Selective oxidation of butane on phosphorus-modified silica supported vanadia catalysts

Triethylphosphate impregnation of 2.8 wt% V/SiO₂ and subsequent controlled calcination produced phosphorus-modified supported vanadium catalysts. Phosphorus modification enhanced the yield of maleic anhydride in the partial oxidation of butane. Varying the phosphorus to vanadium atomic ratio from 0 to 2.8 increased the selectivity to maleic anhydride from 0 to approximately 48%. The selectivity was nearly constant up to 20% butane conversion and for different O₂/C₄H₁₀ ratios. The Raman spectra of the phosphorus-modified samples had bands at 1040 and 930 cm^–1, and broad unresolved bands between 580 and 540 cm^–1. It was concluded that the active phases in these samples were -VOPO₄.     

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.     

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.     

Vanadium-molybdenum phosphates supported by TiO2-anatase as new catalysts for selective oxidation of ethane to acetic acid

Dispersion of vanadium and molybdenum phosphates on titanium oxide (anatase) below the monolayer gives good catalysts for direct oxidation of ethane to acetic acid. By comparison with the dispersion of only vanadium phosphate, the higher selectivity to acetic acid for vanadium and molybdenum phosphates has been explained by an interaction between molybdenum and vanadium as it can be deduced from electron spin resonance and laser Raman spectroscopy studies.     

Partial oxidation of methane with air for methanol production in a post-plasma catalytic system

Partial oxidation of methane to methanol via post-plasma catalysis using a dielectric-barrier discharge was performed under mild reaction conditions. Air was used as the oxidizing co-reactant because of its economical practicality. Three catalysts impregnated with Pt, Fe₂O₃, CeO₂ on ceramic supports located downstream of the discharge zone were examined for increased selectivity towards methanol. It was found that all three catalysts had no significant effect on the conversion of methane, but enhanced methanol selectivity, which could be explained by a two-stage reaction mechanism. The Fe₂O₃-based catalyst showed the best catalytic activity, and high stability in the reaction. The methanol selectivity of the Fe₂O₃-assisted plasma process was 36% higher than that of the non-catalytic system at a rather low catalyst temperature (150 °C). In addition, the effects of input power, discharge frequency, discharge gap distance, total flow rate, and methane/air ratio on methane conversion and methanol yield were also studied.     

Partial oxidation of ethane by in situ generated H2O2

Selective partial oxidation of ethane to ethanol and acetaldehyde by in situ generated H₂O₂ has been achieved under cathodic current passing through a carbon supported Nafion-H catalytic membrane. A correlation between H₂O₂ generation rate and reaction rate has been found.     

Partial oxidation of ethanol over Pd/CeO2 and Pd/Y2O3 catalysts

The effect of the support nature on the performance of Pd catalysts during partial oxidation of ethanol was studied. H₂, CO₂ and acetaldehyde formation was favored on Pd/CeO₂, whereas CO production was facilitated over Pd/Y₂O₃ catalyst. According to the reaction mechanism, determined by DRIFTS analyses, some reaction pathways are favored depending on the support nature, which can explain the differences observed on products distribution. On Pd/Y₂O₃ catalyst, the production of acetate species was promoted, which explain the higher CO formation, since acetate species can be decomposed to CH₄ and CO at high temperatures. On Pd/CeO₂ catalyst, the acetaldehyde preferentially desorbs and/or decomposes to H₂, CH₄ and CO. The CO formed is further oxidized to CO₂, which seems to be promoted on Pd/CeO₂ catalyst.     

Effects of MgO promoter on properties of Ni/Al2O3 catalysts for partial oxidation of methane to syngas

The effects of MgO promoter on the physicochemical properties and catalytic performance of Ni/Al₂O₃ catalysts for the partial oxidation of methane to syngas were studied by means of BET, XRD, H₂-TPR, TEM and performance evaluation. It was found that the MgO promoter benefited from the uniformity of nickel species in the catalysts, inhibited the formation of NiAl₂O₄ spinel and improved the interaction between nickel species and support. These results were related to the formation of NiO-MgO solid solution and MgAl₂O₄ spinel. Moreover, for the catalysts with a proper amount of MgO promoter, the nickel dispersiveness was enhanced, therefore making their catalytic performance in methane partial oxidation improved. However, the excessive MgO promoter exerted a negative effect on the catalytic performance. Meanwhile, the basicity of MgO promoted the reversed water-gas shift reaction, which led to an increase in CO selectivity and a decrease in H₂ selectivity. The suitable content of MgO promoter in Ni/Al₂O₃ catalyst was ∼7 wt-%. Translated from Journal of Fuel Chemistry and Technology, 2006, 34(4): 450–455 [译自: 燃料化学学报]     

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.     

Effect of the support on the mechanism of partial oxidation of methane on platinum catalysts

The partial oxidation of methane was studio on Pt/Al₂O₃, Pt/ZrO₂, Pt/CeO₂ and Pt/Y₂O₃ catalysts. For Pt/Al₂O₃, Pt/ZrO₂ and Pt/CeO₂, temperature programmed surface reaction (TPSR) studies showed partial oxidation of methane comprehends two steps: combustion of methane followed by CO₂ and steam reforming of unreacted methane, while for Pt/Y₂O₃ a direct mechanism was observed. Oxygen Storage Capacity (OSC) evaluated the reducibility and oxygen transfer capacity of the catalysts. Pt/CeO₂ catalyst showed the highest stability on partial oxidation. The results were explained by the higher reducibility and oxygen storage/release capacity which allowed a continuous removal of carbonaceous deposits from the active sites, favoring the stability of the catalyst. For Pt/Al₂O₃ and Pt/ZrO₂ catalysts the increase of carbon deposits around or near the metal particle inhibits the CO₂ dissociation on CO₂ reforming of methane. Pt/Y₂O₃ was active and stable for partial oxidation of methane and its behaviour was explained by a change in the reaction mechanism.     

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 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.     

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 partial oxidation of C4–C6 alkanes to maleic anhydride, 2-methyl maleic anhydride, and acetic acid over MoVO catalysts

Alkanes such as iso-butane, n-pentane, and cyclohexane have been converted effectively to maleic anhydride, 2-methyl maleic anhydride, and acetic acid over MoVO catalysts below 330 °C. In order to explore the possible reaction pathways, the oxidation of iso-butene, cyclohexene, 2-methyl-1-propanol, tert-butanol, and 2-methylacrylic acid were examined over the catalysts. In iso-butene oxidation, acetic acid and 2-methyl maleic anhydride were detected but not maleic anhydride. In cyclohexene oxidation, benzene and phenol were detected as major products but it was not the case in cyclohexane oxidation. The results of our investigation indicate that the oxidation pathway of iso-butane is different from that of iso-butene, 2-methyl-1-propanol, tert-butanol, and 2-methylacrylic acid, whereas the oxidation pathway of cyclohexane is different from that of cyclohexene.     

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.     

129Xe NMR to probe microscopic mixing state of composite catalysts

¹²⁹Xe NMR spectra obtained from microporous solid mixtures such as NaY-Pt/NaY and NaY-Pt/Al₂O₃ have indicated that the NMR peak pattern can depend greatly on the mixing method.¹²⁹Xe NMR can thus be a very simple and useful technique to probe the physical mixing state of many composite catalysts.     

Partial oxidation of CH4 at low pressure over SiO2 prepared from Si

The oxidation of CH₄ with O₂ at low pressure was carried out over SiO₂ prepared from metal Si. The Si showed only total oxidation activity while the Si partly oxidized to SiO₂ showed high selectivities to CH₃OH and HCHO. The results on SiO₂ prepared from Si were compared with those over commercial silicas. The role of SiO₂ in the CH₄ oxidation was discussed.     

Effect of the metal oxide loading on the activity of silica supported MoO3 and V2O5 catalysts in the selective partial oxidation of methane

Precipitated silica catalysts loaded with either MoO₃ (0.2–4.0 wt%) or V₂O₅ (0.2–5.3 wt%) have been studied in the selective partial oxidation of methane to formaldehyde with molecular oxygen at 520 °C. The functionality of the SiO₂ surface towards the formation of HCHO is significantly promoted by V₂O₅, while it is depressed by the MoO₃.     

Selective oxidation of hydrogen sulfide containing excess water and ammonia over Bi-V-Sb-O catalysts

We investigated the selective oxidation of hydrogen sulfide to elemental sulfur and ammonium thiosulfate by using Bi₄V_2-xSb_xO_11-y catalysts. The catalysts were prepared by the calcination of a homogeneous mixture of Bi₂O₃, V₂O₅, and Sb₂O₃ obtained by ball-milling adequate amounts of the three oxides. The main phases detected by XRD analysis were Bi₄V₂O₁₁, Bi_1.33V₂O₆, BiSbO₄ and BiVO₄. They showed good H₂S conversion with less than 2% of SO₂ selectivity with a feed composition of H₂S/O₂/NH₃/H₂O/He=5/2.5/5/60/27.5 and GHSV=12,000 h^-1 in the temperature ranges of 220–260 ‡C. The highest H₂S conversion was obtained for x=0.2 in Bi₄V_2-xSb_xO_11-y catalyst. TPR/TPO results showed that this catalyst had the highest amount of oxygen consumption. XPS analysis before and after reaction confirmed the least reduction of vanadium oxide phase for this catalyst during the reaction. It means that the catalyst with x=0.2 had the highest reoxidation capacity among the Bi₄V_2-xSb_xO_11-y catalysts.     

Combined catalytic partial oxidation and CO2 reforming of methane over supported cobalt catalysts

The combined partial oxidation and CO₂ reforming of methane to synthesis gas was investigated over the reduced Co/MgO, Co/CaO, and Co/SiO₂ catalysts. Only Co/MgO has proved to be a highly efficient and stable catalyst. It provided about 94–95% yields to H₂ and CO at the high space velocity of 105000 mlg^–1h^–1 and for feed ratios CH₄/CO₂/O₂=4/2/1, without any deactivation for a period of study of 110 h. In contrast, the reduced Co/CaO and Co/SiO₂ provided no activity for the formation of H₂ and CO. The structure and reducibility of the calcined catalysts were examined using X-ray diffraction and temperature-programmed reduction, respectively. A solid solution of CoO and MgO, which was difficult to reduce, was identified in the 800°C calcined MgO-supported catalyst. The strong interactions induced by the formation of the solid solution are responsible for its superior activity in the combined reaction. The effects of reaction temperature, space velocity, and O₂/CO₂ ratio in the feed gases (while keeping the C/O ratio constant at 1/1) were investigated over the Co/MgO catalyst. The H₂/CO ratio in the product of the combined reaction increased with increasing O₂/CO₂ ratio in the feed.