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.     

Selective oxidation of H<Subscript>2</Subscript>S to ammonium thiosulfate and elemental sulfur using mixtures of V-Bi-O and Sb<Subscript>2</Subscript>O<Subscript>4</Subscript>

The selective oxidation of hydrogen sulfide in the presence of excess water and ammonia was investigated by using vanadium-bismuth based mixed oxide catalysts. Synergistic effect on catalytic activity was observed for the mechanical mixtures of V-Bi-O and Sb₂O₄. Temperature programmed oxidation (TPO), X-ray photoelectron spectroscopy (XPS), and two separated bed reactivity test results supported the role of Sb₂O₄ for reoxidizing the reduced V-Bi-O during the reaction. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Selective CO oxidation in the presence of hydrogen over supported Pt catalysts promoted with transition metals

Selective CO oxidation in the presence of excess hydrogen was studied over supported Pt catalysts promoted with various transition metal compounds such as Cr, Mn, Fe, Co, Ni, Cu, Zn, and Zr. CO chemisorption, XRD, TPR, and TPO were conducted to characterize active catalysts. Among them, Pt-Ni/γ-Al₂O₃ showed high CO conversions over wide reaction temperatures. For supported Pt-Ni catalysts, Alumina was superior to TiO₂ and ZrO₂ as a support. The catalytic activity at low temperatures increased with increasing the molar ratio of Ni/Pt. This accompanied the TPR peak shift to lower temperatures. The optimum molar ratio between Ni and Pt was determined to be 5. This Pt-Ni/γ A1₂O₃ showed no decrease in CO conversion and CO₂ selectivity for the selective CO oxidation in the presence of 2 vol% H₂O and 20 vol% CO₂. The bimetallic phase of Pt-Ni seems to give rise to stable activity with high CO₂ selectivity in selective oxidation of CO in H₂-rich stream.     

Selective oxidation of H2S to sulfur over vanadia supported on mesoporous zirconium phosphate heterostructure

Vanadium oxide supported on mesoporous zirconium phosphate catalysts has been synthesized, characterized and tested in the selective oxidation of H₂S to sulfur. The nature of the vanadium species depends on the V-loading of catalyst. Catalysts with a V-content lower than 4wt% present both isolated vanadium species and V₂O₅ crystallites. However, V₂O₅ crystallites have been mainly observed in catalysts with higher V-content, although the presence of isolated V-species on the surface of the metal oxide support cannot be completely ruled out. The catalytic behaviour also depends on V-loading of catalysts. Thus, while the catalytic activity of catalysts can be related to the number of V-sites, the catalyst decay is clearly observed in samples with low V-loading. The characterization of catalysts after the catalytic tests indicates the presence of sulfur on the catalyst, which is favoured on catalysts with low V-loading. However, a clear transformation of V₂O₅ to V₄O₉ can be proposed according to XRD and Raman results of used catalysts with high V-loading. The importance of V⁵⁺–O–V⁴⁺ pairs in activity and selectivity is also discussed.     

Selective oxidation of h2s in the presence of ammonia and water using co3o4/sio2 catalyst

The catalytic performance of some metal oxides in the selective oxidation of H₂S in the stream containing water vapor and ammonia was investigated in this study. Among the catalysts tested, Co₃O₄SiO₂ was the most promising catalyst for practical application. It showed very small amount of SO₂ emission even in the presence of excess water and ammonia. The solid product formed in the reaction was a mixture of elemental sulfur, ammonium thiosulfate and ammonium sulfate.     

Selective oxidation of hydrogen sulfide over LaCoO<Subscript>3</Subscript> and LaSrCoO<Subscript>4</Subscript> mixed oxides

Perovskite LaCoO₃ and perovskite-like LaSrCoO₄ mixed oxides were prepared by polyglycol gel method, and their catalytic performance was compared for the selective oxidation of hydrogen sulfide in a stream containing excess amount of ammonia and water for the first time. These samples were investigated by using XRD, BET, O₂-TPD and XPS. The catalytic activity and the selectivity to solid products (ammonium thiosulfate and elemental sulfur) of LaCoO₃ were better than those of LaSrCoO₄, and this is explained in terms surface contents of oxygen and cobalt, oxidation state of cobalt, and BET surface area.     

Selective oxidation of methanol to dimethoxymethane over acid-modified V2O5/TiO2 catalysts

Selective oxidation of methanol to dimethoxymethane (DMM) was conducted in a fixed-bed reactor over an acid-modified V₂O₅/TiO₂ catalyst. The influence of the acid modification on its structure, redox and acidic properties, and catalytic performance for methanol oxidation were investigated. The results indicated that the content of vanadia in the catalyst exhibits a vital influence on the dispersion of vanadium species, while the acid modification can enhance its surface acidity. Proper amounts of the acid (W() = 15%) and V₂O₅ (W(V₂O₅) = 15%) components loaded in the acid-modified V₂O₅/TiO₂ catalyst are able to build a bi-functional circumstance that is favorable for the formation of DMM with high activity and selectivity. As a result, for the selective oxidation of methanol, the H₂SO₄-modified V₂O₅/TiO₂ catalyst gives a much higher DMM yield at 150 °C than the unmodified one.     

The study on the selective oxidation of H<Subscript>2</Subscript>S over the mixture zeolite NaX-WO<Subscript>3</Subscript> catalysts

At temperatures lower than 250 °C the deactivation of zeolite NaX catalyst occurred in the presence of water vapor. The gradual accumulation of water vapor on the surface of catalyst could cause deactivation of catalyst. The zeolite NaX-WO₃ catalysts were prepared to study a method preventing deactivation of catalysts from the adsorption of water vapor. The zeolite NaX-WO₃ (9 : 1) with a low content of WO₃ showed the highest conversion of H₂S. It is believed that the addition of WO₃ caused either a decrease of the strong adsorption of water vapor on the zeolite NaX or an increase of the reducibility of WO₃ by some interactions between zeolite NaX and WO₃. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Partial oxidation of methane over nickel catalysts supported on various aluminas

Partial oxidation of methane (POM) was systematically investigated in a fixed bed reactor over 12 wt% Ni catalysts supported on α-A1₂O₃, γ-A1₂O₃ and θ-A1₂O₃ which were prepared at different conditions. Results indicate that the catalytic activity toward POM strongly depends on the BET surface area of the support. All the Ni/ θ-Al₂O₃ catalysts showed high activity toward POM due to the less formation of inactive NiAl₂O₄ species, the existence of NiO, species and stable θ-Al₂O₃ phase. Although Ni/γ-Al₂O₃ showed the highest activity toward POM, long-time stability cannot be expected as a result of the deterioration of the support at higher temperature, which is revealed from BET results. From the reaction and characterization results, it is inferred that the optimal conditions for the preparation of θ-Al₂O₃ are 1,173 K and 12 h.     

Influence of homogeneous decane oxidation on the catalytic performance of lean NO x catalysts

Extensive homogeneous gasphase reactions were observed when decane was used as the hydrocarbon reductant for the selective reduction of NO _x . The catalytic performance of a SnO₂/CoO _x /Al₂O₃ catalyst was found to be strongly dependent on the extent of the homogeneous reaction in the precatalytic volume. The effect of the homogeneous reaction on the catalytic performance also depended on whether SO₂ was present in the feed. By filling the precatalytic volume with 25–35 mesh irregularly shaped quartz chips, gasphase reaction was suppressed significantly. This methodology was used to evaluate the inherent catalytic performance of SnO₂/CoO _x /Al₂O₃ and SnO₂/Al₂O₃ catalysts with decane as a reductant. It was found that in the absence of SO₂, SnO₂/Al₂O₃ was a better catalyst than SnO₂/CoO _x /Al₂O₃, but in the presence of 30 ppm of SO₂ the latter was a far better catalyst.     

Selective catalytic reduction of NOx using propene and ethanol over catalysts of Ag/Al2O3 prepared by microemulsion and promotional effect of hydrogen

The present study explores the possibilities of catalysts of Ag/Al₂O₃, in which silver has been deposited using reverse microemulsions with the aim of getting maximum dispersion and homogeneity in the active superficial species, for the selective catalytic reduction of NO_x in excess of oxygen, using both propene and ethanol as reductants and in the scope of the control of the emissions produced by vehicles that operate in conditions of lean mixture like the diesel engine or those of gasoline direct injection. The promotional effect of the hydrogen presence in the reactive mixture has also been analyzed. For both reductants, when in presence of hydrogen, an important enhancement in NO_x conversion is produced, in particular for a catalyst with 3 wt.% silver. The production of acetaldehyde during the reaction employing ethanol is also analyzed and its role on the NO_x reduction process has been examined. The interpretation of catalytic properties has been complemented by means of in-situ DRIFTS.     

Detoxication of water containing 1,1-dimethylhydrazine by catalytic oxidation with dioxygen and hydrogen peroxide over Cu- and Fe-containing catalysts

A number of Cu- and Fe-hydroxide containing catalysts, supported on oxide carriers, were prepared to provide the removal of 1,1-dimethylhydrazine from aqueous solutions via its oxidation by hydrogen peroxide and air oxygen. The Cu-containing samples as well as Fe/ZSM-5 are the most active catalysts in this reaction. The reaction products were analyzed by gas chromatography and UV–Vis spectroscopy. The effect of nature of the oxidizer and catalyst, pH and temperature on both the reaction rate and product composition was studied.     

Selective oxidation of methane to methanol and formaldehyde over V2O5/SiO2 catalysts. Role of NO in the gas phase

The role of nitric oxide incorporation into the reaction feed for the partial oxidation of methane to C₂-hydrocarbons and C₂-oxygenates is evaluated. The addition of NO increases the conversion of methane under all the experimental conditions studied and has a strong effect on the product distribution. At low NO concentration the catalysts yield mainly C₂H_n hydrocarbons, but at higher NO concentrations, carbon oxides dominate. Amongst the C₁-oxygenates produced, methanol is the major compound observed and its proportion increases with increasing NO concentration. The highest C₁-oxygenates yield was 7% at atmospheric pressure. This revised version was published online in July 2006 with corrections to the Cover Date.     

Partial oxidation of methane over ruthenium catalysts

The catalytic partial oxidation of methane with oxygen to produce synthesis gas was studied under a wide range of conditions over supported ruthenium catalysts. The microreador results demonstrated the high activity of ruthenium catalysts for this reaction. A catalyst having as little as 0.015% (w/w) Ru on Al₂O₃ gave a higher synthesis gas selectivity than a catalyst having 5% Ni on SiO₂. XANES measurements for fresh and used catalyst samples confirmed that ruthenium is reduced from ruthenium dioxide to ruthenium metal early during the experiments. Ruthenium metal is thus the active element for the methane partial oxidation reaction.     

Biomass to hydrogen via catalytic steam reforming of bio-oil over Ni-supported alumina catalysts

Production of hydrogen (H₂) from catalytic steam reforming of bio-oil was investigated in a fixed bed tubular flow reactor over nickel/alumina (Ni/Al₂O₃) supported catalysts at different conditions. The features of the steam reforming of bio-oil, including the effects of metal content, reaction temperature, W_bHSV (defined as the mass flow rate of bio-oil per mass of catalyst) and S/C ratio (the molar ratio of steam to carbon fed) on the hydrogen yield were investigated. Carbon conversion (moles of carbon in the outlet gases to moles of the carbon feed) was also studied, and the outlet gas distributions were obtained. It was revealed that the Al₂O₃ with 14.1% Ni content gave the highest yield of hydrogen (73%) among the catalysts tested, and the best carbon conversion was 79% under the steam reforming conditions of S/C = 5, W_bHSV = 13 1/h and temperature = 950 °C. The H₂ yield increased with increasing temperature and decreasing W_bHSV; whereas the effect of the S/C ratio was less pronounced. In the S/C ratio range of 1 to 2, the hydrogen yield was slightly increased, but when the S/C ratio was increased further, it did not have an effect on the H₂ production yield.     

Selective reduction of NOx by hydrogen and methane in natural gas stationary sources over alumina supported Pd, Co and Co/Pd catalysts: Part B: On the effect of bimetallic catalyst preparation

The aim of the present work is to study the selective reduction of NO_x from natural gas sources using unburned methane or hydrogen as reducing agents. The results suggest that the NO_x are reduced by H₂ at low temperature, when methane is not activated and at higher temperature the methane is then the main reducing agent. Similar results are obtained for alumina supported palladium and alumina supported cobald-palladium catalysts at low temperature in presence of hydrogen suggesting that the active phase for the reaction NO/H₂ is the palladium. However, at high temperature the higher activity is obtained on bimetallic catalyst. The presence of cobalt enhances the catalytic activity. This result suggests that cobalt and palladium both in cationic form are the active sites when the reducing agent is the methane.     

Pulse study of methane partial oxidation to syngas over SiO2-supported nickel catalysts

Methane was pulsed over pure CuO and NiO as well as Cu/La₂O₃ and Ni/La₂O₃ catalysts at 600° C. Results indicate that the mechanisms for methane activation over copper and nickel are quite different. Over CuO, methane is converted to CO₂ and H₂O, most likely via the combustion mechanism; whereas metallic copper does not activate methane. Over NiO in the presence of metallic nickel sites, methane activation follows the pyrolysis mechanism to give CO, CO₂, H₂ and H₂O. Similar results were obtained over the Cu/La₂O₃ and Ni/La₂O₃ catalysts. XRD investigations indicate that copper and nickel existed as CuLa₂O₄ and LaNiO₃ respectively in the La₂O₃-supported catalysts. The effect of La₂O₃ on the activation of methane is discussed.     

Low temperature oxidation of CO over supported PdCl2-CuCl2 catalysts

PdCl₂-CuCl₂ catalyst supported on activated carbon was examined for the low temperature oxidation of CO. The catalyst developed in the present study was active and stable at ambient conditions if water were existing in the feed gas stream. The addition of Cu(NO₃)₂ into the PdCl₂-CuCl₂ catalyst significantly enhanced the CO oxidation activity. X-ray diffraction study revealed that the role of Cu(NO₃)₂ was to stabilize active Cu(II) species, Cu₂Cl(OH)₃, on the catalyst surface which maintains the redox property of palladium. When HC1 and SO₂ were also existing in the feed, they easily inactivated the catalyst. It was found that HC1 and SO₂ inhibited the formation of active Cu(II) species on the catalyst surface.     

Selective reduction of NOx by hydrogen and methane in natural gas stationary sources over alumina-supported Pd, Co and Co/Pd catalysts: Part A. On the effect of palladium precursors and catalyst pre-treatment

The aim of the present work is to study the selective reduction of NO_x from natural gas sources. The unburned methane can be used as reductant. Another reductant such as hydrogen can be created in situ, using a microreformer. The results suggest that the NO_x are reduced by H₂ at low temperature, when methane is not activated and at higher temperature the methane is then the main reductant. However, the catalytic behaviour depends on the metal precursor and the catalyst treatment. The most prominent result is obtained on the palladium catalyst prepared from Pd(NH₃)₄(NO₃)₂ precursor. Comparing the reduction and the calcination step in the course of catalyst preparation, one can conclude that calcination lead to the higher activity in deNO_x, since reduced catalysts are oxidized during the deNO_x process.     

Catalytic oxidation of hydrogen over Au/TiO2 catalysts

Selective catalytic oxidation of hydrogen in the presence of hydrocarbons was studied in a fixed bed quartz reactor, over 3 wt%Au/TiO₂ and 5 wt%Au/TiO₂ catalysts. This reaction can be utilised in the production of light alkenes via catalytic dehydrogenation, providing in situ heat to the endothermic dehydrogenation reaction and simultaneously removing a fraction of the produced hydrogen. It is important to avoid the non-selective combustion of the hydrocarbons in the mixture. Both 3 wt%Au/TiO₂ and 5 wt%Au/TiO₂ are active for the combustion of hydrogen, but in a gas mixture with propane and oxygen the selectivity is dependent upon the feed ratio of hydrogen and oxygen. At 550 °C, with propane present, no carbon oxides are formed when the H₂:O₂ ratio is four, but at lower ratios some CO₂ and some CO is formed.