Iron—molybdenum—oxide catalysts for selective oxidation of hydrogen sulfide to sulfur

The selective oxidation of hydrogen sulfide to sulfur was studied over iron-molybdenum oxides with various Fe-Mo ratios. Strong synergistic phenomenon in catalytic activity was observed for the Fe-Mo-O binary oxides. Under identical reaction conditions, the areal rates of the binary oxides were superior to those of the corresponding single oxide catalysts, which suggest that the new compound Fe₂(MO₄)₃ formed in the binary oxide is more active than Fe₂O₃ and MoO₃. The oxidation rates of H₂S were found to exhibit first-order dependence on the hydrogen sulfide concentration, which implies that the activation of H₂S is the rate-limiting step.     

Low-temperature prepared highly effective ferric hydroxide supported gold catalysts for carbon monoxide selective oxidation in the presence of hydrogen

Ferric hydroxide supported Au catalysts prepared with co-precipitation method at room temperature without any heat treatment hereafter exhibited high catalytic activity and selectivity for CO oxidation in air and CO selective oxidation in the presence of H₂. With calcination temperature rising, both activity and selectivity decreased. X-ray Photoelectron Spectra (XPS) indicated that Au existed as Au⁰ and Au⁺ in the catalyst without heat treatment and even after being calcined at 200 °C, while after being calcined at 400 °C, Au existed as Au⁰ completely. X-ray Diffraction (XRD) and High Resolution Transmission Electron Microscopic (HRTEM) investigations indicated that both the supports and Au species were highly dispersed as nano or sub-nano particles even after being calcined at 200 °C, but after being calcined at 400 °C the supports transformed to crystal Fe₂O₃ with typical diameter of 30 nm and Au species aggregated to nano-particles with typical diameter of 2–4 nm. HRTEM investigations also suggested that the supports calcined at 200 °C were composed of amorphous ferric hydroxide and crystal ferric oxide. Results of computer simulation (CS) showed that O₂ was adsorbed on Au crystal cell and then were activated, which should be the key factor for the subsequent reaction. It also suggested that O₂ species were more easily adsorbed on Au⁺ than on Au⁰, indicating that higher positive charge of the Au species possessed the higher activity for CO oxidation.     

Pyrolysed carbon supported cobalt porphyrin: a potent catalyst for oxidation of hydrogen sulfide

Pyrolysed carbon supported cobalt porphyrin, an electrocatalyst that is frequently used for oxygen reduction in fuel cells, is evaluated for catalytic oxidation of hydrogen sulfide by dissolved dioxygen. The catalyst performs best after heat treatment at 880 °C_, at pH 8. Analysis of the reaction products reveals that sulfur is the dominant product throughout the investigated pH range 5–10. The catalyst performs much better than powdered activated carbon, granular activated carbon and different other forms of unmodified carbon catalysts. This is as far as we know the first time that heat treated cobalt porphyrins are evaluated for non-electrocatalytic applications.     

Selective oxidation of hydrogen sulfide containing excess water and ammonia over vanadia–titania aerogel catalysts

A series of V₂O₅–TiO₂ aerogel catalysts were prepared by sol–gel method with subsequent supercritical drying with CO₂. The aerogel catalysts showed much higher surface areas and total pore volumes than V₂O₅–TiO₂ xerogel and impregnated V₂O₅–TiO₂ catalysts. Two species of surface vanadium in the aerogel catalysts were identified by Raman measurements: monomeric vanadyl and polymeric vanadates. The selective oxidation of hydrogen sulfide in the presence of excess water and ammonia was studied over these catalysts. Aerogel catalysts showed very high conversion of H₂S without harmful emission of SO₂. Temperature programmed reduction (TPR), XRD and Raman analyses revealed that the high catalytic performance of the aerogel catalysts originated from their highly dispersed VO_x species and high reducibility.     

Catalytic synthesis of methanethiol from hydrogen sulfide and carbon monoxide over vanadium-based catalysts

The direct synthesis of methanethiol, CH₃SH, from CO and H₂S was investigated using sulfided vanadium catalysts based on TiO₂ and Al₂O₃. These catalysts yield high activity and selectivity to methanethiol at an optimized temperature of 615 K. Carbonyl sulfide and hydrogen are predominant products below 615 K, whereas above this temperature methane becomes the preferred product. Methanethiol is formed by hydrogenation of COS, via surface thioformic acid and methylthiolate intermediates. Water produced in this reaction step is rapidly converted into CO₂ and H₂S by COS hydrolysis.

Titania was found to be a good catalyst for methanethiol formation. The effect of vanadium addition was to increase CO and H₂S conversion at the expense of methanethiol selectivity. High activities and selectivities to methanethiol were obtained using a sulfided vanadium catalyst supported on Al₂O₃. The TiO₂, V₂O₅/TiO₂ and V₂O₅/Al₂O₃ catalysts have been characterized by temperature programmed sulfidation (TPS). TPS profiles suggest a role of V₂O₅ in the sulfur exchange reactions taking place in the reaction network of H₂S and CO.     

Measuring oxygen, carbon monoxide and hydrogen sulfide diffusion coefficient and solubility in Nafion membranes

A Devanathan-Stachurski type diffusion cell made from a fuel cell assembly is designed to evaluate the gas transport properties of a proton exchange membrane as a function of cell temperature and gas pressure. Data obtained on this cell using the electrochemical monitoring technique (EMT) is used to estimate solubility and diffusion coefficient of oxygen (O₂), carbon monoxide (CO) and hydrogen sulfide (H₂S) in Nafion membranes. Membrane swelling and reverse-gas diffusion due to water flux are accounted for in the parameter estimation procedure. Permeability of all three gases was found to increase with temperature. The estimated activation energies for O₂, CO and H₂S diffusion in Nafion 112 are 12.58, 20 and 8.85 kJ mol⁻¹, respectively. The estimated enthalpies of mixing for O₂, CO and H₂S in Nafion 112 are 5.88, 3.74 and 7.61 kJ mol⁻¹, respectively. An extensive comparison of transport properties estimated in this study to those reported in the literature suggests good agreement. Oxygen permeability in Nafion 117 was measured as a function of gas pressures between 1 and 3 atm. Oxygen diffusion coefficient in Nafion 117 is invariant with pressure and the solubility increases with pressure and obeys Henry's law. The estimated Henry's constant is 3.5 × 10³ atm.     

纳米金催化剂在CO低温氧化和选择性氧化中的研究进展

介绍了纳米金催化剂在CO低温氧化和丙烯直接环氧化反应中的研究进展。在CO低温氧化反应中,催化剂的活性相和载体都具有明显的尺寸效应,纳米金颗粒和载体之间的相互作用主要表现载体不仅可以改变纳米金颗粒的大小和形状,而且也影响了氧的活化,从而提高反应活性;在丙烯直接环氧化反应中,由H2和O2在金颗粒表面反应生成的过氧化物种是反应中间体;在选择性氧化和选择性加氢反应中,金催化剂表现出优良的活性和稳定性。     

氧化吸收硫化氢的新工艺研究

研究了二氧化锰氧化法吸收硫化氢的新工艺，考查了酸度、时间、温度等条件对吸收硫化氢工艺的影响，确定了适合的工艺参数。较合适的条件为：一段，溶液体积0．3L、硫酸浓度0．4mol／L、温度为室温、二氧化锰用量10g；二段，溶液体积0．5L、硫酸浓度0．4mol／L、温度为室温、二氧化锰用量10g。氧化剂二氧化锰被还原为硫酸锰可用氧化水解的方法再生，循环使用。研究结果表明，采用氧化吸收新工艺可以使硫化氢气体的吸收率大于97％，而且二氧化锰可以通过氧化水解的方式再生，实现了氧化剂的再生和循环利用。     

Oxidative dehydrogenation of propane over catalysts based on carbon nanofibers

Carbon nanofibers (CNF) and CNF-supported phosphoric oxides were tested as the catalysts for oxidative dehydrogenation of propane (ODP). The catalysts were characterized by SEM, TEM, X-ray diffraction (XRD), N₂ adsorption and temperature-programmed surface reaction (TPSR). CNF itself is an effective catalyst for ODP, but the high propene yield can only be achieved at high reaction temperature, which would cause CNF gasification. CNF-supported phosphoric oxides can operate at 500 °C without gasification and a 39.63% propene selectivity could be reached at a 42.07% propane conversion. Carbonyl-like groups on the CNF surface could be the active sites for ODP.     

丙烷选择氧化制丙烯酸MoVTeNbO催化剂研究进展

对丙烷选择氧化制丙烯酸的3类催化剂进行了分析,指出了它们未来的研究方向,重点对MoVTeNbO催化剂上丙烷氧化反应机理进行了探讨,总结了人们对该催化剂晶相结构认识的差异,复合金属氧化物催化剂研究的重点是准确掌握催化剂结构．性能关系,实现具有特定晶相结构催化剂的重现性。     

Selective oxidation of hydrogen sulfide over mixture catalysts of V–Sb–O and Bi2O3

The selective oxidation of hydrogen sulfide containing excess water and ammonia was studied over vanadium–antimony mixed oxide catalysts. The investigation was focused on the phase cooperation between V–Sb–O and Bi₂O₃ in this reaction. Strong synergistic phenomenon in catalytic activity was observed for the mechanically mixed catalysts of V–Sb–O and Bi₂O₃. Temperature-programmed reduction (TPR) and oxidation (TPO), two separated bed reaction tests, and XPS analyses were carried out to explain this synergistic effect by the reoxidation ability of Bi₂O₃.     

Microporous and mesoporous materials with isolated vanadium species as selective catalysts in the gas phase oxidation reactions

The preparation of V-containing micro- and mesoporous (silicates, aluminosilicates and aluminophosphates) materials as well as the nature of V species incorporated in framework positions is reviewed. In addition, the catalytic performance of V-silicalite, VAPO-5 and V-MCM-41 in the gas phase selective oxidation of hydrocarbons has also been compared.     

Recent applications of carbon nanotubes in hydrogen production and storage

Hydrogen is actually of great interest because it is the cleanest, sustainable and renewable energy carrier with a significantly reduced impact on the environment. In the future, hydrogen energy systems are expected to progressively replace the existing fossil fuels. Although hydrogen possesses significant advantages, it also exhibits major drawbacks in its utilization. The most important of them are production costs and storage characteristics. Carbon nanotubes (CNTs) have proven to possess ability as support for the fabrication of efficient heterogeneous catalysts in hydrogen production processes. Moreover, CNTs represent convenient adsorbent material that could form the basis of technologically viable hydrogen storage systems. This paper gives an overview of technologies used in the carbon nanotubes production and in the production and storage of hydrogen. In particular, it investigates the feasibility of CNTs and CNTs based catalyst materials in the mentioned processes. Our purpose is to overview the challenges of hydrogen production and storage technologies based on CNTs, to discuss and compare the different results published, and to emphasize recently developed modifications of CNTs that show potential to enhance hydrogen production and storage.     

Catalytic oxidation of hydrogen sulfide by dioxygen on CoN4 type catalyst

A new catalyst based on the formation of carbon supported “CoN₄” structures by heat treatment of Co(CH₃COO)₂ and imidazole impregnated carbon black is introduced. The performance of the new catalyst is compared to the performance of other catalysts including activated carbon powder, granular activated carbon, and pyrolysed cobalt(II) mesotetra-4-methoxyphenylporphyrin. The optimized form of the new catalyst outperforms all these catalysts. The underlying concept is borrowed from fuel cell technology, which uses electrocatalysts that activate triplet dioxygen and facilitate its reduction. The same concept is used to reduce oxygen by hydrogen sulfide. In electrochemistry oxygen reduction is carried out by heterogeneous electron transfer, whereas in dehydrosulfurization the reduced sulfur moieties serve as the electron donors. We postulate that the reason for the improved performance of the new catalyst compared to pyrolysed carbon supported cobalt porphyrin, which is also a Me–N₄ type catalyst, stems from the ability to load a larger amount of cobalt chelates rather than from a change of oxidation mechanism.     

A study on selective oxidation of hydrogen sulfide over zeolite-NaX and-KX catalysts

Selective oxidation of hydrogen sulfide (H₂S) was studied on zeolite-NaX and zeolite-KX. Elemental sulfur yield over zeolite-NaX was achieved about 90% at 225 °C for the first 4 hours, but it gradually decreased to 55% at 40 hours after the reaction started. However, yield of elemental sulfur on zeolite-KX was obtained within the range of 86% at 250 °C after 40 hours. The deactivation of the zeolite-NaX and -KX catalysts was caused by the coverage of a sulfur compound, produced by the selective oxidation of H₂S over the catalysts. The coverage of a sulfur compound over the zeolite-NaX and -KX was confirmed by the TPD (temperature-programmed desorption) tests utilizing thermogravimetric analysis and FT-IR analysis. Even though high temperature was required to prevent the deactivation of zeolite-NaX, the temperature cannot be raised to 250 °C or above due to the SO₂ production and the decrease of thermodynamic equilibrium constant. Zeolite-KX was superior to the zeolite-NaX for both its selectivity to elemental sulfur and its resistance to deactivation in the selective oxidation of H₂S.     

Vanadium oxide catalysts on structured microfiber supports for the selective oxidation of hydrogen sulfide

Vanadium(V) oxide catalysts for the selective oxidation of hydrogen sulfide to sulfur on a nonporous glass-fiber support with a surface layer of a porous secondary support (SiO₂) are studied. The catalysts are obtained by means of pulsed surface thermosynthesis. Such catalysts are shown to have high activity and acceptable selectivity in the industrially important region of temperatures below 200°C. A glass-fiber catalyst containing vanadium oxide (10.3 wt % of vanadium) in particular ensures the complete conversion of H₂S at a temperature of 175°C and a reaction mixture hourly space velocity (RMHSV) of 1 cm³/(g_cat s) with a sulfur yield of 67%; this is at least 1.35 times higher than for the traditional iron oxide catalyst. Using a structured glass-fiber woven support effectively minimizes diffusion resistance and greatly simplifies the scaleup of processes based on such catalysts. Such catalysts can be used for the cleansing of tail gases from Claus units and in other processes based on the selective oxidation of H₂S.     

Bimetallic gold/palladium catalysts for the selective liquid phase oxidation of glycerol

A new methodology for the preparation of single phase bimetallic Au–Pd on activated carbon (AC) has been recently developed and now used for preparing Au/Pd catalysts at different atomic ratio. The bimetallic catalysts have been tested in the liquid phase oxidation on glycerol in water using oxygen as the oxidant and compared with monometallic Au and Pd catalysts. We observed that strong synergistic effect is present in a large range of Au/Pd ratio, being maximized for Au₉₀–Pd₁₀ composition. Gold-rich composition showed an increased durability compared to palladium-rich alloy.     

Co-production of hydrogen and multi-wall carbon nanotubes from ethanol decomposition over Fe/Al2O3 catalysts

The co-production of hydrogen and carbon nanotubes (CNTs) from the decomposition of ethanol over Fe/Al₂O₃ at different temperatures and feeding rates of ethanol was investigated systematically. The results indicated that Fe/Al₂O₃ was a quite active catalyst for the co-production of hydrogen and CNTs and that its activity and stability depended strongly on the Fe loading. Among all catalysts tested, 10 mol% Fe/Al₂O₃ was the most effective catalyst based on the ratio of hydrogen production, the total H₂ yield, and the quality of the CNTs formed. The efficiency of hydrogen production from ethanol decomposition over 10 mol% Fe/Al₂O₃ reached a maximum of 80% at 800 °C and the yield of CNTs with well-oriented growth and uniform diameter was 141%. In addition, the reaction of hydrogen and CNTs co-produced from ethanol decomposition was proposed.     

Simple method for the simultaneous evaluation of combustion and selective oxidation catalysts

The conventional rapid combustion technique used for microanalysis of organic compounds has been modified for the simultaneous evaluation of combustion and selective oxidation catalysts. Using this technique, MnO₂ has been confirmed to be a good combustion catalyst. It was also possible to conclude that Fe₂O₃ and V₂O₅ are good selective oxidation catalysts at 250°C and 300°C, respectively. This simple and rapid method offers much scope for probing into the mechanism of oxidation of hydrocarbons.     

Supported base metal catalysts for the preferential oxidation of carbon monoxide in the presence of excess hydrogen (PROX)

Supported base metal catalysts were tested for the preferential oxidation of CO (CO PROX). The catalysts we investigated covered a wide range of transition metals (Co, Cr, Cu, Ni, Zn) supported on oxides with very different acidic, basic and redox properties (MgO, La₂O₃, SiO₂–Al₂O₃, CeO₂, Ce_0.63Zr_0.37O₂). The influence of the metal loading (Cu), the support properties (acidity, basicity, redox, surface area) and the reaction conditions (reaction temperature, feed composition) on the catalyst activity and selectivity was evaluated. The activity of ceria and ceria–zirconia supported copper catalysts was comparable to the performances of noble metal samples classically used for the PROX reaction. In addition, Cu–CeO₂ catalysts showed a practically constant and high selectivity towards CO oxidation in the temperature range of 50–150 °C. Due to the strong synergetic effect between copper and ceria, only a small amount of copper (0.3 wt.%) was necessary to get an active catalyst. The best catalytic performances were obtained for the samples containing 1–3 wt.% copper. The presence of small copper particles in close interaction with the ceria support was shown to be responsible for the enhanced activity. Except for the hydrogen oxidation, no parallel reactions (CO or CO₂ methanation reactions, coking, RWGS) could be detected over these catalysts. Classically, an increase of the oxygen excess led to an increased CO conversion with a simultaneous loss of selectivity towards CO₂. Finally, the presence of CO₂ in the feed negatively affected the catalytic activity. This effect was attributed to the adsorption of CO₂ on the copper sites, probably as CO.