Dehydrogenation of isobutane over Sn/Pt/Na-ZSM-5 catalysts: The effect of SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ratio,amount and distribution of Pt nanoparticles on the catalytic behavior

Sn/Pt/Na-ZSM-5 was used as catalyst for the dehydrogenation of isobutane, and the effect of SiO₂/Al₂O₃ ratio and the dispersion of Pt nanoparticles on the conversion and product selectivity were studied under atmospheric pressure at 848 K. The catalysts were characterized by various techniques such as H₂ chemisorption, TEM, SEM, EDX, XRD, FT-IR, TG/DTG, elemental analysis by XRF and ICP techniques. Higher dispersion of Pt nanoparticles in the catalyst with SiO₂/Al₂O₃ ratio of 40 resulted in higher selectivity for isobutene.     

Catalytic cracking of isobutane over HZSM-5, FeHZSM-5 and CrHZSM-5 catalysts with different SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ratios

Several systems of HZSM-5, FeHZSM-5 and CrHZSM-5 zeolite catalysts with different ratios of SiO₂/Al₂O₃ (25,38,50,80, and 150) were prepared and they were characterized by means of X-ray diffraction (XRD), UV–Vis, NH₃-TPD and BET techniques. The results indicated that, compared with uncalcined HZSM-5 zeolites, the total acid amounts, acidic site density and acidic strength of HZSM-5, FeHZSM-5 and CrHZSM-5 zeolite catalysts obviously decreased, while those of weak acid amounts obviously enhanced with the decrease of SiO₂/Al₂O₃ molar ratio. When the ratio of SiO₂/Al₂O₃ is less than 50, the three systems of HZSM-5, FeHZSM-5 and CrHZSM-5 zeolite catalysts with same ratio of SiO₂/Al₂O₃ gave similar and high isobutane conversions. However, when the ratio of SiO₂/Al₂O₃ was equal to or greater than 80, these three systems of catalysts possessed different altering tendencies of isobutane conversions, thus their isobutene conversions were different. High yields of light olefins were obtained over the FeHZSM-5 and CrHZSM-5 zeolite catalysts with high ratio of SiO₂/Al₂O₃ (≥80). The ratio of SiO₂/Al₂O₃ has large effects on the surface area, and acidic characteristics of HZSM-5, FeHZSM-5 and CrHZSM-5 zeolites catalysts, and thus further affect their catalytic performances for isobutane cracking. That is the nature of SiO₂/Al₂O₃ ratio effect on the catalytic performances.     

Preparation and application of zeolite beta with super-low SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ratio

This paper presents the direct synthesis of super-low SiO₂/Al₂O₃ ratio zeolite beta molecular sieve through a novel route, by which some of aluminium species are added during crystaling process. The IR results show that with the increase of aluminium content in the framework, the frequency of the band in the range of framework vibration (1060–1090 cm⁻¹) shifts to the lower wave-number; the BET surface-area decreases and the basicity of zeolite becomes stronger. In a second step, new adsorbents were obtained by solid-state ion exchanging zeolite beta with Cu(I), Ag(I) cations. The deep-desulfurization (sulfur levels of <1 ppmw) tests were performed using fixed-bed adsorption technique, the sulfur content of the treated and untreated gasoline was analyzed by microcoulometry. The experimental results show that the desulfurization performance of sorbents decreases in order: Cu(I)beta > Ag(I)beta > Na-beta. The best sorbent, Cu(I)beta, has breakthrough adsorption capacities of 0.236 mmolS/g of sorbent for model gasoline.     

The Structure of Fusion-Cast High-Chrome Oxide Refractories in the Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> - MgO - Al<Subscript>2</Subscript>O<Subscript>3</Subscript> System

The phase composition and structure of fusion-cast refractories composed of 57.0 – 84.2% Cr₂O₃, 4.3 – 36.1% MgO, 2.0 – 9.7% Al₂O₃, and 2.4 – 6.9% SiO₂ have been studied by petrographic and x-ray spectral microprobe analysis methods. Refractories high in MgO with modulus M = (Cr₂O₃ +Al₂O₃)/MgO = 1.64 – 3.1 are shown to consist of spinel phase Mg(Cr, Al)₂O₄ and silicate glass. Refractory materials (80.8 – 84.2% Cr₂O₃, 4.3 – 4.7% MgO, 2.0 – 9.7% Al₂O₃, and 2.7 – 6.9% SiO₂ with M = 18.7 – 20.2) are three-phase systems composed of spinel, escolaite, and glass phase. These materials, owing to their high corrosion resistance, have promising potentiality for practical applications.__________Translated from Novye Ogneupory, No. 12, pp. 69 – 74, December, 2004.     

Migration processes in the glass forming melts of the Na<Subscript>2</Subscript>O–BaO–Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system

The specific conductivity and tracer of diffusion of sodium and barium ions have been determined and the values of the transport numbers and correlation factor for diffusion have been calculated in two melts of the Na₂O–BaO–Ga₂O₃–SiO₂ system.     

Characterization of Fischer–Tropsch Cobalt-Based Catalytic Systems (Co/SiO<Subscript>2</Subscript> and Co/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) by X-ray Diffraction and Magnetic Measurements

Results of the characterization of six Co-based Fischer–Tropsch (FT) catalysts, with 15% Co loading and supported on SiO₂ and Al₂O₃, are presented. Room temperature X-ray diffraction (XRD), temperature and magnetic field (H) variation of the magnetization (M), and low-temperature (5 K) electron magnetic resonance (EMR) are used for determining the electronic states (Co⁰, CoO, Co₃O₄, Co²⁺) of cobalt. Performance of these catalysts for FT synthesis is tested at reaction temperature of 240 °C and pressure of 20 bars. Under these conditions, 15% Co/SiO₂ catalysts yield higher CO and syngas conversions with higher methane selectivity than 15% Co/Al₂O₃ catalysts. Conversely the Al₂O₃ supported catalysts gave much higher selectivity towards olefins than Co/SiO₂. These results yield the correlation that the presence of Co₃O₄ yield higher methane selectivity whereas the presence of Co²⁺ species yields lower methane selectivity but higher olefin selectivity. The activities and selectivities are found to be stable for 55 h on-stream.     

Synthesis of nickel catalysts supported on Zr-doped ordered mesoporous Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and their catalytic performance for low-temperature CO<Subscript>2</Subscript> reforming of CH<Subscript>4</Subscript>

A series of Zr-doped ordered mesoporous Al₂O₃ with various Zr contents were synthesized by evaporation-induced self-assembly strategy and the Ni-based catalysts supported on these Al₂O₃ materials were prepared by impregnation method. These catalysts with large specific surface area, big pore volume, uniform pore size possess excellent catalytic performance for the low-temperature carbon dioxide reforming of methane. The activities of these catalysts were tested in carbon dioxide reforming of methane reaction with temperature increasing from 500 to 650?°C and the stabilities of these catalysts were evaluated for long time reaction at 650?°C. It was found that when Zr/(Zr?+?Al) molar ratio?=?0.5%, the Ni/0.5ZrO₂–Al₂O₃ catalyst showed the highest activity, and exhibited superior stabilization compared to the Ni-based catalyst supported on traditional ordered mesoporous Al₂O₃. The “confinement effect” from mesoporous channels of alumina matrix is helpful to stabilize the Ni nanoparticles. As a promoter, Zr could stabilize the ordered mesoporous framework by reacting with Al₂O₃ to form ZrO₂–Al₂O₃ solid solution. Since ZrO₂ enhances the dissociation of carbon dioxide, more oxygen intermediates are given to remove the carbon formed during the reaction.     

Europium(II) in glasses of the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>-MnO-Eu<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Triply and doubly charged states of europium are revealed by ¹⁵¹Eu Mössbauer spectroscopy in the structure of glasses of the composition (mol %) 19.5Al₂O₃, 31.5SiO₂, 26.5MnO, and 22.5Eu₂O₃. The isomer shifts in the Mössbauer spectra of Eu³⁺ and Eu²⁺ ions in the structure of glasses differ from the isomer shifts in the spectra of the Eu₂O₃ and EuO compounds. This difference is explained by the fact that the electron density at ¹⁵¹Eu nuclei is affected by the manganese and aluminum atoms, which are not bound directly to the europium atoms. The broadening of the spectra of the Eu²⁺ ions in glasses is caused by the nonuniform isomer shift.     

Unexpected Support Effect in Hydrotreating: Evidence of a Metallic Character for ReS<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and ReS<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> Catalysts

Abstract  

Rhenium sulfide based catalysts were prepared by the incipient wetness impregnation method over alumina and silica supports and evaluated for 4,6-dimethyldibenzothiophene hydrodesulfurization in a high-pressure stirred-tank reactor. The catalyst prepared over silica was about six times more active for hydrodesulfurization than the corresponding catalyst prepared over alumina and a NiMo/Al₂O₃ industrial reference catalyst. This surprising and positive SiO₂ support effect was explained by a metallic character of the supported sulfide, which was demonstrated using a kinetic approach of competitive hydrogenations and by XPS characterization.     

Influence of pressure on the refractive index and relative density of glasses in the CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The pressure dependences of the refractive index for aluminosilicate glasses of the compositions 0.167CaO · 0.167Al₂O₃ · 0.666SiO₂ and 0.157CaO · 0.177Al₂O₃ · 0.666SiO₂ at pressures up to 6.0 GPa are determined using a polarizing interference microscope and an apparatus with diamond anvils. The compressibilities of the glasses are calculated from the measured refractive indices within the framework of the theory of photoelasticity. The structural-chemical parameters NBO/T (where NBO is the number of gram-ions of nonbridging oxygen atoms and T is the total number of gram-ions of network formers) are calculated for the glasses under investigation with allowance made for the formation of triclusters and highly coordinated aluminum.     

Polystyrene-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite solid polymer electrolyte for lithium secondary battery

In a common salt-in-polymer electrolyte, a polymer which has polar groups in the molecular chain is necessary because the polar groups dissolve lithium salt and coordinate cations. Based on the above point of view, polystyrene [PS] that has nonpolar groups is not suitable for the polymer matrix. However, in this PS-based composite polymer-in-salt system, the transport of cations is not by segmental motion but by ion-hopping through a lithium percolation path made of high content lithium salt. Moreover, Al₂O₃ can dissolve salt, instead of polar groups of polymer matrix, by the Lewis acid-base interactions between the surface group of Al₂O₃ and salt. Notably, the maximum enhancement of ionic conductivity is found in acidic Al₂O₃ compared with neutral and basic Al₂O₃ arising from the increase of free ion fraction by dissociation of salt. It was revealed that PS-Al₂O₃ composite solid polymer electrolyte containing 70 wt.% salt and 10 wt.% acidic Al₂O₃ showed the highest ionic conductivity of 9.78 × 10^-5 Scm^-1 at room temperature.     

Synthesis and properties of flux-cast refractories in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Details are given of the synthesis and testing of flux-cast refractory materials in the alumina-rich region of the Al₂O₃-MgO-B₂O₃ system; XRD and petrography indicate that the main structure-forming phases are corundum and magnesian spinel. In subordinate amounts there are the boroaluminate 9Al₂O₃·2B₂O₃ and the previously unknown compound 4Al₂O₃·MgO·2B₂O₃, whose composition has been established by microprobe analysis. Corrosion tests showed that three-component systems containing magnesium and boron oxides at levels of 5–10% do not increase the corrosion resistance of refractories in molten sodium-calcium-silicate glass and electrovacuum borosilicate glass. __________ Translated from Novye Ogneupory, No. 3, pp. 161–163, March, 2008.     

ZrO<Subscript>2</Subscript>-and HfO<Subscript>2</Subscript>-based electrochemical sensors intended for investigation of glass-forming oxide melts

A theoretical analysis was made of the possible use of solid electrolytes with oxygen-ion conductivity for investigation of the relative basicity of silicate melts, and the optimum design of the electrochemical cell was chosen. Glasses in the SiO₂-Na₂O system were synthesized, and ceramic sensory membranes based on the cubic solid solution (ZrO₂)_0.92(Y₂O₃)_0.08 were prepared. An electrochemical cell based on ZrO₂ and HfO₂ and intended for investigation of glass-forming melts with the use of a platinum electrode and a reference electrode with oxygen-ion conductivity was designed and fabricated. The concentration dependence of the electromotive force of the electrochemical cells was examined for melts in the SiO₂-Na₂O system containing alkali oxide in different concentrations. A mathematical treatment of the obtained dependence of the electromotive force on the Na₂O concentration in this system was performed. The results obtained were used to calculate the relative oxygen ion activities and the corresponding pO values for alkali silicate melts under investigation.     

Phase separation in melts of the ZrO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The morphology of the quenched and slowly crystallized samples in the ZrO₂-Al₂O₃ system is investigated in the composition range 25–70 wt % ZrO₂. It is revealed that, irrespective of the cooling rate, the samples contain large baddeleyite (or corundum) crystals, eutectic mixtures, and characteristic regions of intergrown elongated baddeleyite and corundum grains with micron sizes. These regions have the same phase composition at any initial ratio between zirconium and aluminum oxides and at any cooling rates of the melt. A hypothesis is put forward that these regions are products of the decomposition of ZrO₂ · 2Al₂O₃ associates.     

On the fluctuation structure of single-phase glasses in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The structure of single-phase glasses in the SrO-B₂O₃-SiO₂ system has been studied by the small-and large-angle X-ray scattering technique. The glasses containing 35, 40, and 45 mol % SrO upon equimolar replacement of B₂O₃ by SiO₂ have been investigated. It has been demonstrated that the glasses do not contain chemical inhomogeneity regions. The inhomogeneity of the glasses is determined only by thermal density fluctuations. The isothermal compressibility varies insignificantly upon replacement of B₂O₃ by SiO₂ and decreases with an increase in the SrO content. The glass structure is consistent with the model of ideal associated solutions.     

Fabrication of SAPO-34 Crystals with Different Morphologies by Microwave Heating

The crystal size and shape of the silicoaluminophosphate molecular sieve SAPO-34 have been effectively controlled in the reaction system of Al₂O₃–P₂O₅–SiO₂–TEAOH–H₂O under microwave radiations. Nano sheet-like SAPO-34 crystals are obtained when using colloidal silica as the silica source. When TEOS is used as the source of silica, homogeneous SAPO-34 crystals with a particle size of about 100 nm are formed, and the morphology of the crystals changes from uniform nano particles (~100 nm) to microspheres (~1.5 μm) by varying the H₂O/Al₂O₃ molar ratio. To further investigate the morphology control of SAPO-34, the synthetic factors, such as the silica source, water content, crystallization time and aging time have been studied in detail.     

Glass formation region and order of formation of crystalline phases in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The glass formation region in the SrO-B₂O₃-SiO₂ system has been refined. The order of formation of crystalline phases in the system has been investigated at SrO contents of 50–75 mol %. It has been demonstrated that, at low temperatures, the 2SrO · SiO₂ and 3SrO · B₂O₃ phases crystallize first irrespective of the composition. The congruent melting temperature of the 3SrO · B₂O₃ · SiO₂ compound is determined to be 1180 ± 10°C. The triangulation previously performed for the SrO-B₂O₃-SiO₂ system in the concentration range 50–75 mol % SrO has been confirmed.     

Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and CeO<Subscript>2</Subscript>-promoted MgO sorbents for CO<Subscript>2</Subscript> capture at moderate temperatures

A series of Al₂O₃ and CeO₂ modified MgO sorbents was prepared and studied for CO₂ sorption at moderate temperatures. The CO₂ sorption capacity of MgO was enhanced with the addition of either Al₂O₃ or CeO₂. Over Al₂O₃-MgO sorbents, the best capacity of 24.6 mg- CO₂/g-sorbent was attained at 100 °C, which was 61% higher than that of MgO (15.3 mg-CO₂/g-sorbent). The highest capacity of 35.3 mg-CO₂/g-sorbent was obtained over the CeO₂-MgO sorbents at the optimal temperature of 200 °C. Combining with the characterization results, we conclude that the promotion effect on CO₂ sorption with the addition of Al₂O₃ and CeO₂ can be attributed to the increased surface area with reduced MgO crystallite size. Moreover, the addition of CeO₂ increased the basicity of MgO phase, resulting in more increase in the CO₂ capacity than Al₂O₃ promoter. Both the Al₂O₃-MgO and CeO₂-MgO sorbents exhibited better cyclic stability than MgO over the course of fifteen CO₂ sorption-desorption cycles. Compared to Al₂O₃, CeO₂ is more effective for promoting the CO₂ capacity of MgO. To enhance the CO₂ capacity of MgO sorbent, increasing the basicity is more effective than the increase in the surface area.

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Effect of the relative volume of the conducting phase on the electroconductivity of glasses in the Na<Subscript>2</Subscript>O–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system

The effect of the relative volume of the conducting phase on the electroconductivity of phase-separated glasses in the ternary system Na₂O–B₂O₃–SiO₂, whose compositions are on the same glass transition isotherm at 550°C, is investigated. It is demonstrated that the electroconductivity of phase-separated sodium borosilicate glasses does not depend on the relative volume of the conducting phase (within the limits from 0.3 to 0.9) under the condition that its composition invariable.     

Effect of CeO<Subscript>2</Subscript>-addition sequence on the performance of CeO<Subscript>2</Subscript>-modified Ni/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst in autothermal reforming of iso-octane

Two types of CeO₂-modified Ni/Al₂O₃ catalysts were prepared by a consecutive impregnation method with different sequences in the impregnation of Ni and CeO₂, and their performance in autothermal reforming (ATR) of isooctane was investigated. Catalysts prepared by adding CeO₂ prior to the addition of Ni, Ni/CeO₂-Al₂O₃, produced larger amounts of hydrogen than those obtained using catalysts prepared by adding the two components in an opposite sequence, Ni-CeO₂/Al₂O₃. The results of H₂ chemisorption and temperature-programmed reduction revealed that added CeO₂ increased the dispersion of the Ni species on Al₂O₃ and suppressed the formation of NiAl₂O₄ in the catalyst such that large amounts of Ni species were present as NiO, the active species for the ATR. The elemental and thermogravimetric analyses of deactivated catalysts indicated that Ni/CeO₂-Al₂O₃, which showed a longer lifetime than Ni-CeO₂/Al₂O₃, contained lesser amounts and different types of coke on the surface.