Regeneration behaviors of Fe/Si‐2 and Fe–Mn/Si‐2 catalysts for C2H6 dehydrogenation with CO2 to C2H4

The catalytic performance of Fe/Si‐2 and Fe–Mn/Si‐2 catalysts for conversion of C₂H₆ with CO₂ to C₂H₄ was examined in a continuous‐flow and fixed‐bed reactor. The results show that the Fe–Mn/Si‐2 catalyst exhibits much better reaction activity and selectivity to C₂H₄ than those of the Fe/Si‐2 catalyst. Furthermore, the coking–decoking behaviors of these catalysts were studied through TG. The catalytic performances of the catalysts after regeneration for conversion of C₂H₆ or dilute C₂H₆ in FCC off‐gas with CO₂ to C₂H₄ were also examined. The results show that both activity and selectivity of the Fe–Mn/Si‐2 catalyst after regeneration reached the same level as those of the fresh catalyst, whereas it is difficult for the Fe/Si‐2 catalyst to refresh its reaction behavior after regeneration. This revised version was published online in July 2006 with corrections to the Cover Date.     

M/BCS (M=Ni, Co; BCS=30 mol% BaCl2/Sm2O3): Effective Catalysts for the Partial Oxidation of Ethane to a Feedstock Gas Suitable for Ethene Hydroformylation

The M (M = Ni, Co)-loaded BaCl₂-promoted Sm₂O₃ (BCS) catalysts have been investigated for the partial oxidation of ethane to a feedstock gas suitable for ethene hydroformylation. It is found that at a temperature of 700 °C and a C₂H₆/O₂ molar ratio of 2/1, the product mixtures over 5 wt% Ni/BCS and 7 wt% Co/BCS were with C₂H₄/CO/H₂ and C₂H₄/CO_x/H₂ (CO_x=CO+CO₂) molar ratios close to 1/1/1 at a contact time of 1.19×10^-4 h g ml^-1 and close to 1/1/2 at a contact time of 2.78×10^-4 h g ml^-1. It is suggested that, besides reaction conditions, defect structures, M loading, and M dispersion of the catalysts are governing factors for the generation of the required feedstock gas.     

Synthesis and photocatalytic properties of H2La2Ti3O10/TiO2 intercalated nanomaterial

H₂La₂Ti₃O₁₀/ TiO₂ intercalated nanomaterial was fabricated by successive intercalation reactions of H₂La₂Ti₃O₁₀ with n-C₆H₁₃NH₂/C₂H₅OH mixed solution and acid TiO₂ sol, followed by irradiating with a high-pressure mercury lamp. The intercalated materials possess a gallery height of 0.46 nm and a specific surface area of 31.58 m²·g⁻¹, which indicate the formation of a porous material. H₂La₂Ti₃O₁₀/TiO₂ shows photocatalytic activity for the decomposition of organic dye under irradiation with visible light and the activity of TiO₂ intercalated material was superior to the unsupported one.     

Enhancement of C2H6 Oxidation by O2 in the Presence of N2O over Fe Ion-Exchanged BEA Zeolite Catalyst

Selective catalytic reduction (SCR) of N₂O with C₂H₆ took place effectively over Fe ion-exchanged BEA zeolite catalyst (Fe-BEA) even in the presence of excess oxygen. The mechanism in the SCR of N₂O with C₂H₆ over Fe-BEA catalyst was studied by a transient response experiment and an in situ DRIFT spectroscopy. No oxidation of C₂H₆ by O₂ took place below 350 °C (in C₂H₆/O₂). In the N₂O/C₂H₆/O₂ system, however, it was found that the reaction of C₂H₆ with O₂ was drastically enhanced by the presence of N₂O even at low temperatures (200-300 °C). Therefore, it was concluded that N₂O played an important role in the oxidation of C₂H₆ (i.e., activation of C₂H₆ at an initial step). On the basis of these findings, the mechanism in the SCR of N₂O with C₂H₆ is discussed.     

Simultaneous Production of Syngas and Ethylene from Methane by Combining its Catalytic Oxidative Coupling over Mn/Na2WO4/SiO2 with Gas Phase Partial Oxidation

A new route of methane utilization is presented, in which methane is converted to H₂, CO and C₂H₄ simultaneously with equal mole ratio, in order that the produced mixture could be used in the synthesis of propanal via hydroformylation. Kinetically controlled free radical gas phase methane oxidation was combined with its catalytic oxidative coupling over Mn/Na₂WO₄/SiO₂ to concomitantly acquire ethylene and syngas with close concentration. Under the optimal reaction condition, a mole ratio of CO:H₂:C₂H₄=1.0:1:0.9 was obtained with a yield of 11.6% and a selectivity of 68% to the target products based on C, while the selectivity to CO₂ is as low as 18.1%.     

Catalyst’s Sulfur Displacement by Thiophene, as Monitored by Exchange of 35S Radiotracer

The isotopic exchange has been studied between catalyst radiosulfur and H₂S, formed in thiophene hydrodesulfurization (HDS) (named S-displace) on alumina supported molybdena, on CoMoO_x, PdMoO_x, PtMoO_x and on silica–alumina supported NiWO_x. S-displace was compared with radiosulfur exchange data between catalyst radiosulfur and gas phase H₂S (S^exc) determined previously. The extent of S^exc was higher than that of the S-displace for Mo, CoMo in and NiW, whereas the extent of S-displace from PdMoO and PtMoO was significantly higher, than that of S^exc. Thiophene HDS product distribution data are discussed in terms of increased C=C hydrogenation and C–C hydrogenolysis activity, explained by increasing H₂S production with longer circulation time of the thiophene/H₂ mixture, The C₁/C₃<1 ratios among C₄-hydrogenolysis products indicate some coke formation. The decrease of thiophene HDS activity is presumably a consequence of increasing site-blocking with the formation of more H₂S and coke with longer duration of thiophene treatment.     

Synergism Between Pt/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Au/TiO<Subscript>2</Subscript> in the Low Temperature Oxidation of Propene

CO impedes the low temperature (<170 °C) oxidation of C₃H₆ on supported Pt. Supported Au catalysts are very effective in the removal of CO by oxidation, although it has little propene oxidation activity under these conditions. Addition of Au/TiO₂ to Pt/Al₂O₃ either as a physical mixture or as a pre-catalyst removes the CO and lowers the light-off temperature (T ₅₀) for C₃H₆ oxidation compared with Pt catalyst alone by ~54 °C in a feed of 1% CO, 400 ppm C₃H₆, 14% O₂, 2% H₂O.     

The intermolecular interaction studies in the complexes of isothiocyanic acid (HNCS) and its derivatives with H2S: a computational study

The computational investigations are carried out on the complexes of isothiocyanic acid (HNCS) and its derivatives with H₂S through MP2/aug-cc-PVTZ//MP2/aug-cc-PVDZ level. Five, four, three and four structures are located on the potential energy surface of the HNCS?H₂S, HSCN? H₂S, HCNS? H₂S and HSNC?H₂S heterodimers, respectively. The calculated results reveal that the most stable heterodimers among all heterodimers obtained for the HNCS?H₂S, HSCN?H₂S, HCNS?H₂S and HSNC?H₂S systems belong to HSCN?H₂S system. Therefore, HSCN?H₂S system has a key role in the atmosphere.     

The effects of a potassium overlayer on the reaction pathway of CH2 and C2H5 on Rh(111)

The effect of potassium on the reaction pathways of adsorbed CH₂ and C₂H₅ species on Rh(111) was investigated by means of reflection absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TDS). Hydrocarbon fragments were produced by thermal and photo-induced dissociation of the corresponding iodo compounds. Potassium adatoms markedly stabilized the adsorbed CH₂ and converted it into C₂H₄, the formation of which was not observed for K-free Rh(111). New routes of the surface reactions of C₂H₅ have been also opened in the presence of potassium, namely its transformation into butane and butene.     

Two-step hydrothermal synthesis of Ru-Sn oxide composites for electrochemical supercapacitors

A two-step hydrothermal process was developed to synthesize hydrous 30RuO₂-70SnO₂ composites with much better capacitive performances than those fabricated through the normal hydrothermal process, co-annealing method, or modified sol-gel procedure. A very high specific capacitance of RuO₂ (C_S,Ru), ca. 1150 F g⁻¹, was obtained when this composite was synthesized via this two-step hydrothermal process with annealing in air at 150 °C for 2 h. The voltammetric currents of this annealed composite were found to be quasi-linearly proportional to the scan rate of CV (up to 500 mV s⁻¹), demonstrating its excellent power property. From Raman, UV-vis spectroscopic and TEM analyses, the reduction in mean particulate size is clearly found for this two-step oxide composite, attributable to the co-precipitation of (Ru_δSn_1−δ)O₂·xH₂O onto partially dissolved SnO₂·xH₂O and the formation of (Ru_δSn_1−δ)O₂·xH₂O crystallites in the second step. This effect significantly promotes the utilization of RuO₂ (i.e., very high C_S,Ru). The excellent capacitive performances, very similar to that of RuO₂·xH₂O, suggest the deposition of RuO₂-enriched (Ru_δSn_1−δ)O₂·xH₂O onto SnO₂·xH₂O seeds as well as the individual formation of (Ru_δSn_1−δ)O₂·xH₂O crystallites in the second hydrothermal step.     

H2S–CO2 Separation Using Room Temperature Ionic Liquid [BMIM][Br]

Solubility and selective absorption of hydrogen sulfide (H₂S) over carbon dioxide (CO₂) in a room temperature ionic liquid, 1-butyl-3-methylimidazolium bromide ([BMIM][Br]) has been evaluated under ambient temperature and pressure. [BMIM][Br] demonstrated its potential as a solvent for selective removal of H₂S from CO₂/H₂S mixture. Our investigation indicated that H₂S solubility in [BMIM][Br] is comparable to or better than that in commercially available MDEA-based solvents. Meanwhile, CO₂ solubility in [BMIM][Br] is lower than that in the same amine resulting in H₂S/CO₂ absorption selectivity of within 3.5 to 3.75. The solubility behavior is relatively maintained after 4 times absorption-desorption cycles. A computational molecular study suggested that intramolecular hydrogen bonding interaction between anion Br and hydrogen atom of H₂S could stabilize the complex and resulted lower complexation energy than CO₂ interaction with [BMIM][Br]. Based on the experiment results, a separation process employing [BMIM][Br] is proposed to control the CO₂/H₂S ratio existing in a natural gas feed.     

Halogenated La1.6Sr.04CuO4 catalysts active for ethane selective oxidation to ethene

The catalytic performances and characterization of the catalysts La_1.6Sr_0.4CuO_3.852, La_1.6Sr_0.4CuO_3.857F_0.143, and La_1.6Sr_0.4 CuO_3.856Cl_0.126 have been investigated for the oxidative dehydrogenation of ethane (ODE) to ethene. X‐ray diffraction results indicated that the three catalysts have a single‐phase tetragonal K₂NiF₄-type structure. The incorporation of fluoride or chloride ions in the La_1.6Sr_0.4CuO_4-δ lattice can significantly enhance C₂H₆ conversion and C₂H₄ selectivity. We observed 83.2% C₂H₆ conversion, 76.7% C₂H₄ selectivity, and 63.8% C₂H₄ yield over La_1.6Sr_0.4CuO_3.857F_0.143> and 79.6% C₂H₆ conversion, 74.6% C₂H₄ selectivity, and 59.4% C₂H₄ yield over La_1.6Sr_0.4CuO_3.856Cl_0.126 under the reaction conditions of C₂H₆/O₂/N₂ molar ratio 2/1/3.7, temperature 660°C, and space velocity 6000 ml h^-1 g^-1. With the rise in space velocity, C₂H₆ conversion decreased, whereas C₂H₄ selectivity increased. Life studies showed that the two catalysts were durable within 60 h of on‐stream ODE reaction. Based on the results of X‐ray photoelectron spectroscopy, O₂ temperature-programmed desorption, and C₂H₆ and C₂H₆/O₂/N₂ (2/1/3.7 molar ratio) pulse studies, we conclude that (i) the inclusion of halide ions in the La_1.6Sr_0.4CuO_4δ lattice could promote lattice oxygen mobility, and (ii) the O^- species accommodated in oxygen vacancies and desorbed below 600°C favor ethane complete oxidation whereas the lattice oxygen species desorbed in the 600–700°C range are active for ethane selective oxidation to ethene. By regulating the oxygen vacancy density and Cu³/Cu ratio in the K₂NiF₄-type halo-oxide catalyst, one can generate a durable catalyst with good performance for the ODE reaction. This revised version was published online in July 2006 with corrections to the Cover Date.     

The effects of titania overlayers on C2H4/CO/H2 reactions over a Rh foil

The effects of submonolayer deposits of titania on the activity and selectivity of a Rh foil catalyst for C₂H₄/CO/H₂ reactions have been investigated. Reactions were carried out at 1 atm total pressure and at temperature of 488 K and 523 K. The addition of titania to the catalyst enhances the total rate of C₃-oxygenate formation. This rate enhancement is due entirely to an increase in the rate of 1-propanol formation, which reaches a maximum at a TiO _x . coverage of 0.2 ML. The rate of propanal formation, by contrast, is not enhanced. The rates of formation of methane, ethane, and C₃-hydrocarbons also exhibit rate maxima at a TiO _x . coverage of 0.2 ML. The rates of formation of C₄- and C₅-hydrocarbons, on the other hand, are suppressed by titania addition. The higher rate of 1-propanol production in the presence of titania is attributed to an interaction between Ti³⁺ ions at the edge of TiO _x . islands and the carbonyl bond of adsorbed C₃-oxygenated species. Such interactions are envisioned to facilitate hydrogenation of the carbonyl bond.     

Adsorbate-assisted NO decomposition in NO reduction by C3H6 over Pt/Al2O3 catalysts under lean-burn conditions

The rates and product selectivities of the C₃H₆-NO-O₂ and NO-H₂ reactions over a Pt/Al₂O₃ catalyst, and of the straight, NO decomposition reaction over the reduced catalyst have been compared at 240C. The rate of NO decomposition over the reduced catalyst is seven times greater than the rate of NO decomposition in the C₃H₆-NO-O₂ reaction. This is consistent with a mechanism in which NO decomposition occurs on Pt sites reduced by the hydrocarbon, provided only that at steady state in the lean NO _x reaction about 14% of the Pt sites are in the reduced form. However, the (extrapolated) rate of the NO-H₂ reaction at 240C is about 10⁴ times faster than the rate of the NO decomposition reaction thus raising the possibility that NO decomposition in the former reaction is assisted by H_ads. It is suggested that adsorbate-assisted NO decomposition in the C₃H₆-NO-O₂ reaction could be very important. This would mean that the proportion of reduced Pt sites required in the steady state would be extremely small. The NO decomposition and the NO-H₂ reactions produce no N₂O, unlike the C₃H₆-NO-O₂ reaction, suggesting that adsorbed NO is completely dissociated in the first two cases, but only partially dissociated in the latter case. It is possible that some of the associatively adsorbed NO present during the C₃H₆-NO-O₂ reaction may be adsorbed on oxidised Pt sites.     

Adsorption and Reactions of CH2I2 on Clean and Oxygen-Modified Ag(111): a RAIRS and TPD Study

The surface chemistry of CH₂I₂ on Ag(111) in the presence and absence of pre-adsorbed O, produced by NO₂ adsorption at elevated temperature, has been examined using temperature-programmed desorption and reflection absorption infrared spectroscopy. There is good evidence for the formation of adsorbed methylene, CH₂(a), that reacts with another CH₂(a) to form and desorb ethylene, C₂H₄(g), in a reaction-limited process. Increasing the surface coverage of CH₂I₂ hinders both the dissociation and recombination processes indicated by the upward temperature shift in the formation of C₂H₄. Co-adsorbed O atoms strengthen the bonding of CH₂I₂ to the surface; the increased thermal stability is up to 60 K. The formation of C₂H₄ decreases with increasing amounts of pre-adsorbed O; the main reaction product is CH₂O produced in a reaction-limited process. CH₂O forms either on the chemisorbed or on the oxide phase with desorption peak temperatures of 225 and 270 K, respectively. The formation of gas-phase carbon dioxide suggests that a formate intermediate is involved in a secondary reaction pathway.     

Influence of the Type of Reducing Agent (H2, CO, C3H6 and C3H8) on the Reduction of Stored NOX in a Pt/BaO/Al2O3 Model Catalyst

In this investigation, a comparative study for a NO _X storage catalytic system was performed focusing on the parameters that affect the reduction by using different reductants (H₂, CO, C₃H₆ and C₃H₈) and different temperatures (350, 250 and 150 °C), for a Pt/BaO/Al₂O₃ catalyst. Transient experiments show that H₂ and CO are highly efficient reductants compared to C₃H₆ which is somewhat less efficient. H₂ shows a significant reduction effect at relatively low temperature (150 °C) but with a low storage capacity. We find that C₃H₈does not show any NO _X reduction ability for NO _X stored in Pt/BaO/Al₂O₃ at any of the temperatures. The formation of ammonia and nitrous oxide is also discussed.     

Promoting Effect of Pt Addition to V2O5/ZrO2 Catalyst on Reduction of NO by C3H6

The effect of Pt addition to a V₂O₅/ZrO₂ catalyst on the reduction of NO by C₃H₆ has been studied by FTIR spectroscopy as well as by analysis of the reaction products. Pt loading promoted the catalytic activity remarkably. FTIR spectra of NO adsorbed on the catalysts doped with Pt show the presence of two different types of Pt sites, Pt oxide and Pt cluster, on the surface. The amount of these sites depends on Pt contents and the catalyst state. Pt atoms highly disperse on the surface as Pt oxide at low Pt content, being aggregated into Pt metal clusters by increasing Pt amount or reducing the catalysts. The spectral behavior of V=O bands on the surface also supports the formation of Pt clusters. It is concluded that Pt promotes the NO–C₃H₆ reaction through a reduction–oxidation cycle between its oxide and cluster form.     

Method of estimating absolute concentrations of C<Subscript>2</Subscript>H<Subscript>5</Subscript> and H radicals in hydrocarbon diffusion flames

A method for estimating absolute concentrations of C₂H₅ and H radicals in hydrocarbon diffusion flames is proposed and substantiated. Concentration profiles of C₂H₅ and H on the flame axis are obtained. In the method proposed, the concentration of C₂H₅ is determined from the equality of two quantities — the rate of loss of n-butane by diffusion and the rate of its formation by recombination of two C₂H₅ radicals. The concentration of H radicals is determined from the relation between the ratio C₂H₅/H and experimental profiles of C₂H₄, C₂H₆, and O₂. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 6, pp. 13–20, November–December, 2007.     

Synthesis of di(methylphenyl)methane over heteropolyacids (H3PW12O40) catalysts

Catalytic synthesis of di(methylphenyl)methane (CH₃C₆H₄CH₂C₆H₄CH₃, DMPMs) from toluene and formaldehyde were investigated over various solids acids. At 140 °C and toluene/HCHO = 5/1, the conversion of HCHO over zeolite (Hβ, H-mordenite, HX, HY and HZSM-5) is limited, while heteropolyacids (H₃PW₁₂O₄₀, H₄SiW₁₂O₄₀ and H₃PMo₁₂O₄₀) exhibited higher activity and DMPMs selectivity. The best yield of DMPMs reached 81.5% (conversion of HCHO nearly 100%). H₃PW₁₂O₄₀ could be recovered by simply drying and the recycle-used catalyst remained its activity and structure in five runs.