A comparative study of catalytic partial oxidation of methane over CeO2 supported metallic catalysts

In the present study, the catalytic partial oxidation of methane (CPOM) over various active metals supported on CeO2 (M/CeO2, M = Ir, Ni, Pd, Pt, Rh and Ru) has been investigated. The catalysts were characterized by X-ray diffraction (XRD), BET surface area, H2-temperature programmed reduction (H2-TPR), CO chemisorption and transmission electron microscope (TEM) analysis. Ir/CeO2 catalysts showed higher BET surface area, higher metal dispersion, small active metal nano-particles (approximately 3 nm) than compared to other M/CeO2 catalysts. The catalytic tests were carried out in a fixed R(mix) ratio of 2 (CH4/O2) in a fixed-bed reactor, operating isothermally at atmospheric pressure. From time-on-stream analysis at 700 degrees C for 12 h, a high and stable catalytic activity has been observed for Ir/CeO2 catalysts. TEM analysis of the spent catalysts showed that the decrease in the catalytic activity of Ni/CeO2 and Pd/CeO2 catalysts is due to carbon formation whereas no carbon formation has been observed for Ir/CeO2 catalysts.     

Synergistic effect of transition metal oxides and ozone on PCDD/F destruction

Catalytic oxidations of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) with ozone on the transition metal oxides (iron oxide or manganese oxide) at the temperature range of 120-180 degrees C were investigated. These two catalysts were prepared by precipitation methods. Iron oxide has a higher surface area (330 m(2)/g) than manganese oxide (53 m(2)/g). In the absence of ozone, the removal efficiencies of PCDD/Fs achieved with iron oxide or manganese oxide were between 83% and 85%, while the destruction efficiencies were only between 20% and 25% at 180 degrees C. It indicates that adsorption was the main removal mechanism of PCDD/Fs over these two catalysts. On the other hand, ozone addition greatly enhanced the catalytic activity of iron oxide or manganese oxide catalysts on the oxidation of gaseous PCDD/Fs. At 180 degrees C, the destruction efficiencies of gaseous PCDD/Fs achieved with iron oxide or manganese oxide with 100 ppm O(3) exceeded 90%. It indicates that catalytic ozonation achieved with iron oxide or manganese oxide is effective in decomposing PCDD/Fs and the application of ozone lowers the reaction temperature of PCDD/F oxidation below 200 degrees C. Furthermore, the synergistic effect of iron oxide and ozone is superior to that of manganese oxide due to the fact that the surface of iron oxide has more hydroxyl groups, which easily form hydrogen bonds with ozone and decompose to form atomic oxygen for the further reaction with dioxin molecules.     

Stabilization of heavy metals in ceramsite made with sewage sludge

In order to investigate stabilization of heavy metals in ceramsite made with sewage sludge as an additive, the configuration of heavy metals in ceramsite was analysed by XRD and while leaching tests were conducted to find out the effect of sintering temperature (850 degrees C, 900 degrees C, 950 degrees C, 1000 degrees C, 1100 degrees C, and 1200 degrees C), pH (1, 3, 5, 7, 9, and 12), and H2O2 concentration (0.5molL(-1), 1molL(-1), 1.5molL(-1), 3molL(-1), and 5molL(-1)) on stabilization of heavy metals (Cd, Cr, Cu, and Pb) in ceramsite. The results indicate that leaching contents of heavy metals do not change above 1000 degrees C and sintering temperature has a significant effect on stabilization of heavy metals in ceramsite; leaching contents of heavy metals decrease as pH increases and increase as H2O2 concentration increases. XRD analysis reveals that the heavy metals exist in steady forms, mainly Pb2O(CrO(4)), CdSiO3, and CuO at 1100 degrees C. It is therefore concluded that heavy metals are properly stabilized in ceramsite and cannot be easily released into the environment again to cause secondary pollution.     

Supported Cu(II) polymer catalysts for aqueous phenol oxidation

Supported Cu(II) polymer catalysts were used for the catalytic oxidation of phenol at 30 degrees C and atmospheric pressure using air and H(2)O(2) as oxidants. Heterogenisation of homogeneous Cu(II) catalysts was achieved by adsorption of Cu(II) salts onto polymeric matrices (poly(4-vinylpyridine), Chitosan). The catalytic active sites were represented by Cu(II) ions and showed to conserve their oxidative activity in heterogeneous catalysis as well as in homogeneous systems. The catalytic deactivation was evaluated by quantifying released Cu(II) ions in solution during oxidation, from where Cu-PVP(25) showed the best leaching levels no more than 5 mg L(-1). Results also indicated that Cu-PVP(25) had a catalytic activity (56% of phenol conversion when initial Cu(II) catalytic content was 200 mg L(Reaction)(-1)) comparable to that of commercial catalysts (59% of phenol conversion). Finally, the balance between activity and copper leaching was better represented by Cu-PVP(25) due to the heterogeneous catalytic activity had 86% performance in the heterogeneous phase, and the rest on the homogeneous phase, while Cu-PVP(2) had 59% and CuO/gamma-Al(2)O(3) 68%.     

Studies on the dehydration of glycerol over niobium catalysts

The dehydration of glycerol over nanosize niobium catalysts was conducted in a stainless steel autoclave reactor. The catalysts were prepared by the calcination of niobium oxalate between 200 and 700 degrees C. Catalysts were characterized by N2 Physisorption, XRD and TPD of ammonia to investigate the effect of the calcination temperature and water on catalytic performance, catalysts' structures and acidity. Acrolein was mainly produced about 51-71% with useful by-products such as acetaldehyde and methanol. Amorphous Nb2O5 catalysts calcined at 200-400 degrees C significantly showed higher conversion of glycerol than the crystallized Nb2O5 catalyst calcined at 500-700 degrees C. Also the conversion of glycerol and selectivity of acrolein was increased with increasing the acidity of catalyst, which can be controlled by calcination temperature.     

Influence of physicochemical treatments on iron-based spent catalyst for catalytic oxidation of toluene

The catalytic oxidation of toluene was studied over an iron-based spent and regenerated catalysts. Air, hydrogen, or four different acid solutions (oxalic acid (C2H2O4), citric acid (C6H8O7), acetic acid (CH3COOH), and nitric acid (HNO3)) were employed to regenerate the spent catalyst. The properties of pretreated spent catalyst were characterized by the Brunauer Emmett Teller (BET), inductively coupled plasma (ICP), temperature programmed reduction (TPR), and X-ray diffraction (XRD) analyses. The air pretreatment significantly enhanced the catalytic activity of the spent catalyst in the pretreatment temperature range of 200-400 degrees C, but its catalytic activity diminished at the pretreatment temperature of 600 degrees C. The catalytic activity sequence with respect to the air pretreatment temperatures was 400 degrees C>200 degrees C>parent>600 degrees C. The TPR results indicated that the catalytic activity was correlated with both the oxygen mobility and the amount of available oxygen on the catalyst. In contrast, the hydrogen pretreatment had a negative effect on the catalytic activity, and toluene conversion decreased with increasing pretreatment temperatures (200-600 degrees C). The XRD and TPR results confirmed the formation of metallic iron which had a negative effect on the catalytic activity with increasing pretreatment temperature. The acid pretreatment improved the catalytic activity of the spent catalyst. The catalytic activity sequence with respect to different acids pretreatment was found to be oxalic acid>citric acid>acetic acid>or=nitric acid>parent. The TPR results of acid pretreated samples showed an increased amount of available oxygen which gave a positive effect on the catalytic activity. Accordingly, air or acid pretreatments were more promising methods of regenerating the iron-based spent catalyst. In particular, the oxalic acid pretreatment was found to be most effective in the formation of FeC2O4 species which contributed highly to the catalytic combustion of toluene.     

Growth and analysis of C nanotubes on ceramic polymer-additives

C nanotubes are synthesized by catalytic route on ceramic supports (Al2O3, MgO and CaO), usually utilized for polymer reinforcing/flame-retardancy, aiming at nanotube-based hybrid preparation. Chemical vapor deposition is carried out in i-C4H10+H2 atmosphere over 17 wt% Fe-catalysts upon different conditions. In order to clarify the influence of support material, calcination (450 degrees C or 750 degrees C) and reduction temperature (500 degrees C or 600 degrees C) of the catalysts, and synthesis temperature (600 degrees C or 700 degrees C), catalysts utilized and nanotubes obtained are systematically investigated by the use of several analysis techniques (electron microscopy, X-ray diffraction, thermo-gravimetry and Raman spectroscopy). The results obtained show that, in the considered range of variation, support material is the most influential parameter. The most catalytically active alumina supports allow achieving higher yields, but involve larger metallic inclusions and lower crystalline quality. Remaining supports behave oppositely. The reasons for such differences are discussed in the light of the current assessments on the nanotube growth and the results obtained are compared with those available in literature for similar catalysts.     

One-dimensional TiO2 nanomaterials: preparation and catalytic applications

This work reports on the syntheses of one-dimensional (1D) H2Ti3O7 materials (nanotubes, nanowires and their mixtures) by autoclaving anatase titania (Raw-TiO2) in NaOH-containing ethanol-water solutions, followed by washing with acid solution. The synthesized nanosized materials were characterized using XRD, TEM/HRTEM, BET and TG techniques. The autoclaving temperature (120-180 degrees C) and ethanol-to-water ratio (V(EtOH)/V(H2O) = 0/60 approximately 30/30) were shown to be critical to the morphology of H2Ti3O7 product. The obtained H2Ti3O7 nanostructures were calcined at 400-900 degrees C to prepare 1D-TiO2 nanomaterials. H2Ti3O7 nanotubes were converted to anatase nanorods while H2Ti3O7 nanowires to TiO2(B) nanowires after the calcination at 400 degrees C. The calcination at higher temperatures led to gradual decomposition of the wires to rods and phase transformation from TiO2(B) to anatase then to rutile. Photocatalytic degradation of methyl orange was conducted to compare the photocatalytic activity of these 1D materials. These 1D materials were used as new support to prepare Au/TiO2 catalysts for CO oxidation at 0 degrees C and 1,3-butadiene hydrogenation at 120 degrees C. For the CO oxidation reaction, Au particles supported on anatase nanorods derived from the H2Ti3O7 nanotubes (Au/W-180-400) were 1.6 times active that in Au/P25-TiO2, 4 times that in Au/Raw-TiO2, and 8 times that on TiO2(B) nanowires derived from the H2Ti3O7 nanotubes (Au/M-180-400). For the hydrogenation of 1,3-butadiene, however, the activity of Au particles in Au/M-180-400 was 3 times higher than those in Au/W-180-400 but similar to those in Au/P25-TiO2. These results demonstrate that the potential of 1D-TiO2 nanomaterials in catalysis is versatile.     

Analysis of the state and size of silver on alumina in effective removal of NOx from oxygen rich exhaust gas

Ag/alumina catalysts with different silver contents for octane-SCR were prepared by impregnation and incipient wetness methods. Activity tests revealed that the decisive factor for high activity is not only a high dispersion of silver, but also the ability of the system to redisperse clustered silver. Determination of dispersion by TEM/HAADF and O2-chemisorption experiments resulted in values close to each other even if the results were not directly comparable. This is suggested to be due to not complete silver reduction below 700 degrees C and the samples being very heterogeneous in terms of particle size, e.g., having a bimodal size distribution. Small charged Agsigman+ clusters containing 2-8 silver atoms highly prevailed in the samples containing <2 wt% Ag and exhibiting high octane-SCR activity. In highly loaded Ag/alumina samples or those reduced and reoxidized at high temperature (>400 degrees C), large metallic particles are stabilized, resulting in poor conversion of NOx to N2.     

Complete oxidation of formaldehyde at ambient temperature over supported Pt/Fe2O3 catalysts prepared by colloid-deposition method

The catalytic properties of iron oxide supported platinum catalysts (Pt/Fe(2)O(3)), prepared by a colloid deposition route, were investigated for the complete oxidation of formaldehyde. It is found that all the Pt/Fe(2)O(3) catalysts calcined at different temperatures (200-500°C) were active for the oxidation of formaldehyde. Among them, the catalysts calcined at lower temperatures (i.e., 200 and 300°C) exhibited relatively high catalytic activity and stability, which could completely oxidize HCHO even at room temperature. Based on a variety of physical-chemical characterization results, it is proposed that the presence of suitable interaction between Pt particles and iron oxide supports, which is mainly in the form of Pt-O-Fe bonds, should play a positive role in determining the catalytic activity and stability of the supported Pt/Fe(2)O(3) catalysts.     

Effect of MoO3 on the synthesis of boron nitride nanotubes over Fe and Ni catalysts

Synthesis of boron nitride nanotubes at reduced temperature is important for industrial manufactures. In this study boron nitride nanotubes were synthesized by thermal evaporation method using B/Fe2O3/MoO3 and B/Ni2O3/MoO3 mixtures separately with ammonia as the nitrogen source. The growth of boron nitride nanotubes occurred at 1100 degrees C, which was relatively lower than other metal oxides assisted growth processes requiring higher than 1200 degrees C. MoO3 promoted formation of B2O2 and aided boron nitride nanotubes growth at a reduced temperature. The boron nitride nanotubes with bamboo shaped, nested cone structured and straight tubes like forms were evident from the high resolution transmission electron microscopy. Metallic Fe and Ni, formed during the process, were the catalysts for the growth of boron nitride nanotubes. Their formation was established by X-ray diffraction. FT Raman showed a peak due to B-N vibration of BNNTs close to 1370 cm(-1). Hence MoO3 assisted growth of boron nitride nanotubes is advantageous, as it significantly reduced the synthesis temperature.     

Preparation and application of granular ZnO/Al2O3 catalyst for the removal of hazardous trichloroethylene

Trichloroethylene (TCE) is a volatile and nerve-toxic liquid, which is widely used in many industries as an organic solvent. Without proper treatment, it will be volatilized into the atmosphere easily and hazardous to the human health and the environment. This study tries to prepare granular ZnO/Al(2)O(3) catalyst by a modified oil-drop sol-gel process incorporated the incipient wetness impregnation method and estimates its performance on the catalytic decomposition of TCE. The effects of different preparation and operation conditions are also investigated. Experimental results show that the granular ZnO/Al(2)O(3) catalyst has good catalytic performance on TCE decomposition and the conversion of TCE is 98%. ZnO/Al(2)O(3)(N) catalyst has better performance than ZnO/Al(2)O(3)(O) at high temperature. Five percent of active metal concentration and 550 degrees C calcination temperature are the better and economic preparation conditions, and the optimum operation temperature and space velocity are 450 degrees C and 18,000 h(-1), respectively. The conversions of TCE are similar and all higher than 90% as the oxygen concentration in feed gas is higher than 5%. By Fourier transform infrared spectrography (FT-IR) analyses, the major reaction products in the catalytic decomposition of TCE are HCl and CO(2). The Brunauer-Emmett-Teller (BET) surface areas of catalysts are significantly decreased as the calcination temperature is higher than 550 degrees C due to the sintering of catalyst materials, as well as the reaction temperature is higher than 150 degrees C due to the accumulations of reaction residues on the surfaces of catalysts. These results are also demonstrated by the results of scanning electron micrography (SEM) and energy disperse spectrography (EDS).     

Synthesis and thermal behaviour of alkaline earth cyclo-octaphosphates

Hydrated alkaline earth cyclo-octaphosphates were made by adding an aqueous solution of alkaline earth chlorides into an aqueous solution of sodium cyclo-octaphosphate. Thermal properties of the compounds were studied by TG-DTA analysis. The water of crystallization was removed below 200°C. The cyclo-octaphosphates decomposed to produce many phosphate species up to about 500°C, and they finally reorganized to metaphosphates. The overall thermal reaction of alkaline earth cyclo-octaphosphates can be written by the equation. M4(PO3)8 · nH2O 4M(PO3)2 + nH2O     

Studies on nanosized iron based modified catalyst for Fischer-Tropsch synthesis application

To improve catalytic performance iron based catalyst, the effects of some metal promoters, especially potassium, copper and other transition metal oxides as well as different supports have been reported. A series of Fe/K/Cu catalysts promoted with magnesium and ceria by precipitation method, followed by impregnation method; keeping Cu and K content same. The catalysts were characterized by XRD, N2 physisorption, TPR and TEM techniques. From XRD, the presence of hematite (Fe2O3) phase was detected in all precipitated iron catalysts and CFe2.5 phase in all used catalysts. TPR results showed that addition of Mg facilitated the reduction of Fe2O3 and decrease in reduction temperature. The catalytic performance was investigated in a fixed-bed reactor at 250 degrees C, 2 MPa pressure and H2/CO molar ratio of 2. Concentration of Mg was found to affect the CO conversion and product distribution. It was found that precipitated iron catalyst Fe/Mg/Cu/K with Mg/Fe ratio of 0.1 showed highest conversion (60.6%) and C5(+) selectivity (92.4%) among all catalysts tested.     

Electrocatalytic activity of PtAu/C catalysts for glycerol oxidation

The electrocatalytic oxidation of glycerol on PtAu/C catalysts has been investigated by cyclic voltammetry. PtAu bimetallic nanoparticles are prepared by chemical reduction. Carbon-supported PtAu catalysts are found to exhibit high electrocatalytic activity for the oxidation of glycerol in alkaline solution in terms of oxidation potential and current density as well as stability, and PtAu/C catalysts with different Pt:Au composition ratios show no much difference in catalytic activity. In acidic solution, PtAu/C catalysts exhibit similar to Pt/C catalysts in activity, but the advantage of the PtAu/C catalysts in terms of per unit mass of platinum is still obvious. The PtAu/C catalysts, in a wide Pt:Au ratio range, show a remarkable enhancement in the mass specific activity of platinum with decreasing platinum content in both alkaline and acidic solutions. This is of significance for reducing the usage of platinum and indicates that though platinum acts as main active sites, gold also plays an important role in the function of PtAu/C catalysts.     

Oriented nanostructured titanates array from low concentration alkaline solution via hydrothermal process

Na2Ti2O5 x H2O nanowire/nanobelt array and other nanostructures were hydrothermally prepared on Ti substrate in low concentration NaOH solution (< 5 mol/L). Then the Na2Ti2O5 x H2O nanostructures were converted to H2Ti2O5 x H2O through an ion-exchange process and finally to TiO2 anatase by calcination at 450 degrees C without changing their nanostructures. The morphology of the prepared Na2Ti2O5 x H2O nanostructures could be controlled by varying the experimental parameters such as hydrothermal temperature and alkaline solution. The formation mechanism of the nanoarray was also discussed.     

具可变价态稀土氧化物对Mg2Ni合金储氢性能的催化作用

采用球磨法制备Mg2Ni-Ni-5%RExOy(CeO2,Nd2O3,Tb4O7)复合材料。通过XRD,SEM,面扫描能谱分析,电化学及动力学测试系统研究材料的组织及储氢性能。结果表明:添加稀土氧化物后复合材料的结晶程度降低,稀土氧化物催化剂在合金表面分布均匀。复合材料的最大放电容量明显提高,含Tb4O7样品室温下最大放电容量达871mAh·g-1,且具有较高循环稳定性。CeO2及Tb4O7催化剂可有效提高合金电极表面电荷转移能力,增大氢原子在合金内部的传输速率。稀土氧化物催化剂还可提高复合材料的气态吸氢容量,其中含Tb4O7样品的吸氢量最高,在250℃时吸氢量达到2.02%(质量分数),但在较低温度时吸氢速率稍慢。稀土氧化物的催化作用主要与稀土离子的变价特性有关,离子的易变价性越强,则催化活性越高。催化活性由大到小的顺序为Tb4O7>CeO2>Nd2O3。     

Complete oxidation of ethylene over supported gold nanoparticle catalysts

Complete oxidation of ethylene was performed over supported noble metals or transition metals oxide catalysts and on monoliths under atmospheric pressure. Gold nanoparticles on Al2O3 or MxOy(M = Mo, Fe, Mn) were prepared by impregnation, coprecipitation, deposition, and dispersion methods. Nanoparticles prepared by impregnation method were irregular and very large above 25 nm, but those by coprecipitation and deposition method were uniformly nanosized at 4-5 nm. The gold nanoparticle were outstandingly active in catalyzing oxidation of ethylene. The activity order of these catalysts with preparation methods was deposition > coprecipitation > impregnation, and Au/Co3O4 prepared by deposition method showed the best performance in ethylene oxidation. The addition of gold particles to MxOy/Al2O3 catalyst enhanced the ethylene oxidation activity significantly. The main role of the gold nanoparticles apparently was to promote dissociative adsorption of oxygen and to enhance the reoxidation of the catalyst.     

Nano-structured gold catalysts supported on CeO2 and CeO2-Al2O3 for NOx reduction by CO: effect of catalyst pretreatment and feed composition

Gold catalysts supported on ceria and ceria-alumina were studied in NOx reduction by CO. Gold was loaded using deposition-precipitation method. The ceria-alumina (20 wt% alumina) support was synthesized by co-precipitation. The average size of gold and ceria nano-particles was bellow 10 nm. It was established that the type of pretreatment do not have a substantial effect on the catalytic activity. The presence of O2 in the feed leads to a high conversion of CO to CO2 but no NO conversion was registered. Both NO and CO conversion was increased adding H2 to the feed. The catalytic activity became higher upon adding higher amount of H2. Supplementary to the main reaction parallel reactions took place. Bellow 200 degrees C N2O formation and at 250 degrees C and above the NH3 formation was detected. At around 200 degrees C it was established 100% selectivity to N2. The addition of water to the feed influenced positively the CO conversion and did not influence negatively the conversion of NO. The selectivity to N2 at around 200 degrees C remained 100% independent of the presence of moisture. Alumina in the mixed support prevents the sintering of both gold and ceria nano-particles. The results obtained make the catalysts containing gold supported on ceria-alumina promising for practical application.