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.     

Synthesis and characterization of zeolite mazzite analogue in Na<Subscript>2</Subscript>O–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–Piperazine–H<Subscript>2</Subscript>O

Zeolite Mazzite (MAZ) analogue was synthesized directly using piperazine as a structure directing agent. The reactive gel composition used was (5.0–7.0) piperazine:(6.0–7.0) Na₂O:Al₂O₃:20.0SiO₂:400H₂O. Using this composition, the reaction time was shortened greatly to 4 days and the crystallization time was reduced as well. The DTA data showed that piperazine, in as-synthesized zeolite omega decomposed easily. The decomposition of the piperazine occurred at 400–480°C. NH₃-TPD analysis proved that zeolite H-omega from piperazine had strong surface acidity with ammonia desorption temperature up to 590°C.     

Preparation of zeolite A membranes by microwave heating

Molecular sieve membranes consisting of NaA zeolite crystals have been successfully synthesized on symbol -Al₂O₃ substrate by means of microwave heating. In this way, the reaction time is greatly reduced to only 15–20 min and the membranes obtained are very stable and dense. Moreover, the thickness of the membranes can be easily controlled by varying the amount of the reaction mixture. To study the formation process of the membranes, the samples in various reaction stages have been characterized by field emission scanning electron microscopy and X-ray diffraction.     

Microwave-assisted dissolution of UO<Subscript>2</Subscript> with TBP-HNO<Subscript>3</Subscript> complex

The direct dissolution of UO₂ in TBP-HNO₃ complex by microwave heating in this study suggests the possibility of dissolving spent nuclear fuels. This new technique offers many benefits for reduction in aqueous and organic waste generation and improved efficiency of chemical processing. The dissolution rate of UO₂ particles with TBP-HNO₃ complex by microwave assisted heating is highly dependent on the temperature and the particle size.     

Some characteristics of heat-resisting concretes modified by SiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript> nanoparticles

Nanoparticles of SiO₂ or TiO₂ have been added in the preparation of heat-resisting concretes of two types. The major technical and chemical characteristics have been determined. Features have been found in some of the technological operations in making the concretes of both types, and also aspects of the physicomechanical properties. Higher chemical stability has been found for heat-resisting concrete containing TiO₂ nanoparticles in an NaOH solution.     

Separation characteristics of tetrapropylammoniumbromide templating silica/alumina composite membrane in CO<Subscript>2</Subscript>/N<Subscript>2</Subscript>, CO<Subscript>2</Subscript>/H<Subscript>2</Subscript> and CH<Subscript>4</Subscript>/H<Subscript>2</Subscript> systems

Nanoporous silica membrane without any pinholes and cracks was synthesized by organic templating method. The tetrapropylammoniumbromide (TPABr)-templating silica sols were coated on tubular alumina composite support ( γ-Al₂O₃/ α-Al₂O₃ composite) by dip coating and then heat-treated at 550 °C. By using the prepared TPABr templating silica/alumina composite membrane, adsorption and membrane transport experiments were performed on the CO₂/N₂, CO₂/H₂ and CH₄/H₂ systems. Adsorption and permeation by using single gas and binary mixtures were measured in order to examine the transport mechanism in the membrane. In the single gas systems, adsorption characteristics on the α-Al₂O₃ support and nanoporous unsupport (TPABr templating SiO₂/ γ-Al₂O₃ composite layer without α-Al₂O₃ support) were investigated at 20–40 °C conditions and 0.0–1.0 atm pressure range. The experimental adsorption equilibrium was well fitted with Langmuir or/and Langmuir-Freundlich isotherm models. The α-Al₂O₃ support had a little adsorption capacity compared to the unsupport which had relatively larger adsorption capacity for CO₂ and CH₄. While the adsorption rates in the unsupport showed in the order of H₂> CO₂> N₂> CH₄ at low pressure range, the permeate flux in the membrane was in the order of H₂≫N₂> CH₄> CO₂. Separation properties of the unsupport could be confirmed by the separation experiments of adsorbable/non-adsorbable mixed gases, such as CO₂/H₂ and CH₄/H₂ systems. Although light and non-adsorbable molecules, such as H₂, showed the highest permeation in the single gas permeate experiments, heavier and strongly adsorbable molecules, such as CO₂ and CH₄, showed a higher separation factor (CO₂/H₂=5-7, CH₄/H₂=4-9). These results might be caused by the surface diffusion or/and blocking effects of adsorbed molecules in the unsupport. And these results could be explained by surface diffusion. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Photodegradation of benzene,toluene, ethylbenzene and xylene by fluidized bed gaseous reactor with TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> photocatalysts

The photodegradation of BTEX (benzene, toluene, ethylbenzene and xylene) in a photocatalytic fluidized bed reactor with TiO₂/SiO₂ was investigated. The TiO₂ film was prepared using the sol-gel method and coated onto silica-gel powder. The effects of the superficial gas velocity and SiO₂ size on the photodegradation of BTEX were examined in a fluidized bed reactor. At steady-state operation, above 79, 79, 99, 98, and 98% removal efficiencies were achieved for benzene, toluene, ethylbenzene, m, p-xylene and o-xylene, respectively, under optimal conditions (2.0 U _mf of superficial gas velocity and 1.43 of height/diameter ratio). The reaction product such as CO₂ was detected and intermediate products such as benzaldehyde, malonic acid, acetaldehyde, and formic acid were identified from the photocatalytic reaction. Also, small amounts of benzoic acid and benzyl alcohol were found through analyzing the intermediate species adsorbed on the photocatalysts. The experimental results can lead to the development of an efficient photocatalytic treatment system that utilizes solar energy and TiO₂/SiO₂ photocatalysts.     

Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> hollow spheres and their activity in methylene blue photodecomposition

PSA [poly-(styrene-methyl acrylic acid)] latex particle has been taken into account as template material in SiO₂ hollow spheres preparation. TiO₂-doped SiO₂ hollow spheres were obtained by using the appropriate amount of Ti(SO₄)₂ solution on SiO₂ hollow spheres. The photodecomposition of the MB (methylene blue) was evaluated on these TiO₂-doped SiO₂ hollow spheres under UV light irradiation. The catalyst samples were characterized by XRD, UV-DRS, SEM and BET. A TiO₂-doped SiO₂ hollow sphere has shown higher surface area in comparison with pure TiO₂ hollow spheres. The 40 wt% TiO₂-doped SiO₂ hollow sphere has been found as the most active catalyst compared with the others in the process of photodecomposition of MB (methylene blue). The BET surface area of this sample was found to be 377.6 m²g⁻¹. The photodegradation rate of MB using the TiO₂-doped SiO₂ catalyst was much higher than that of pure TiO₂ hollow spheres.     

Controllable synthesis of EU-1 molecular sieve with high SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ratios in thermodynamic stable sol system

A new green chemical route was designed in this paper for the synthesis of high-silica EU-1 molecular sieve in TEAOH–SiO₂–Al₂O₃–HMBr₂–H₂O system in which tetraethylammonium hydroxide (TEAOH) substituted for sodium hydroxide (NaOH) as an alkali source. The physicochemical properties of the synthesized samples characterized by such means as X-ray powder diffraction (XRD), electrophoresis apparatus, precise pH meter, scanning electron microscope, Fourier infrared spectrometer (FT-IR), thermo gravimetric analyzer (TG) and temperature programmed desorption (NH₃-TPD). The research results showed that the SiO₂/Al₂O₃ ratio of EU-1 molecular sieve could reach 706 with TEAOH as an alkali source. The SiO₂/Al₂O₃ ratio of the product was improved greatly to 1046 with the template agent increasing. The new synthetic route has also significantly expanded the synthetic phase region. The absolute value of zeta potential of the TEAOH sol system was obviously higher than that of the NaOH sol system, indicating the thermodynamic stability of the former sol system was higher and better for the synthesis of pure high-silica EU-1 molecular sieve. The FT-IR spectra and TG/DTG diagrams of products indicated that TEA⁺ occluded in the final products could balance electronegative framework. The amount of strong, weak and the total acidity reduced with the increase of SiO₂/Al₂O₃ ratio. The catalytic results of methanol-to-hydrocarbon demonstrated that the molecular sieve prepared by the new method has better catalytic performance.     

Structure of an atmospheric-pressure H<Subscript>2</Subscript>/O<Subscript>2</Subscript>/N<Subscript>2</Subscript> flame doped with iron pentacarbonyl

This paper presents the measurement and simulation data on the thermal and chemical structure of an atmospheric-pressure premixed H₂/O₂/N₂ flame doped with iron pentacarbonyl Fe(CO)₅. Soft ionization molecular beam mass spectrometry was used to measure concentration profiles of the combustion products of iron pentacarbonyl: Fe, FeO₂, FeOH, and Fe(OH)₂. A comparison of experimental and simulated concentration profiles showed that they are in satisfactory agreement for FeO₂ and Fe(OH)₂ and differ significantly for Fe and FeOH. Thus, the previously proposed kinetic model for the oxidation of iron pentacarbonyl was tested and it was shown that the mechanism needs further elaboration.     

Degradation kinetics of recalcitrant organic compounds in a decontamination process with UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> and UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> processes

In this study, degradation aspects and kinetics of organics in a decontamination process were considered in the degradation experiments of advanced oxidation processes (AOP),i.e., UV, UV/H₂O, and UV/H₂O,/TiO₂ systems. In the oxalic acid degradation with different H₂O₂ concentrations, it was found that oxalic acid was degraded with the first order reaction and the highest degradation rate was observed at 0.1 M of hydrogen peroxide. Degradation rate of oxalic acid was much higher than that of citric acid, irrespective of degradation methods, assuming that degradation aspects are related to chemical structures. Of methods, the TiO₂ mediated photocatalysis showed the highest rate constant for oxalic acid and citric acid degradation. It was clearly showed that advanced oxidation processes were effective means to degrade recalcitrant organic compounds existing in a decontamination process.     

Interaction of O<Subscript>2</Subscript>, O<Subscript>3</Subscript>, and H<Subscript>2</Subscript>O<Subscript>2</Subscript> with an activated carbon

The results of the modification of AG-OV-1 activated carbon under various conditions (by atmospheric oxygen at elevated temperatures and by hydrogen peroxide or ozone) are given. The effect of the used modifier on changes in the porosity, surface state, and adsorption capacity of activated carbon is evaluated.     

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.     

Phase evolution during mechanochemical coreduction of V<Subscript>2</Subscript>O<Subscript>5</Subscript> and TiO<Subscript>2</Subscript> with A

The direct preparation of V-Ti solid solution alloy by coreduction of V₂O₅ and TiO₂ with Al in an attritor mill was investigated. The reduction of V₂O₅ with Al is highly exothermic, whereas reduction of TiO₂ with Al is not sufficiently exothermic for a self-sustaining reaction. A range of compositions of a mixture of V₂O₅ and TiO₂ can be so chosen as to make the overall reduction of V₂O₅ and TiO₂ with Al sufficiently exothermic for a self-sustaining reaction. Initial studies were done to identify the reaction products obtained by reducing V₂O₅ with Al. The reaction yielded the intermetallic phase (Al₃V), V, and Al₂O₃. SEM images indicated melting and solidification of the phases, leading to agglomeration. Further experiments involved mixing appropriate amounts of TiO₂ with V₂O₅ and reducing the mixture with Al. XRD data for products showed the presence of V, V₅Al₈, and Al₂O₃. X-Ray Florescence (XRF) analysis and energy dispersive analyzer (EDAX) of SEM sample images indicated the formation of V-Ti solid solution. Microstructure of the milled charges taken out prior to reaction initiation indicated morphology change in Al powder and agglomeration/segregation of reactants. As a result, the reaction of V₂O₅ with the excess Al at certain regions also promoted the formation of vanadium aluminide.     

Fabrication of covalently-bonded polystyrene/SiO<Subscript>2</Subscript> composites by Pickering emulsion polymerization

Pickering emulsion polymerization has attracted considerable attention in material fabrication due to its unique surfactant-free character and versatile association of oil, water and particles for a large set of materials. In this study, SiO₂ modified with Methacryloxypropyltrimethoxysilane (MPTMS) was employed to prepare Pickering emulsion, and subsequently covalently-bonded polystyrene/SiO₂(PS/SiO₂) composites were synthesized by Oil-in-water Pickering emulsion polymerization. Optical micrograph, contact angle, thermogravimetric analysis (TGA), Fourier transform infrared spectra (FT-IR), scanning electron microscope (SEM) and dynamic laser scattering (DLS) were employed to characterize the modified SiO₂, Pickering emulsion and prepared composites. It was found that prepared composites possess ragged surface morphology and SiO₂ concentration has an important effect on the morphology of as-prepared composites. In addition, covalent bond between PS core and SiO₂ shell was evidenced by FT-IR.     

Adsorption of CO<Subscript>2</Subscript> by iron-exchanged heteropolyacid Fe<Subscript>1.5</Subscript>PMo<Subscript>12</Subscript>O<Subscript>40</Subscript> supported on mesoporous cellular foams

Novel low-temperature swing adsorbents that preferably adsorb CO₂ were synthesized by varying loading of heteropolyacid Fe_1.5PMo₁₂O₄₀ (Fe–PMA) supporting on mesoporous cellular foams (MCFs) by wetting impregnation. The synthesized materials were characterized by various physicochemical, thermal and spectral techniques and the CO₂ adsorption capacity of the materials were evaluated. Solid adsorbents showed a significantly high adsorption capacity toward CO₂ due to the chemisorptions of CO₂. The CO₂ adsorption capacities of the materials decreased as the temperature increased. The results showed that the adsorption capacity reached a level of 81.8 mg CO₂/g-adsorbent at 25 °C for the 20 wt% Fe–PMA–MCFs. These results indicated that the iron (Fe²⁺) complexes acted as efficient catalysts for the separation of CO₂. The as-synthesized adsorbents were selective, thermally stable, long-lived, and could be recycled at a temperature of 110 °C.     

Increasing Cristobalitization and Mullitization in Fired Clays by Mechanochemical Activation and the Use of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>- and SiO<Subscript>2</Subscript>-Containing Additives

Results of the x-ray phase and derivatographic studies of refractory clays activated mechanochemically by means of planetary, vibratory, and screw grinding techniques are reported. The activation makes it possible to enhance cristobalitization and mullitization of the fired clays and to use lower firing temperatures. Good results giving the same effect is reached using Al₂O₃ and SiO₂-containings additives such as clays, oxidal, and nepheline syenite. __________ Translated from Novye Ogneupory, No. 8, pp. 57 – 65, August, 2005.     

Optimization of High Conducting Na<Subscript>3</Subscript>Zr<Subscript>2</Subscript>Si<Subscript>2</Subscript>PO<Subscript>12</Subscript> Phase by new Phosphate Salt for Solid Electrolyte

A composition of NASICON (Na₃Zr₂Si₂PO₁₂) was synthesized by the solid-state reaction method using a new compound Na₂HPO₄2H₂O. The X-ray diffraction patterns of all samples exhibit monoclinic Na₃Zr₂Si₂PO₁₂ as a major phase with a very small amount of monoclinic-ZrO₂. The maximum relative density (97 %) and maximum conductivity is obtained in the samples sintered at 1200 °C (N3) which is slightly higher than β-Al₂O₃. The activation energy is ～ 0.20 eV for the N3 sample which is lower than for β-Al₂O₃. The dilatometeric study and Arrhenius plots confirmed a phase transition of NASICON from monoclinic to rhombohedral. The micro-structural study of the samples done by scanning electron microscopy (SEM) indicated a significant influence of the processing conditions on the microstructures. Raman spectroscopy demonstrated that the sample N3 exhibits minor structural changes compared to other samples.     

Phase cooperation of V<Subscript>2</Subscript>O<Subscript>5</Subscript> and Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> in the selective oxidation of H<Subscript>2</Subscript>S containing ammonia and water

The selective oxidation of hydrogen sulfide containing excess water and ammonia was studied over vanadium oxide-based catalysts. The investigation was focused on the role of V₂O₅, and phase cooperation between V₂O₅ and Bi₂O₃ in this reaction. The conversion of H₂S continued to decrease since V₂O₅ was gradually reduced by treatment with H₂S. The activity of V₂O₅ was recovered by contact with oxygen. A strong synergistic phenomenon in catalytic activity was observed for the mechanically mixed catalysts of V₂O₅ and Bi₂O₃. Temperature-programmed reduction (TPR) and oxidation (TPO) and two bed reaction tests were performed to explain this synergistic effect by the reoxidation ability of Bi₂O₃. This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University.