Synthesis of highly active superacids of SO4/ZrO2 with Ir,Pt, Rh,Ru, Os,and Pd substances for reaction of butane

Highly acidic catalysts stronger than the SO₄/ZrO₂ superacid with an acid strength of Ho –16.04 were obtained by kneading Zr(OH)₄ with ammonium sulfate together with chlorides of Ir, Pt, Rh, Ru, Os, and Pd followed by calcining in air at 600°C, the metal concentration being equivalent to Pt of 7.5 wt% based on the hydroxide. The catalysts with Ir and Pt materials were highest in activity for the skeletal isomerization of butane to isobutane. The present catalysts were not obtained by treating the crystallized oxide, ZrO₂ calcined at 700°C, but the amorphous form followed by calcination to the crystallization.Superacids by metal oxides, VI. For previous publication in this series see ref. [1].     

Effect of iron oxide on the phase composition of zirconia refractories

Conclusions It has been established that in the compositions ZrO₂Y₂O₃Fe₂O₃ and ZrO₂Nd₂O₃Fe₂O₃ the processes of formation of rare earth ferrites and ZrO₂ cubic solid solutions occur simultaneously. At temperatures of up to 1300°C the ferrite-formation process is fastest; with a further increase in the temperature the synthesis of ZrO₂ cubic solid solutions is significantly intensified.In the mixture of CaO, ZrO₂, and Fe₂O₃, the calcium oxide reacts only with ZrO₂.The greatest stability in relation to the action of Fe₂O₃ is clearly found in the case of the zirconia-calcium oxide solid solutions.In the mixtures of cubic solid solutions of Nd₂Zr₂O₇-ZrO₂ or ZrO₂-Y₂O₃ and Fe₂O₃, an interaction is only possible in the case where the synthesis of ferrites is not accompanied by the restructuring of the crystal lattice of ZrO₂, i. e., by destabilization of the material.The presence of Fe₂O₃ prevents the decomposition of zirconia-calcium oxide and zirconia-neodymium oxide solid solutions under conditions of prolonged heating in air at 1300°C. The zirconia-yttria cubic solid solution is the most stable and does not decompose, regardless of the concentration of Fe₂O₃, after a dwell of 250 h at 1300°C.Translated from Ogneupory, No. 1, pp. 45–49, January, 1980.     

Recycling of waste lubricant oil into chemical feedstock or fuel oil over supported iron oxide catalysts

The recycling of waste lubricant oil from automobile industry was found to be best alternative to incineration. Silica (SiO₂), alumina (Al₂O₃), silica-alumina (SiO₂-Al₂O₃) supported iron oxide (10 wt% Fe) catalysts were prepared by wet impregnation method and used for the desulphurisation of waste lubricant oil into fuel oil. The extent of sulphur removal increases in the sequence of Fe/SiO₂-Al₂O₃<Fe/Al₂O₃<Fe/SiO₂ and this might be due to the presence of smaller crystalline size (7.4 nm) of Fe₂O₃ in Fe/SiO₂ catalyst. X-ray diffraction results suggest the presence of iron sulphide in the used catalyst. Gas chromatography with thermal conductivity detector analysis confirms the presence of H₂S in gaseous products. In addition, Fe/SiO₂ catalyst facilitated the formation of lower hydrocarbons by cracking higher hydrocarbons (≈C₄₀) present in waste lubricant oil.     

Effects of bismuth oxide on the sinterability of hydroxyapatite

The sinterability of Bi₂O₃-doped hydroxyapatite (HA) has been studied and compared with the undoped HA. Varying amounts of Bi₂O₃ ranging from 0.05 wt% to 1.0 wt% were mixed with the HA. The study revealed that most sintered samples composed of the HA phase except for compacts containing 0.3, 0.5 and 1.0 wt% Bi₂O₃ and when sintered above 1100 °C, 1000 °C and 950 °C, respectively. In general, the addition of 0.5 wt% Bi₂O₃ was identified as the optimum amount to promote densification as well as to improve the mechanical properties of sintered HA at low temperature of 1000 °C. Throughout the sintering regime, the highest value of relative bulk density of 98.7% was obtained for 0.5 wt% Bi₂O₃-doped HA when sintered at 1000 °C. A maximum Young's modulus of 119.2 GPa was measured for 0.1 wt% Bi₂O₃-doped HA when sintered at 1150 °C. Additionally, the ceramic was able to achieve highest hardness of 6.08 GPa and fracture toughness of 1.21 MPa m^1/2 at sintering temperature of 1000 °C.     

Effect of the addition ZrO2–Al2O3 on nanocrystalline hydroxyapatite bending strength and fracture toughness

Nanocrystalline hydroxyapatite powder has been synthesized from a Ca(NO₃)₂·4H₂O and (NH₄)₂HPO₄ solution by the precipitation method. In the next step we prepared ZrO₂–Al₂O₃ powder. After preparation, the powder was dried at 80 °C and calcined at 1200 °C for 1 h. Various amounts (HAP–15 wt% ZA, HAP–30 wt% ZA) of powder were mixed with the hydroxyapatite by ball milling. The powder mixtures were pressed and sintered at 1000 °C, 1100 °C and 1200 °C for 1 h. In order to study the structural evolution, X-ray diffraction (XRD) was used. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were used to estimate the particle size of the powder and observe fracture surfaces. Results show that the bending strength of pressed nanocrystalline HAP was improved significantly by the addition 15 wt% of ZrO₂–Al₂O₃ powders at 1200 °C, but the fracture toughness was not changed, however when 30 wt% of ZA powders were added to nanocrystalline HAP, the bending strength and fracture toughness of the specimens decreased at all sintering temperature.     

In situ TEM investigations of reactions of Ni, Fe and Fe-Ni alloy particles and their oxides with amorphous carbon

Ni, Fe and Ni-Fe alloy particles were vapour deposited on thin films of amorphous carbon (a-C) inside a specially equipped transmission electron microscope, and reactions with the substrate were observed at elevated temperatures. The influence of oxidation of the particles was also investigated. In contrast to Ni, which was found in earlier work to graphitise the carbon at above 600 °C without bulk carbide being involved, pure Fe reacted with the a-C support at about 500 °C to Fe₃C, which graphitised the carbon similar to Ni, starting at about 600 °C. No carbide was formed from oxidised Fe particles. FeO decomposes above 500 °C, higher oxides (Fe₃O₄, Fe₂O₃) only above 750 °C. The remaining Fe particles graphitised the carbon support directly. Alloy particles with composition Ni80:Fe20 (permalloy) graphitised a-C in the same way as pure Ni, without any phase separation. Annealing of a mixed phase of finely dispersed Ni-Fe-oxide or deposition of Ni-Fe under oxygen at above 300 °C resulted in nucleation of three-dimensional crystallites of virtually pure Ni, which graphitised the carbon, while the remaining phase of small particles was converted to inactive Ni-ferrite, NiFe₂O₄.     

A study of “superacidic” MoO3/ZrO2 catalysts for methane oxidation

A series of zirconia-supported molybdenum oxide catalysts with different molybdenum loadings prepared using conditions reported to generate “superacidity” have been evaluated for their performance as catalysts for methane oxidation. A marked dependence of Mo content on activity has been observed, with the most active material being that with intermediate molybdenum content. 5 wt% MoO₃/ZrO₂ compares favourably with Zr_xCe_1-xO₂ for methane combustion. The presence of MoO₃ is observed to stabilise the tetragonal polymorph of ZrO₂ and, as Mo content is increased, dispersed MoO₃ crystallites are formed as evidenced by Raman spectroscopy. Temperature-programmed reduction studies evidence differences in the reduction behaviour of the materials as a function of loading. The results indicate that molybdenum oxide supported on monoclinic zirconia gives rise to the most active catalyst. It is tentatively suggested that the formation of a MoO₃ monolayer during reaction may be of importance. This revised version was published online in August 2006 with corrections to the Cover Date.     

Reduction of NO by CO on Cu/ZrO2/Al2O3 catalysts: Characterization and catalytic activities

ZrO₂, γ-Al₂O₃ and ZrO₂/γ-Al₂O₃-supported copper catalysts have been prepared, each with three different copper loads (1, 2 and 5 wt%), by the impregnation method. The catalysts were characterized by nitrogen adsorption (BET), X-ray diffraction (XRD), temperature programmed reduction (TPR) with H₂, Raman spectroscopy and electronic paramagnetic resonance (EPR). The reduction of NO by CO was studied in a fixed-bed reactor packed with these catalysts and fed with a mixture of 1% CO and 1% NO in helium. The catalyst with 5 wt% copper supported on the ZrO₂/γ-Al₂O₃ matrix achieved 80% reduction of NO. Approximately the same rate of conversion was obtained on the catalyst with 2 wt% copper on ZrO₂. Characterization of these catalysts indicated that the active copper species for the reduction of NO are those in direct contact with the oxygen vacancies found in ZrO₂.     

Development of iron oxide sorbents for Hg removal from coal derived fuel gas: Sulfidation characteristics of iron oxide sorbents and activity for COS formation during Hg removal

The aim of this study is to develop a process for the removal of Hg⁰ using H₂S over iron oxides sorbents, which will be located just before the wet desulfurization unit and catalytic COS converter of a coal gasification system. It is necessary to understand the reactions between the iron oxide sorbent and other components of the fuel gas such as H₂S, CO, H₂, H₂O, etc. In this study, the sulfidation behavior and activity for COS formation during Hg⁰ removal from coal derived fuel gas over iron oxides prepared by precipitation and supported iron oxide (1 wt% Fe₂O₃/TiO₂) prepared by conventional impregnation were investigated. The iron oxide samples were dried at 110 °C (designated as Fe₂O₃-110) and calcined at 300 and 550 °C (Fe₂O₃-300 and Fe₂O₃-550). The sulfidation behavior of iron oxide sorbents in coal derived fuel gas was investigated by thermo-gravimetric analysis (TGA). COS formation during Hg⁰ removal over iron oxide sorbents was also investigated using a laboratory-scale fixed-bed reactor. It was seen that the Hg⁰ removal activity of the sorbents increased with the decrease of calcinations temperature of iron oxide and extent of sulfidation of the sorbents also increased with the decrease of calcination temperature. The presence of CO suppressed the weight gain of iron oxide due to sulfidation. COS was formed during the Hg⁰ removal experiments over Fe₂O₃-110. However, in the cases of calcined iron oxides (Fe₂O₃-300, Fe₂O₃-550) and 1 wt% Fe₂O₃/TiO₂, formation of COS was not observed but the Hg⁰ removal activity of 1 wt% Fe₂O₃/TiO₂ was high. Both FeS and FeS₂ were active for Hg⁰ removal in coal derived fuel gas without forming any COS.     

Adsorptive desulfurization of model gasoline by using modified bentonite

This work involved the investigation on the removal of organic sulfur compounds from the model liquid fuels by using adsorption desulfurization (ADS) method. For this purpose, removal of 4-methyl dibenzothiophene (4-MDBT) in model gasoline streams with raw bentonite, nanobentonite and nanobentonite modified by nanomagnetite, active carbon and Ni(NO₃)₂.9H₂O was considered. Various factors influencing the desulfurization capability, including loading and baking temperature were investigated. Thermo-gravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDX) showed that the ability of modified bentonite to adsorb 4-MDBT depends strongly on surface chemistry, particularly on the presence of basic oxygen-containing groups and acid content. The adsorbents tested for desulfurization capacity at breakthrough followed the order: 30wt% Fe₃O₄/30wt% Active carbon/40% Na -Nanobentonite?>?30wt% Fe₃O₄/30wt% Active carbon/40% Ca – Nanobentonite > 30wt % Fe₃O₄/70% Ca-Nanobentonite?>?15wt % Fe₃O₄/15wt% Ni/70% Ca– Nanobentonite. The results of preliminary tests for raw bentonite and nanobentonite were not significant in comparison with the modified nanobentonites: a, b, c, d samples, (about 40% lower than the four sample models). The optimum calcination temperature was 800°C. The multivariate methods were used for optimization of acceptance parameters. A Plackett–Burman design (PBD) was chosen as a screening method to estimate the relative influence of the factors that can be affected on the analytical response. Results show that surface area, pore size and pore volume of the bentonite can be increased several times using the impregnation method by 30wt% Fe₃O₄/30% active carbon. Also, the surface morphology of the bentonite is changed with this modification.     

Formation and properties of solid solutions of zirconium dioxide with oxides of rare earth elements

Conclusions Interaction of zirconium dioxide with oxides of cerium, yttrium and lanthanum in solid phases occurs at 1400°C with the formation of solid solutions with the cubic structure.Sintering of the specimens may result at 1700–1750°C with a 3-h soak. At 1400°C and a 6-h soak the porosity of the specimens was 30–40%.Complete stabilization of the zirconia is attained by heating to 1700–1750°C with additions of 20 mol.% CeO₂, 15% Y₂O₃ or 25% La₂O₃. An addition of ceria and yttria displaces the effects of polymorphic inversion of the zirconia to the lower temperature region.New highly refractory materials may be obtained from solid solutions of ZrO₂-20% CeO₂, ZrO₂-80% CeO₂, ZrO₂-15% Y₂O₃, ZrO₂-80% Y₂O₃ and ZrO₂-25% La₂O₃ and firing to 1750°C. Some of them have a low coefficient of thermal expansion compared with ZrO₂, stabilized with calcium oxide and magnesium oxide, and apparently better thermal-shock resistance. The advantage in regard to resistance during prolonged heating at 1200°C is possessed by the solution ZrO₂-Y₂O₃. The region of the most effective use of goods made from solid solutions of ZrO₂ with CeO₂, Y₂O₃ and La₂O₃ as highly refractory materials should be determined by extra studies.The possibility of reducing CeO₂ (fusing temperature about 2700°C) to Ce₂O₃ (fusing temperature about 1700°C) limits the use of cerium-containing materials as refractories in chiefly oxidizing conditions.     

Influence of Fe2O3 content on the dielectric behavior of aluminous porcelain insulators

Due to the increasing availability of substitute materials for electrical porcelain, research is needed to adapt formulations involving these materials to the current economic realities of the industry. This study assessed the effect of iron oxide concentration (0, 1, 2, 3, 5, and 8 wt%) on the dielectric properties of an aluminous porcelain composition commonly employed for electrical insulation based on different values of temperature and frequency. Samples with iron oxide contents of 0, 3, and 5 wt% were analyzed using dilatometry, X-ray diffraction, and scanning electron microscopy to evaluate the thermal, structural, and microstructural changes related to their Fe₂O₃ concentrations. Both the dielectric constant (ε_r) and the loss tangent (tan δ) were measured and evaluated in every sample. Results indicated that the presence of Fe₂O₃ increased the dielectric constant and loss tangent, which could result in an increase in heating by dielectric losses. Fe₂O₃ contents of up to 5 wt% had no significant effect on the performance of these insulators at room temperature (∼30 °C) and a high frequency (1 MHz), especially when the hematite phase was completely solubilized in the porcelain phases.     

Thermodynamic analysis and experimental verification of interface reactions of iron aluminide/tetragonal zirconia composite

Abstract

This paper described the thermodynamic analysis and experimental verification of interface reactions between iron aluminide intermetallic and tetragonal zirconia. Thermodynamic analysis confirmed that chemical reactions between Fe–Al intermetallic and ZrO₂ (3 mol.–%Y₂O₃ stabilised zirconia) mainly depended on the Al content in Fe–Al intermetallic. For ZrO₂(3Y)/Fe₃Al composite, the interface reactions to form Al₂O₃ and ZrAl₂ would take place when Al content was >40 at-% in Fe–Al intermetallic, while no interface reaction occurred when using Fe₃Al as toughening phase. ZrO₂(3Y)/Fe₃Al composite was synthesised by hot press sintering to further verify the thermodynamic analysis of interface reactions between iron aluminide intermetallic and tetragonal zirconia. The phase composition, morphology and interface structure of ZrO₂(3Y)/Fe₃Al were investigated by X-ray diffraction, SEM and TEM. The results show that Fe₃Al was thermodynamic stable in ZrO₂(3Y) matrix, which was in good agreement with thermodynamically analysis.     

A comparative study of thermal conductivity and thermal emissivity of high temperature solar absorber of ZrO2 /Fe2O3 and Al2O3/CuO ceramics

Oxide ceramics are considered as promising high temperature solar absorber materials. The major aim of this work is the development of a new solar absorber material with promising characteristics, high efficiency and low-cost processing. Hence, this work provides a comparative and inclusive study of densification behavior, microstructure features, thermal emissivity and thermal conductivity values of the two new high temperature solar absorbers of ZrO₂/Fe₂O₃ and Al₂O₃/CuO ceramics. Ceramic composites of ZrO₂/(10–30 wt%) Fe₂O₃ and Al₂O₃/(10–30 wt%) CuO were prepared by pressureless sintering method at a temperature of 1700 °C/2hrs. Identification of the solar to thermal efficiency of the composites was evaluated in terms of their measured thermal emissivity. Thermal efficiency and heat transfer homogeneity were investigated in terms of thermal conductivity and diffusivity measurement. The results showed that both composites exhibited comparable densification behavior, homogenous and harmonious microstructure. However, Al₂O₃/10 wt% CuO composite showed higher thermal and solar to thermal efficiencies than ZrO₂/Fe₂O₃ composites. It gave the lowest and the best thermal emissivity of 0.561 and the highest thermal conductivity of 15.4 W/m. K. These values proved to be the best amongst all those of the most known solar absorber materials made from the expensive SiC and AlN ceramics. Thus, Al₂O₃/CuO composites have succeeded in obtaining outstanding properties at a much lower price than its other competitive materials. These results may strongly identify Al₂O₃/CuO composites as promising high-temperature solar absorber materials instead of ZrO₂ and the other carbide and nitride ceramics.     

Methane Combustion in the Presence of Zirconia-Based Catalysts

The influence of “superacidic” modification has been shown to enhance the methane combustion activity of ZrO₂ at 800 °C. Modification with SO₄ ²⁻, Fe/Mn/SO₄ ²⁻ and MoO₃ has been investigated, with the latter showing the most marked effect although this is a critical function of loading. Ceria–zirconia catalysts are also active, although the compositions studied are not as effective as 5 wt% MoO₃/ZrO₂ which shows a greater mass normalised activity than Fe₂O₃.     

Oxidative dehydrogenation of 4-vinylcyclohexene into styrene over ZrO2 catalyst promoted with Fe2O3 and CaO

The oxidative dehydrogenation of 4-vinylcyclohexene (VCH) into styrene was carried out in the presence of oxygen over a ZrO₂ catalyst promoted with Fe₂O₃ and CaO. Intrinsically, ZrO₂ showed high dehydrogenation activity, which resulted in 80% styrene selectivity with 45% conversion at 425 °C and LHSV 3 h⁻¹. When the ZrO₂ was further promoted with calcium and iron, CaO/Fe₂O₃/ZrO₂, the highest styrene selectivity of 88.9% was obtained as well as the lowest deactivation. The deactivation of catalyst was prohibited properly through the introduction of oxygen in the reactant together with the modification of Fe₂O₃/ZrO₂ with CaO. The CaO/Fe₂O₃/ZrO₂ showed constant catalytic activity and selectivity for more than 50 h without deactivation. The selectivity of styrene was strongly influenced by the mole ratio of O₂/VCH and 95% selectivity with 80% conversion was obtained at O₂/VCH mole ratio of 6 over Fe₂O₃/ZrO₂. It is thought that the oxidative dehydrogenation proceeds through the dehydrogenation (DH) of ring-hydrocarbon of VCH followed by selective combustion of hydrogen (SHC) and the high selectivity of styrene was achieved by the bi-functional role of ZrO₂ for DH and SHC reactions. This revised version was published online in July 2006 with corrections to the Cover Date.     

不同制备方法对MgFe氧化物催化吸附SO2性能的影响

用不同的制备方式得到了 3种MgFe复合氧化物和混合物 ,即机械混合的Fe₂O₃ +MgO ;以MgO为载体 ,浸渍法制备的Fe₂O₃ /MgO ;以MgFe水滑石类为前驱体 ,经焙烧制得MgFeO_x.分别测定了 3种材料对SO₂ 氧化吸附的速率和硫容量 ,发现MgFeO_x 脱硫性能最好 ,硫容量达到 1.4gSO₂/g吸附剂 .通过BET、XRD和IR的表征 ,分析了材料脱硫性能好的原因 .主要是高度分散状态的MgFeO_x 中Mg和Fe的协同作用 ,Fe起到了催化氧化的作用 ,Mg是吸附中心 ,氧化和吸附的耦合加快了MgFeO_x 对SO₂ 的吸附速率 ,增加了硫容量     

Flame‐retardant action of red phosphorus/magnesium oxide and red phosphorus/iron oxide compositions in recycled PET

Red phosphorus was combined with metallic oxides Fe₂O₃ and MgO to improve the fire properties of recycled PET. Both Fe₂O₃ and MgO act as co‐synergist agents at a total loading of 5 wt%. The analysis by diffraction X of the char formed during combustion shows that transformation of Fe₂O₃ to Fe₃O₄ occurs. Fe₂O₃ favours the oxidation and improves the effectiveness of red phosphorus. It is suggested that MgO interacts with acidic end groups of PET and forms a thermal stable residue. The thermal decomposition of recycled PET containing red phosphorus combined with Fe and Mg oxides was studied by thermal analysis and leads to an increase in char formation. While the incorporation of Fe₂O₃ in this ternary blend maintains the mechanical properties of PET, the reactivity of MgO leads to a brittle material. The use of reinforcements (talc and glass fibres) to mechanically stabilize the char formed during combustion of ternary blend with Fe₂O₃ entails a further decrease in heat release rate, nevertheless impact resistance of the material decreases dramatically. Copyright © 2005 John Wiley & Sons, Ltd.     

Innovative methodology for co-treatment of mill scale scrap and manganese ore via oxidization roasting-magnetic separation for preparation of ferrite materials

Mill scale scrap, which contains vast amounts of valuable metals, is a solid waste produced in the iron and steel industry. Conventional mill scale scrap treatment methods for metal extraction are characterized by high energy consumption and low value addition. In this study, co-treatment of mill scale scrap and manganese ore via the oxidization roasting-magnetic separation process was investigated for the synchronous preparation of higher-value materials and recovery of valuable metals. Thermodynamic and magnetism analyses indicated that a higher temperature (>1100 °C) and a MnO₂/Fe₂O₃ molar ratio of 0.75–1 are essential for the preparation of manganese ferrite. The experimental validation revealed that soft magnetic manganese ferrite powders with a purity of 97.5 wt% were obtained when the test was conducted at 1300 °C for 120 min, followed by a two-stage grinding and magnetic separation process; the corresponding yield and the Mn and Fe recoveries were 78.99 wt%, 86.14 wt%, and 84.60 wt%, respectively. During the oxidization process, [Fe²⁺]O was initially oxidized to the anti-form spinel-type structure of [Fe³⁺][Fe²⁺Fe³⁺]O₄, and thereafter, it reacted with the decomposition product of [Mn³⁺][Mn²⁺Mn³⁺]O₄ to form a hybrid spinel-type structure [Me²⁺_xMe³⁺_l-x][Me²⁺_1-xMe³⁺_1+x]O₄ (Me refers to Mn and Fe) via the Mn²⁺/Fe²⁺/Mn³⁺/Fe³⁺ ions exchange at the tetrahedral and octahedral sites. Moreover, the as-purified ferrite can be used as an ingredient for the preparation of high-performance MnZn ferrite.     

The long-term high-temperature behavior of refractories produced from ZrO2 stabilized with Nd2O3

Conclusions A technology was developed for the production of zirconia refractories from ZrO₂ stabilized with Nd₂O₃. The thermal strength of the product is adequate for long-term service at a large (200–300°C/mm) temperature gradient. Products based on a zirconia — neodymium solid solution can be used several times.It was established that no appreciable Nd₂O₃ vaporization and, consequently, no appreciable destabilization of the ZrO₂ develops in a neutral medium at 2100–2500°C.The solid-phase processes developing at 2100–2500°C in products from a mixture of 70% cubic solid solution (88 mole % ZrO₂+12 mole % Nd₂O₃) and 30% unstabilized ZrO₂ fired at 1750°C consist of the redistribution of the Nd₂O₃ between the cubic solid solution Nd₂Zr₂O₇-ZrO₂ and the unstabilized ZrO₂, and the diffusion of some of the Nd₂O₃ from the cooler to the working zone.Translated from Ogneupory, No. 3, pp. 52–55, March, 1976.