Effects of silicalite-1 nanoparticles on rheological and physical properties of HDPE

The addition of silicalite-1 nanoparticles (0.2-20 wt%) increased slightly the crystallization temperature of HDPE with silicalite-1 content, at 20 wt% loading by ca. 2.5 °C, but it had little effect on the melting temperature. The nanocomposites displayed a little higher onset degradation temperature than pure polymer by 7-11 °C. The WAXD profiles showed that the intensity of diffraction peaks for HDPE was decreased with increasing silicalite-1 content from 5 wt% but that the peak position of every crystal plane did not shift in the presence of silicalite-1 nanoparticles. The incorporation of the nanoparticles increased the melt viscosity of HDPE with silicalite-1 content. It also increased both storage (G′) and loss modulus (G″). In the so-called Cole-Cole plot, pure HDPE showed a single master curve whose slope was 1.37, while the nanocomposites with 10 and 20 wt% silicalite-1 exhibited the inflection in the low frequency range before which the slopes were 1.22 and 1.02, respectively. Much more accelerated crystallization behavior under shear was observed with silicalite-1 content at the isothermal crystallization temperature of 125 °C than at 120 °C.     

Transformation of olefin over Ni/HZSM-5 catalyst

Olefins in the cracked naphtha can be transformed into aromatics and isoparaffin to reduce the olefin content as well as to improve the octane number. In this work, Ni/HZSM-5 bifunctional catalyst was prepared and was characterized by nitrogen adsorption, FT-IR analysis with adsorbed pyridine as well as by X-ray powder diffraction analysis. The activity of the catalyst was investigated with the transformation of 1-hexene. The experimental results show that the main reactions occurring over Ni/HZSM-5 at relatively low temperature are cracking and isomerization of 1-hexene, which results in the high concentration of olefin in the hydrotreated product. The double-bond isomerization of 1-hexene is dominant at low temperature (<220 °C) while the skeletal isomerization is elevated at high temperature, and the aromatization activity of the Ni/HZSM-5 catalyst is promoted by high temperature. The sulfided Ni/HZSM-5 catalyst shows higher aromatization activity than the reduced one and the zeolite supported Ni catalysts show comparatively better stability than that without metal components.     

Aromatization of n-hexane over Ga,Mo and Zn modified H-ZSM-5 zeolite catalysts

n-Hexane aromatization was investigated at 500 °C on parent and metal (i.e. Ga, Mo and Zn) modified H-ZSM-5 zeolite catalysts. Conversion reached 88% over H-ZSM-5 and was stable. Addition of metal resulted in lower conversion (< 80%). Formation of aromatic compounds was favored on Ga/H-ZSM-5 (> 35%) and Zn/H-ZSM-5 (> 40%) while H-ZSM-5 and Mo/H-ZSM-5 showed higher cracking activity. Gallium and zinc favored aromatization. At 600 °C a decrease in activity with increasing TOS was observed. A decrease in aromatics selectivity was also observed. The aromatics selectivity with increase in TOS of Ga/H-ZSM-5 (43–27%) and Mo/H-ZSM-5 (35–27%) catalysts was higher than for Zn/H-ZSM-5 (46–7%).     

IR study of adsorption and reaction of 1-butene on H-ZSM-5

Adsorption and reaction of 1-butene on H-ZSM-5 were studied by FT-IR spectroscopy. The adsorbed 1-butenes were converted to cis- and trans-2-butenesbelow 250 K under evacuation, and dimerization of the adsorbed 2-butenes was observed at room temperature. The produced dimer was tentatively assigned to3,4-dimethyl-3-hexene which hydrogen-bonded to the acidic OH groups with its alkyl chains. Therefore, the reaction terminated at the dimerization since proton transfer from H-ZSM-5 to the dimer did not occur. This revised version was published online in July 2006 with corrections to the Cover Date.     

Performance of zeolites and product selectivity in the gas-phase oxidation of 1,2-dichloroethane

The deep oxidation of 1,2-dichloroethane (DCE) over H-type zeolites (H-Y, H-ZSM-5 and H-MOR) was evaluated. Experiments were performed on conditions of lean chlorocarbon concentration (around 1000 ppmv) under dry and humid conditions, between 200 and 550°C in a conventional fixed-bed reactor. The high density of Brønsted acid sites, proved by temperature-programmed desorption (TPD) of ammonia and diffuse reflectance FT-IR of adsorbed pyridine measurements, make H-ZSM-5 zeolite an effective catalyst for DCE decomposition. Vinyl chloride was identified as an intermediate in 250–400°C range. When vinyl chloride was destroyed at higher temperatures, all the zeolites showed a great selectivity (>90%) to HCl. CO was promoted in quantity reflecting the difficulty of its oxidation over these zeolite catalysts. The activity of the zeolites was reduced in the presence of water vapour (15,000 ppmv). It was noticed that the addition of water to the feed stream did not alter the order of activity observed in the dry experiments. Moreover, the presence of water in the DCE decomposition changed significantly the reaction product distribution. Vinyl chloride formation was found to be significantly lowered over the three zeolites, and selectivity to CO₂ formation was largely enhanced. The X-ray powder diffraction (XRD) analysis of the deactivated samples indicated partial destruction of the zeolite crystal structure during reaction.     

Sorption kinetics study of the diethylbenzene isomers in MFI-type zeolites

The uptake rates of the three diethylbenzene isomers in MFI-type zeolites were studied with a sorption kinetics apparatus of the barometric type. It was observed that the uptake rates depend crucially on the position of the substituted ethyl groups. While p-diethylbenzene was adsorbed with uptake rates of the same order of magnitude as benzene and the monosubstituted benzenes, diffusion of m-diethylbenzene was approximately four orders of magnitude slower. No sorption uptake was observed for o-diethylbenzene. In the experiments with H-ZSM-5, sorption kinetics were partly determined by a secondary process additional to Fickian diffusion. Comparison to the results obtained with silicalite-1 and earlier results proved that the secondary process is correlated with the existence of acidic sites inside the zeolite and can be tentatively ascribed to an isomerization reaction.     

Role of zeolite structure on reduction of NOx with methane over In- and Pd-based catalysts

Catalytic performances of ZSM-5 based catalysts containing indium or palladium were examined for NO reduction with CH₄ and NO_x chemisorption. The amounts of NO_x chemisorbed on In/H-ZSM-5 were well proportional to the catalytic activities for NO_x reduction. Pd/H-ZSM-5, on the other hand, hardly chemisorbed NO₂, while the catalytic activity for NO₂ reduction with CH₄ is very high. Furthermore, Pd loaded on SiO₂ showed comparably high catalytic activity for NO₂ reduction with CH₄ at 400°C in the absence of oxygen as Pd/H-ZSM-5. CH₄ combustion during NO_x reduction with CH₄ in the presence of oxygen significantly occurred over PdO on SiO₂, while less over Pd/H-ZSM-5. The role of zeolite might be slightly different between In/H-ZSM-5 and Pd/H-ZSM-5: the zeolitic porous structure is needed for In/H-ZSM-5 in order to concentrate NO₂ adspecies on InO⁺ sites, which is important for NO reduction with CH₄ on In/H-ZSM-5 based catalysts, while the ion-exchangeable ability of zeolite is needed for Pd/H-ZSM-5 in order to make Pd²⁺ located in a highly dispersed state, on which NO is strongly chemisorbed.     

Catalytic activity of titanium oxide for oxygen reduction reaction as a non-platinum catalyst for PEFC

A non-platinum cathode electrocatalyst must have the stability and catalytic activity for the oxygen reduction reaction (ORR) in order to be used in polymer electrolyte fuel cells (PEFCs). Titanium oxide catalysts as the non-platinum catalyst were prepared by the heat treatment of titanium sheets in the temperature range from 600 to 1000 °C. The prepared catalysts were chemically and electrochemically stable in 0.1 mol dm⁻³ H₂SO₄. The titanium oxide catalysts showed different catalytic activities for the ORR. The ORR of the catalysts heat-treated at around 900 °C occurred at the potential of about 0.65 V versus RHE. It is considered that the deference in the catalytic activity for the ORR of the heat-treated titanium oxide catalysts was due to the fact that the heat-treatment condition changed the material property of the catalyst surface. In particular, it was found that the catalytic activity for the ORR of the Ti oxide catalysts increased with the increase in the specific crystalline structure, such as the TiO₂ (rutile) (1 1 0) plane and the work function. It is considered that a surface state change, such as the crystalline structure and work function, might affect the catalytic activity for the ORR.     

Ir/H-ZSM-5 Catalysts in the Selective Reduction of NOx with Hydrocarbons

Three different Ir catalysts supported on H-ZSM-5 were prepared and tested for the selective catalytic reduction of NO under net oxidizing conditions using propene as reducing agent. The preparation of highly active Ir catalysts and the elaboration of a procedure for enhancing activity by on stream conditioning was targeted. Structural changes of the catalyst during conditioning were investigated by means of XRD, TEM and activity measurements. Under reaction conditions Ir was present as Ir⁰ and IrO₂. The presence of Ir⁰ was essential for high DeNOx activity. The ratio of Ir⁰/Ir⁴⁺ was found to depend on the size of Ir-containing crystallites. Larger crystallites contained predominantly Ir⁰. Crystallite size and oxidation state of Ir have been identified to be crucial for the NO reduction behaviour of Ir/H-ZSM-5.     

Remarkable enhancement in durability of Pd/H-ZSM-5 zeolite catalysts for CH4-SCR

Effect of second components on the catalytic performance of Pd/H-ZSM-5 zeolite (Pd: 0.4 wt.%) was evaluated by a durability test of NO reduction with CH₄ at a relatively high temperature of 500°C in the presence of water vapor for a prolonged period. The Pd/H-ZSM-5 showed high stable activity for this reaction without H₂O in the reactant feed, while immediate and irreversible deactivation was observed in the presence of H₂O, resulting in no activity after 7 h. The second components such as Co, Rh, Ag, Ce, and Fe introduced individually to the Pd/H-ZSM-5 enhanced the durability, and in particular the addition of 3.3 wt.% Co led to a stable NO conversion for more than 40 h in the presence of H₂O.     

Fabrication and application of silicalite-1 and TS-1 hollow fibers with polyethylene imine (PEI) fibers as substrates

Silicalite-1 and titanium containing silicalite-1 (TS-1) hollow fibers were fabricated with polyethylene imine (PEI) fibers as substrates. The acid treated PEI fibers were positively charged and can be effectively coated with silicalite-1 or TS-1 nanocrystals from their colloidal solution. The adsorbed silicalite-1 or TS-1 nanocrystals grew up and became more compact upon two days of vapor phase Ostwald ripening in autoclave. Silicalite-1 and TS-1 hollow fibers were obtained after calcination at 400 °C in air. The shell thickness of the hollow fibers is ～1 μm. Hydroxylation of phenol with H₂O₂ was investigated over TS-1 based catalysts in order to compare influences of nanocrystals composed macrostructure and Al₂O₃ binder on the catalytic activities.     

Liquid-phase dehydrocondensation of 1-pentanol to di-n-pentyl ether (DNPE) over medium and large pore acidic zeolites

The present paper deals with the liquid-phase synthesis of di-n-pentyl ether (DNPE) by dehydration of 1-pentanol over H-Beta, H-ZSM-5, H-mordenite and H-Y zeolites. Their SiO₂/Al₂O₃ ratios were about 25 for H-Beta, 28 for H-ZSM-5, 35 for H-mordenite and 6 for H-Y. Experiments were performed in a batch reactor in the temperature range 140–180 °C at 1.6 MPa. Comparison of the catalysts behaviour shows that H-Beta is the most active and selective to DNPE, although it is less active than microporous ion-exchange resins. Kinetics of DNPE synthesis was studied. The best kinetic model for all the catalysts stems from a reaction mechanism whose rate-limiting step is the surface reaction between two 1-pentanol molecules adsorbed on adjacent sites, to yield DNPE and water both adsorbed on single site. Activation energy, on each single catalyst, was estimated to be in the range 94–118 kJ mol^?1.     

Modification of the ZSM-5 zeolite using Ga and Zn impregnated silica fibre for the conversion ofn-butane into aromatic hydrocarbons

The modification of ZSM-5 by metals is generally performed by methods such as ion-exchange, impregnation, chemical vapour deposition and physical mixing. In this work a silica fibre pre-impregnated with Ga and Zn has been used during the synthesis by which Ga-ZSM-5 and Zn-ZSM-5 zeolite catalysts were prepared. The synthesised zeolite catalysts were characterised by an X-ray powder diffractometer, a scanning electron microscope, an X-ray fluorescence spectrometer, a solid state NMR, an energy dispersive X-ray analyser and a sorptomatic 1900. The acidity of the catalysts was determined by temperature programmed desorption of ammonia. The reaction ofn-butane to aromatic hydrocarbons was carried out over the H-ZSM-5, Ga-ZSM-5 and Zn-ZSM-5 catalysts and it was observed that these catalysts exhibited high catalytic activity in the conversion ofn-butane and formation of aromatic hydrocarbons. The effect of temperature on the conversion ofn-butane and formation of aromatic hydrocarbons was studied at 713, 743, 773 and 803 K with a space velocity (WHSV) of 2.5 h^–1. The effect of time on stream on then- butane conversion and formation of aromatic hydrocarbons over the synthesised catalysts was investigated at 803 K for 4.5 h.     

On the role of gallium for the aromatization of lower paraffins with Ga-promoted ZSM-5 catalysts

Aromatization of butane or propane was conducted with a series of ZSM-5 catalysts. A small amount of oxygen in the feed promoted butane conversion to aromatic hydrocarbons on H-ZSM-5. It suggests that if hydrogen atoms on the zeolite surface are removed effectively, H-ZSM-5 exhibits a high selectivity for aromatic hydrocarbons. A hybrid catalyst composed of the physical mixture of Ga/SiO₂ and H-ZSM-5 showed comparable activity and aromatic selectivity to those of the Ga-supported ZSM-5 zeolite, whereas the Ga/SiO₂ itself exhibited little catalytic activity for the paraffin conversion and olefin aromatization. The excellent promotional effect of Ga/SiO₂for aromatics formation was observed only when it was intimately contacted with H-ZSM-5. These results suggest that the supported Ga promotes the zeolite-catalyzed aromatization of lower paraffins by promoting hydrogen desorption via the ‘reverse spillover’ effects.     

粘结助剂对ZSM-5甲醇制烯烃催化活性的影响

采用机械混合法在H-ZSM-5分子筛中添加不同氧化物粘结剂,考察其对甲醇制烯烃(MTO)催化反应性能的影响,并采用x射线衍射(XRD)、氨气-程序升温脱附(NH3-TPD)实验、傅立叶红外光谱(FT-IR)和热重(TG)分析表征催化剂结构.结果表明:在H-ZSM-5中分别添加不同的氧化物粘结剂SiO2,γ-Al2O3和Kaolin(H-ZSM-5和氧化物质量比2∶1),在催化剂1 g,CH3OH与N2物质的量之比1∶4,催化剂质量与原料流速之比(W/F)为10(g·h)/mol,反应压力0.1 MPa和反应温度723 K的条件下,反应3 h,甲醇转化率为100%;与H-ZSM-5相比,烯烃产物分布发生了变化,添加SiO2使C3=选择性下降,添加γ-Al2O3使C1选择性增加,添加Kaolin使C3=选择性增加,同时添加Kaolin与SiO2(Kaolin和siO2质量比2∶1)的H-ZsM-5具有最高的C2=～C4=选择性,其中C3=选择性为38%.添加氧化物降低了催化剂的总酸量,反应11 h前后催化剂的物相没有发生明显变化,积炭不明显.     

Selective Catalytic Reduction of NO with NH3 over Fe-ZSM-5 Catalysts Prepared by Sublimation of FeCl3 at Different Temperatures

Fe-ZSM-5 catalysts were prepared by subliming FeCl₃ into H-ZSM-5. The method used allowed Fe-ZSM-5 catalyst preparation by FeCl₃ exchange at a desired sublimation temperature and was found to be more precise. The sublimation of FeCl₃ into H-ZSM-5 was carried out at 320 and 700 °C. Fe-ZSM-5 prepared by sublimation of FeCl₃ at 320 °C followed by rapid heating to 700 °C and the catalyst prepared by subliming FeCl₃ at 700 °C were found to be more active for NO reduction with NH₃ in the presence of simulated exhaust gases containing water vapor than catalysts prepared by subliming FeCl₃ at 320 °C. To determine the active sites, the catalysts were characterized by H₂-TPR, in situ DRIFTS of NO adsorption, NH₃-TPD, XRD and chemical analysis methods. The observed NO conversion differences in selective catalytic reduction using NH₃ could be correlated to the iron cation species present at different locations determined from diffuse reflectance infrared spectroscopy. Enhanced NO reduction activity was obtained when positions in Fe-ZSM-5, corresponding to Fe²⁺(NO) band at 1877 cm^-1 in DRIFTS, were preferentially occupied.     

Identification and Influence of Acidity on Alkylation of Phenol with Propylene over ZSM-5

The alkylation of phenol with propylene has been studied over several H-ZSM-5s with different Si/Al ratios and Cs⁺-ion-exchanged H-ZSM-5s at temperature range 373–623°C. Both O- and C-alkylation, which were closely dependent on the reaction temperature and acidity of the catalysts, were observed. O-alkylated compound is found to be formed preferably at temperature lower than 250°C and over Cs⁺-ion-exchanged H-ZSM-5s. However, at higher temperature, only C-alkylation is observed. The acidic properties of the zeolites were characterized by solid-state ³¹P MAS-NMR of the probe molecule trimethylphosphine oxide and NH₃-TPD (temperature-programmed desorption) and it is suggested that in the case of C-alkylation, moderate acid sites are responsible for the formation of para-isopropylphenol, while ortho-isopropylphenol is favorable for weak acid sites.     

Low temperature decomposition of nitrous oxide over Fe/ZSM-5: Modelling of the dynamic behaviour

The kinetics of N₂O decomposition to gaseous nitrogen and oxygen over HZSM-5 catalysts with low content of iron (<400 ppm) under transient and steady-state conditions was investigated in the temperature range of 250–380 °C. The catalysts were prepared from the HZSM-5 with Fe in the framework upon steaming at 550 °C followed by thermal activation in He at 1050 °C. The N₂O decomposition began at 280 °C. The reaction kinetics was first order towards N₂O during the transient period, and of zero order under steady-state conditions. The increase of the reaction rate with time (autocatalytic behaviour) was observed up to the steady state. This increase was assigned to the catalysis by adsorbed NO formed slowly on the zeolite surface from N₂O. The formation of NO was confirmed by temperature-programmed desorption at temperatures >360 °C. The amount of surface NO during the transient increases with the reaction temperature, the reaction time, and the N₂O concentration in the gas phase up to a maximum value. The maximum amount of surface NO was found to be independent on the temperature and N₂O concentration in the gas phase. This leads to a first-order N₂O decomposition during the transient period, and to a zero-order under steady state. A kinetic model is proposed for the autocatalytic reaction. The simulated concentration–time profiles were consistent with the experimental data under transient as well as under steady-state conditions giving a proof for the kinetic model suggested in this study.     

Influence of the support on CO2 methanation over Ru catalysts: an FT-IR study

The hydrogenation of CO₂ to methane has been investigated over Ru catalysts supported on zeolite (H-ZSM-5) and on silica. Supported Ru catalysts were very active for the hydrogenation of CO₂. Ru/ZSM-5 was more selective to methane than Ru/SiO₂. On the basis of FT-IR spectra of CO and CO₂ adsorbed on the catalysts, it has been suggested that this behaviour can be related to a higher positive polarization of ruthenium on the zeolite. This leads to a weaker Ru–CO bond on the H-ZSM-5-supported sample with a corresponding increase of the hydrogen surface coverage that favours the transformation of the intermediate CO to methane. This revised version was published online in July 2006 with corrections to the Cover Date.     

Controllable synthesis of a large TS-1 catalyst for clean epoxidation of a C=C double bond under mild conditions

Development of a titanium silicalite-1 (TS-1) catalyst with good crystallinity and a four-coordinate Ti framework is critical for efficient catalytic oxidation reaction under mild conditions. Herein, a size-controlled TS-1 zeolite (TS-1 0.1ACh (acetylcholine)) was synthesized via steam-assisted crystallization by introducing acetylcholine as a crystal growth modifier in the preparation process, and TS-1 0.1ACh was also employed in epoxidations of different substrates containing C=C double bonds. The crystalline sizes of the as-synthesized TS-1 0.1ACh catalysts were controlled with the acetylcholine content, and characterization results showed that the particle sizes of highly crystalline TS-1 0.1ACh zeolite reached 3.0 μm with a good Ti framework. Throughout the synthetic process, the growth rate of the crystals was accelerated by electrostatic interactions between the connected hydroxyl groups of the acetylcholine modifier and the negatively charged skeleton of the pre-zeolites. Furthermore, the TS-1 0.1ACh catalyst demonstrated maximum catalytic activity, good selectivity and high stability during epoxidation of allyl chloride. Importantly, the TS-1 0.1ACh catalyst was also highly versatile and effective with different unsaturated substrates. These findings may provide novel, easily separable and large TS-1 catalysts for efficient and clean industrial epoxidations of C=C double bonds.