass-derived tar. Rice husk and K₂CO₃ were employed as the biomass feedstock and the alkali, respectively. The catalysts were prepared by a wet impregnation method with γ-Al₂O₃ as a support. A drop-tube fixed bed reactor was used to produce tar from biomass in a pyrolysis zone incorporated with a steam reforming zone. The result indicated that K₂CO₃/NiO/γ-Al₂O₃ is more efficient for steam reforming of tar released from rice husk than NiO/γ-Al₂O₃ in terms of carbon conversion and particularly hydrogen production. Effects of reaction temperature and steam concentration were examined. The optimum temperature was found to be approximately 1,073 K. An increase in steam concentration contributed to more tar reduction. In addition, the K₂CO₃-promoted NiO/γ-Al₂O₃ was found to have superior stability due to lower catalyst deactivation.     

Promotional effect of H2O on the activity of In2O3‐doped Ga2O3–Al2O3 for the selective reduction of nitrogen monoxide

Effect of metal oxide additives on the catalytic performance of Ga₂O₃–Al₂O₃ prepared by the sol–gel method for the selective reduction of NO with propene in the presence of oxygen was studied. Of several metal oxide additives, the addition of In₂O₃ enhanced drastically the activity of Ga₂O₃–Al₂O₃ for NO reduction by propene in the presence of H₂O. In addition, the activity of In₂O₃‐doped Ga₂O₃–Al₂O₃ catalyst was extremely intensified by the presence of H₂O below 350°C. The promotional effect of H₂O was interpreted by the suppression of undesirable propene oxidation and the removal of carbonaceous materials deposited on the catalyst surface. We also found that close interaction of In₂O₃ and Ga₂O₃ is necessary for the enhancement of activity by H₂O. A lot of hydrocarbons except methane and oxygenated compounds served as good reducing agents, among which propene and 2‐propanol were the most efficient ones. In₂O₃‐doped Ga₂O₃–Al₂O₃ catalyst was capable of reducing NO into N₂ quite efficiently in the presence of H₂O at a very high space velocity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Glycerol steam reforming over Ni/γ-Al2O3 catalysts modified by metal oxides

The metal oxides modified Ni/γ-Al₂O₃ catalysts for glycerol steam reforming were prepared by impregnation. Characterization results of fresh catalysts indicated that the molybdates modification abated the acidity and the stronger metal-support interaction of Ni/γ-Al₂O₃ catalysts, leading to a stable catalytic activity. Especially, NiMoLa-CaMg/γ-Al₂O₃ (NiMoLa/CMA) catalyst exhibited no deactivation along with glycerol complete conversion to stable gaseous products containing 69% H₂, 20% CO and 10% CO₂ during time-on-stream of 42 h. TPO of spent Ni/γ-Al₂O₃ catalysts modified by different components showed that the carbon deposit on acidic sites and NiAl₂O₄ species led to catalysts deactivation. A lower reforming temperature and a higher LHSV and glycerol content were helpful to the production of syngas from GSR over NiMoLa/CMA; the reverse conditions would improve the formation of H₂.     

Sintering behavior of Cr2O3–Al2O3 ceramics

We investigated the sintering behavior of Cr₂O₃–Al₂O₃ ceramic materials. In our observation of the isothermal shrinkage behavior of Cr₂O₃–Al₂O₃ ceramic, the activation energy of sintering reaction was measured to be 102 kJ/mol, that is, the near value of the activation energy of diffusion of Al ions in Al₂O₃ single crystal. Therefore the diffusion of cations is believed to control the sintering behavior of this material. With the addition of TiO₂, (the compound chosen to accelerate the diffusion of cations) to Cr₂O₃–Al₂O₃, the sintering behavior was accelerated.     

Effect of P2O5 on evolution of microstructure of MgO–Al2O3–SiO2 glass ceramics

Abstract

MgO–Al₂O₃–SiO₂ (MAS) cordierite based glass ceramics were prepared by volume crystallisation. X-ray diffraction, Scanning electron microscopy and Energy diffraction scanning were used to investigate crystallisation behaviour and the influence of P₂O₅ on microstructure MAS based glass ceramics. The results showed that P⁵⁺ could promote the phase separation of MAS glass and that the glass was divided into two areas, such as Mg₄Al₂Ti₉O₂₅ and the containing P⁵⁺ area at <900°C. Mg₄Al₂Ti₉O₂₅ and Mg₃(PO₄)₂ in the area were both advantageous to the precipitation of μ cordierite, which further transformed to α cordierite due to P⁵⁺ in the residual glassy phase. However, P⁵⁺ inhibited the presence of cordierite when the heat treatment temperature was >900°C.     

Effect of Tungsten Oxide on the Crystallization Properties of Glasses of the B2O3–La2O3–Nb2O5 System

Glass Physics and Chemistry - The effect of tungsten oxide on the crystallization properties of glasses of the 37.5B2O3 22.5La2O3 (40 – x)Nb2O5 xWO3 (where x = 10, 15, 20, 30, 40 mol %)...     

Degradation of orange G by H2O2、S2O82－、S2O82－-H2O2with ferrous ion

以偶氮染料橙黄G（OG）为目标污染物,研究Fe2+分别催化H2O2、S2O82－、H2O2-S2O82－降解0.1 mmol/L OG Fe2+/H2O2体系,[Fe2+]=1 mmol/L, pH=3, [H2O2]0=10 mmol/L,降解30 min OG脱色率为96%,随着pH值增大和[H2O2]0＞10 mmol/L,OG脱色率减小,呈线性变化。Fe2+/S2O82－体系,随着S2O82－初始浓度增加OG脱色率增大,随着pH值增大OG脱色率减小,呈非线性变化。Fe2+/H2O2-S2O82－体系,pH=3, [H2O2]0=2 mmol/L, [S2O82－]0＞10 mmol/L时OG脱色率持续增大。Fe2+/H2O2-S2O82－体系矿化率最高。利用乙醇和硝基苯作为分子探针,采用分子探针竞争实验鉴定该体系中产生的SO4?和OH?。     

Effect of CeO2 and La2O3 on the Activity of CeO2−La2O3/Al2O3-Supported Pd Catalysts for Steam Reforming of Methane

The effect of the addition of CeO₂ or La₂O₃ on the surface properties and catalytic behaviors of Al₂O₃-supported Pd catalysts was studied in the steam reforming of methane. The FTIR spectroscopy of adsorbed CO and the Pd dispersion suggest the partial coverage of Pd⁰ by ceria or lanthana species. This could lead to the formation of an adduct MPd _x O (M = Ce or La) at the surface of the metal crystallites. The addition of ceria or lanthana resulted in an increase of the turnover rate and specific rate for steam reforming of methane. One possible explanation if that the Pd⁰*Pd^δ+O–M interfacial species (M = Ce or La) are oxidized by H₂O or CO₂, promoting the O* transfer to the metal surface. This could facilitate the removal of C* species from the metal surface, resulting in the increase of specific reaction rate and increase of the accessibility of CH₄ to metal active sites.     

Catalytic behavior of V2O5 in rechargeable Li–O2 batteries

The possibility of using vanadium pentoxide (V₂O₅) as a catalyst in rechargeable lithium–oxygen (Li–O₂) batteries was studied. A V₂O₅-carbon composite was cast onto Ni foam to form a cathode. Electrochemical cells designed based on the flat cell manufactured by Hohsen Corporation were fabricated. The initial discharge capacity was 715 mA?h?g^?1, and the maximum discharge capacity reached 2,260 mA?h?g^?1 during the twelfth cycle. The cell had high capacity retention during cycling (1.24?% during cycles 2–8). V₂O₅ acted as a catalyst as well as an active material, improving the specific capacity and capacity retention of the non-aqueous Li–O₂ cell more effectively than do other materials.     

On the Possibility of Forming Complexes with the Participation of O2– Ions in Melts and Glasses of the Na2O–SiO2–Cu2O System

The structural role of copper ions in melts (glasses) of the Na₂O–SiO₂–Cu₂O–CuO system is analyzed in the framework of the acid–base concept with due regard for the geometric (the radius ratio for Cu²⁽¹⁾⁺ and O^2– ions) and energy (the mean enthalpies of the Cu²⁽¹⁾⁺–O bonds) factors. It is demonstrated that copper ions in the structure fulfill the function of modifier cations. In these melts, the Cu¹⁺–Cu²⁺ redox equilibrium can be described without regard for the formation of [Cu²⁽¹⁾⁺O_4/2]^2(3)– ionic complexes (which could be incorporated into the structure of silicon–oxygen anions) and [Cu²⁺O _b/k ]^{2 – b/k} polyhedra providing the interaction between Cu²⁺ ions and anions. The influence of the formation of these polyhedra on the redox equilibrium is considered within the formalism of chemical thermodynamics. The composition dependence of the oxygen ion exponent pO is measured by an electromotive force (emf) technique. The ratio between the numbers of copper atoms with different valences is determined by chemical analysis. The experimental data obtained are in agreement with the theoretical inferences.     

Rh–Sr/Al2O3 Catalyst for N2O Decomposition in the Presence of O2

The improving effect of Sr in the catalytic activity of Rh for N₂O decomposition has been studied under 1,000 ppm N₂O/He and 1,000 ppm N₂O/5% O₂/He (GHSV = 10,000 h^?1). Different techniques have been used for catalysts characterization: TEM, SEM-EDX, XRD, N₂ adsorption at ?196 °C and in situ XPS. Sr favours the Rh dispersion and reduction under reaction conditions, and allows the low temperature removal of N₂O in the presence of O₂ (100% decomposition at 350 °C).     

Effect of adding Y2O3 on structural and mechanical properties of Al2O3–ZrO2 ceramics

The effects of adding 1–8 wt% Y₂O₃ on phase formation and fracture toughness of Al₂O₃–xZrO₂–Y₂O₃(AZY) ceramics were studied. Phase formations of the samples were characterized by the X-ray diffraction (XRD) technique. It was found that the major phase was rhombohedral-Al₂O₃, while the minor phase consisted of the monoclinic-ZrO₂, tetragonal-ZrO₂ and monoclinic-Y₂O₃. It was found that Y₂O₃ contents did not clearly influence grain shape of AZY ceramics. The results obtained from the microhardness test could be used to evaluate the fracture toughness. It was found that the smaller grains had high fracture toughness. The maximum fracture toughness of 4.827 MPa m^1/2 was obtained from 4 wt% Y₂O₃. Refinement of lattice parameters using Rietveld analysis revealed the quantitative phases of AZY ceramics. This shows that under adding Y₂O₃ conditions the proportion of tetragonal-ZrO₂ phase plays an important role for the mechanical properties of AZY ceramics.     

Influence of annealing treatment on magnetic properties of Fe2O3/SiO2 and formation of ε-Fe2O3 phase

Magnetic properties of Fe₂O₃/SiO₂ samples were studied after being produced by sol-gel synthesis and formation of ε-Fe₂O₃ polymorph. Samples were thermally treated, using different annealing temperatures and annealing times. The size and morphological characteristics of the iron oxide nanoparticles were examined using a TEM microscope. We used the “ellipticity of shapes”, which is a measure of how much the shape of a nanoparticle differs from a perfect ellipse, in order to quantitatively describe morphological properties of nanoparticles. Coercivity measurements were used to identify and monitor the formation of the epsilon-iron oxide phase during the thermal treatments (annealing). Coercivity values were in the range from 1.2 to 15.4 kOe, which is in accordance with previous experience regarding the existence of ε-Fe₂O₃. We have determined the optimal formation conditions for the ε-Fe₂O₃ polymorph (t=1050 °C for 7 h, H_C=15.4 kOe), as well as the narrow temperature interval (1050–1060 °C) in which the polymorph abruptly vanished (H_C=2300 Oe), on the basis of results of the magnetic properties. The threshold temperature for the ε-Fe₂O₃ phase transformation was measured as 1060 °C. We found that different annealing temperatures and annealing times significantly affected magnetic properties of the examined samples.