The simultaneous activation of methane and carbon dioxide to C2 hydrocarbons under pulse corona plasma over La2O3/γ-Al2O3 catalyst

The pulse corona plasma has been used as an activation method for reaction of methane and carbon dioxide, the product was C₂ hydrocarbons and by-products were CO and H₂. Methane conversion and the yield of C₂ hydrocarbons were affected by the carbon dioxide concentration in the feed. The conversion of methane increased with increasing carbon dioxide concentration in the feed whereas the yield of C₂ hydrocarbons decreased. The synergism of La₂O₃/γ-Al₂O₃ and plasma gave methane conversion of 24.9% and C₂ hydrocarbons yield of 18.1% were obtained at the power input of plasma was 30 W. The distribution of C₂ hydrocarbons changed by using Pd-La₂O₃/γ-Al₂O₃ catalyst, the major C₂ product was ethylene.     

Conversion of methane through dielectric-barrier discharge plasma

Methane coupling to produce C₂ hydrocarbons through a dielectric-barrier discharge (DBD) plasma reaction was studied in four DBD reactors. The effects of high voltage electrode position, different discharge gap, types of inner electrode, volume ratio of hydrogen to methane and air cooling method on the conversion of methane and distribution of products were investigated. Conversion of methane is obviously lower when a high voltage electrode acts as an outer electrode than when it acts as an inner electrode. The lifting of reaction temperature becomes slow due to cooling of outer electrode and the temperature can be controlled in the expected range of 60°C–150°C for ensuring better methane conversion and safe operation. The parameters of reactors have obvious effects on methane conversion, but it only slightly affects distribution of the products. The main products are ethylene, ethane and propane. The selectivity of C₂ hydrocarbons can reach 74.50% when volume ratio of hydrogen to methane is 1.50.     

Plasma methane conversion using dielectric-barrier discharges with zeolite A

Experimental investigation on plasma methane conversion in the presence of carbon dioxide using dielectric-barrier discharges (DBDs) has been conducted. Zeolite A has been applied to inhibit the formation of carbon black and plasma-polymerized film during such plasma methane conversion. A co-generation of syngas, light hydrocarbons and liquid fuels has been achieved. The conversions and selectivities are determined by the CH₄/CO₂ feed ratio, residence time and input power. Compared to the use of zeolite X within the DBDs, plasma methane conversion with zeolite A leads to a higher selectivity of light hydrocarbons (C₂–C₄).     

Methanol formation from methane partial oxidation in CH4–O2–NO gaseous phase at atmospheric pressure

The reaction condition for high yield of methanol in a gaseous reaction between methane and oxygen in the presence of NO at atmospheric pressure was explored. Methane partial oxidation without NO (CH₄–O₂) gave only 1% conversion of methane at 966 K. The addition of NO led to a remarkable increase in methane conversion and to high selectivity to C₁-oxygenates. The conversion of methane attained 10% at 808 K in the presence of NO (0.5%) where the selectivities to methanol and formaldehyde were 22.1 and 24.1%, respectively. Nitromethane and carbon oxides were also observed in the product gas. The amount of nitromethane was almost equal and/or near to that of initial NO. The carbon monoxide produced was several times higher than carbon dioxide. Influences of NO concentration, ratio of methane to oxygen, water vapor, and dilution with helium gas on product distribution were measured. Low concentration of NO (0.35–0.55%) was favorable for methanol formation. High selectivity to methanol was obtained at low value of the ratio of methane to oxygen (2.0–3.0) or low concentration of dilution gas (<16%). The NO₂ added promoted methane partial oxidation and selectivity to methanol. Therefore, it was assured that NO_x promoted the formation of CH₃√ and CH₃O√ in the gas phase reaction for CH₄–O₂–NO.     

Lithium-doped sulfated-zirconia catalysts for oxidative coupling of methane to give ethylene and ethane

Li-doped sulfated-zirconia catalysts were found to be effective for oxidative coupling of methane (OCM). The catalyst performances depend on the sulfate content and calcination temperature. A maximum C₂ yield is attained over the catalysts, which contain 6 wt.% sulfate and calcined at 923–973 K, being closely related to the preparation conditions of sulfated-ZrO₂ as solid super-acids. When the performances of the Li-doped sulfated-ZrO₂ (Li/SZ) catalysts were tested at 1023 K as a function of reaction time, both the C₂ and CO_x selectivities remained constant over the range of 8 h, but the CH₄ conversion decreased from 17.5% to 11.9%. The nature of Li/SZ catalysts for the OCM was investigated by X-ray diffraction, XPS, and NH₃ and CO₂ TPD measurements. It could be postulated that the sulfated-ZrO₂ surface could play an important role in the formation of a catalytically active structure by Li-doping.     

Production of gasoline range hydrocarbons from catalytic reaction of methane in the presence of ethylene over W/HZSM-5

The catalytic conversion of a methane and ethylene mixture to gasoline range hydrocarbons has been studied over W/HZSM-5 catalyst. The effect of process variables, such as temperature, percentage of volume of ethylene in the methane stream and catalyst loading on the distribution of hydrocarbons was studied. The reaction was conducted in a fixed-bed quartz-micro reactor in the temperature range of 300–500 °C using percentage of volume of ethylene in methane stream between 25 and 75% and catalyst loading of 0.2–0.4 g. The catalyst showed good catalytic performance yielding hydrocarbons consisting of gaseous products along with gasoline range liquid products. The mixed feed stream can be converted to higher hydrocarbons containing a high-liquid gasoline product selectivity (>42%). Non-aromatics C₅–C₁₀ hydrocarbons selectivity in the range of 12–53% was observed at the operating conditions studied. Design of experiment was employed to determine the optimum conditions for maximum liquid hydrocarbon products. The distribution of the gasoline range hydrocarbons (C₅–C₁₀ non-aromatics and aromatics hydrocarbons) was also determined for the optimum conditions.     

Improved performance of non-thermal plasma reactor during decomposition of trichloroethylene: Optimization of the reactor geometry and introduction of catalytic electrode

The decomposition of trichloroethylene (TCE) by non-thermal plasma was investigated in a dielectric barrier discharge (DBD) reactor with a copper rod inner electrode and compared with a plasma-catalytic reactor. The particularity of the plasma-catalytic reactor is the inner electrode made of sintered metal fibers (SMF) coated by transition metal oxides. In order to optimize the geometry of the plasma reactor, the efficiency of TCE removal was compared for different discharge gap lengths in the range of 1–5 mm. Shorter gap lengths (1–3 mm) appear to be more advantageous with respect to TCE conversion. In this case TCE conversion varies between 67% and 100% for input energy densities in the range of 80–480 J/l, while for the 5 mm discharge gap the conversion was lower (53–97%) for similar values of the input energy. As a result of TCE oxidation carbon monoxide and carbon dioxide were detected in the effluent gas. Their selectivity was rather low, in the range 14–24% for CO₂ and 11–23% for CO, and was not influenced by the gap length. Several other chlorinated organic compounds were detected as reaction products.

When using MnOx/SMF catalysts as the inner electrode of the DBD reactor, the TCE conversion was significantly enhanced, reaching 95% at 150 J/l input energy. The selectivity to CO₂ showed a major increase as compared to the case without catalysts, reaching 58% for input energies above 550 J/l.     

CO, H2 or C3H8 assisted catalytic combustion of methane over supported LaMnO3 monoliths

The effect of the addition of a second fuel such as CO, C₃H₈ or H₂ on the catalytic combustion of methane was investigated over ceramic monoliths coated with LaMnO₃/La-γAl₂O₃ catalyst. Results of autothermal ignition of different binary fuel mixtures characterised by the same overall heating value show that the presence of a more reactive compound reduces the minimum pre-heating temperature necessary to burn methane. The effect is more pronounced for the addition of CO and very similar for C₃H₈ and H₂. Order of reactivity of the different fuels established in isothermal activity measurements was: CO>H₂≥C₃H₈>CH₄. Under autothermal conditions, nearly complete methane conversion is obtained with catalyst temperatures around 800 °C mainly through heterogeneous reactions, with about 60–70 ppm of unburned CH₄ when pure methane or CO/CH₄ mixtures are used. For H₂/CH₄ and C₃H₈/CH₄ mixtures, emissions of unburned methane are lower, probably due to the proceeding of CH₄ homogeneous oxidation promoted by H and OH radicals generated by propane and hydrogen pyrolysis at such relatively high temperatures.

Finally, a steady state multiplicity is found by decreasing the pre-heating temperature from the ignited state. This occurrence can be successfully employed to pilot the catalytic ignition of methane at temperatures close to compressor discharge or easily achieved in regenerative burners.     

Reaction mechanism of methane activation using non-equilibrium pulsed discharge at room temperature

The reaction mechanism of methane activation using non-equilibrium pulsed discharge was largely clarified from the emission spectroscopic study and experiments with higher hydrocarbons and some kinds of isotopes. The strong emission of atomic carbon and C₂ swan band system was observed as well as H Balmer series emission. This indicates that methane was highly dissociated into C and H by electron impact, which is consistent with the result of high C₂D₂ composition in produced acetylene when the mixture of CH₄ and D₂ was fed into discharge region. High electron energy contributed to produce atomic carbon directly from methane, and high electron density promoted the dehydrogenation from CH₃, CH₂ and CH to produce atomic carbon consecutively. The reason for the high selectivity to C₂H₂ was the high concentration of CH or C₂ formed from atomic carbon, and the repetition mechanism of decomposition and recombination among C, CH, C₂ and C₂H₂.     

Selective catalytic reduction of NO by C2H2 over MoO3/HZSM-5

Molybdenum impregnated HZSM-5 zeolite catalysts with MoO₃ loading from 1 to 8 wt.% were studied in detail for the selective catalytic reduction (C₂H₂-SCR) of NO by acetylene. A 83.9% of NO could be removed by the reductant at 350 °C under 1600 ppm of NO, 800 ppm of C₂H₂ and 9.95% of O₂ in He over 2%MoO₃/HZSM-5 catalyst with a specific activity of in NO elimination and the competitiveness factor (c.f.) of 33.6% for the reductant. The NO elimination level and the c.f. value were ca. 3–4 times as high as those using methane or propene as reductant over the catalyst in the same reaction condition. About same reaction rate was estimated in NO oxidation as that in the NO reduction over each xMoO₃/HZSM-5 (x = 0–8%) catalyst, which confirms that NO₂ is a crucial intermediate for the aimed reaction over the catalysts. Appropriate amount of Mo incorporation to HZSM-5 considerably enhanced the title reaction, both by accelerating the intermediate formation and by strengthening the adsorption NO_x on the catalyst surface under the reaction conditions. Rather lower adsorption tendency of acetylene compared with propene on the catalysts explains the catalyst's steady performance in the C₂H₂-SCR of NO and rapid deactivation in the C₃H₆-SCR of NO.     

Selective oxidehydrogenation of ethane with CO2 over CeO2-based catalysts

Ceria catalysts were found active and selective to the oxidehydrogenation of ethane (ODE) with CO₂ and the actual contribution for C₂H₄ formation from heterogeneous catalysis was 75–55% in the range 953–993 K. The presence of calcium ions in solid solution in the ceria crystalline network increased significatively the selectivity to ethene and the efficiency of CO₂ as oxidant in the heterogeneous reaction.     

Cu-ZSM-5 zeolite highly active in reduction of NO with decane under water vapor presence: Comparison of decane, propane and propene by in situ FTIR

Selective catalytic reduction of NO_x (SCR-NO_x) with decane, and for comparison with propane and propene over Cu-ZSM-5 zeolite (Cu/Al 0.49, Si/Al 13.2) was investigated under presence and absence of water vapor. Decane behaves in SCR-NO_x like propene, i.e. the Cu-zeolite activity increased under increasing concentration of water vapor, as demonstrated by a shift of the NO_x–N₂ conversion to lower temperatures, in contrast to propane, where the NO_x–N₂ conversion is highly suppressed. In situ FTIR spectra of sorbed intermediates revealed similar spectral features for C₁₀H₂₂– and C₃H₆–SCR-NO_x, where –CH_x, R–NO₂, –NO₃⁻, Cu⁺–CO, –CN, –NCO and –NH species were found. On contrary, with propane –CH_x, R–NO₂, NO₃⁻, Cu⁺–CO represented prevailing species. A comparison of the in situ FTIR spectra (T–O–T and intermediate vibrations) recorded at pulses of propene and propane, moreover, under presence and absence of water vapor in the reaction mixture, revealed that the Cu²⁺–Cu⁺ redox cycle operates with the C₃H₆–SCR-NO_x reactions in both presence/absence of water vapor, while with C₃H₈–SCR-NO_x, the redox cycle is suppressed by water vapor. It is concluded that decane cracks to low-chain olefins and paraffins, the former ones, more reactive, preferably take part in SCR-NO_x. It is concluded that formation of olefinic compounds at C₁₀H₂₂–SCR-NO_x is decisive for the high activity in the presence of water vapor, while water molecules block propane activation. The increase in NO_x–N₂ conversion due to water vapor in C₁₀H₂₂–SCR-NO_x should be connected with the increased reactivity of intermediates. These are suggested to pass from R–NO_x → –CN → –NCO → NH₃; the latter reacts with another activated NO_x molecule to molecular nitrogen. The positive effect of water vapor on the NO_x–N₂ conversion is attributed to increased hydrolysis of –NCO intermediates.     

Partial oxidation of ethane to synthesis gas over Co-loaded catalysts

Attention has been increasingly paid to the partial oxidation of lower alkanes to synthesis gas, due to its intrinsic energy saving process. We studied the partial oxidation of ethane (POE) on Co loaded on various supports. The POE performance varied as follows: Y₂O₃, CeO₂, ZrO₂, La₂O₃  SiO₂, Al₂O₃, TiO₂ > MgO. Comparing Y₂O₃ and CeO₂, the carbon deposition during the POE was negligible on CeO₂ and therefore CeO₂ was the most preferable support. By changing space velocity and O₂ partial pressure, reaction mechanism of POE was studied and it was revealed that two-step mechanism was prevailing; combustion of ethane to H₂O and CO₂ and subsequent reforming of ethane with H₂O and CO₂ to synthesis gas. Co/CeO₂ catalyst exhibited high and stable catalytic activity for 10 h; high ethane conversion of 18% (maximum ethane conversion 20% at O₂/C₂H₆ = 0.2) with H₂ and CO selectivities of 93 and 84%, respectively.     

The selective oxidation of methane to ethane and ethylene in a solid oxide electrolyte reactor

A study of the selective oxidative coupling of methane (OCM) to C₂ hydrocarbons (ethane and ethylene) in a solid-state electrochemical reactor made from yttria-stabilized zirconia (YSZ) has been made. Three different catalyst–electrode systems based on silver and two trimetallic formulations of Mn modified alkali (Na and K) tungstates supported on silica were used. A comparison is made between co-fed and electrochemically-supplied oxygen. The electrochemically-supplied oxygen gave higher overall C₂ selectivities than the co-fed method under low current conditions, which was attributed to differences in local methane to oxygen ratios at the catalyst surface. The potassium tungstate supported catalyst gave the best overall C₂ selectivity (86% at 4% C₂ yield).     

Oxidative transformation of methane over nickel catalysts supported on rare-earth metal oxides

The oxidative transformation of methane over Ni catalysts supported on La, Sm and Ce oxides was investigated at atmospheric pressure, T=723–923 K and CH₄/O₂=1–10. The BET surface areas were low (3–22 m² g⁻¹) and decreased strongly after reaction (down to 0.5  m² g⁻¹). Carbonate species, Ni₂O₃ and supported oxides were identified by XRD or IR spectroscopy studies in both the fresh and used catalysts. The Ni° phase was also probably formed as amorphous phase. The oxidative coupling of methane route passed through a minimum as a function of the Ni percentage and was favored by the Ce or Sm oxide support, Li additive and low reaction temperature. High selectivities (60–90%) and good yields (about 15%) in C₂ hydrocarbons with low carbon balance (0–10%) were obtained at 823 K. La supported oxide, Ba additive and high reaction temperature favored the partial oxidation of methane. The obtained results were discussed in the light of the reducibility and acid–base properties of the catalysts.     

IR spectroscopic analysis of isotopic C2-products of the oxidative coupling of CH4+CD4mixture over manganese oxide catalyst

The composition and structure of the product of mixture CH₄+CD₄ oxidative coupling over natural manganese mineral catalyst at 3% and 25% methane conversion in redox mode at 850°C have been determined by IR-Absorption- Reflection spectroscopy technique. At low methane conversion there were ethanes: H₃OCH₃, H₃OCD₃, D₃CCD₃ and ethylenes: H₂CCH₂, H₂CCD₂, D₂CCD₂ only The data obtained showed that the reaction proceeds by gas-phase CH₃, CD₃ radicals coupling and ethane is the primary C₂-product and ethylene is produced by gas-phase conversion of ethane.     

Partial oxidation of methane to synthesis gas over iridium–nickel bimetallic catalysts

Partial oxidation of methane to synthesis gas was carried out using supported iridium–nickel bimetallic catalysts, in order to reduce loading levels of iridium and nickel, and to avoid carbon deposition on nickel-based catalysts by adding iridium. The performance of supported iridium–nickel bimetallic catalysts in synthesis gas formation depended strongly upon the support materials. La₂O₃ gave the best performance among the support materials tested. Ir(0.25 wt%)–Ni(0.5 wt%)/La₂O₃ afforded 36% conversion of methane (CH₄/O₂=5) to give CO and H₂ with the selectivities of above 90% at 800°C, and those at 600°C were 25.3% conversion of methane and CO and H₂ selectivities of about 80%, respectively. Reduced monometallic Ir(0.25 wt%)/La₂O₃ and Ni(0.5 wt%)/La₂O₃ catalysts did not produce synthesis gas at 600°C. A higher conversion of methane was obtained by synergistic effects. The product concentrations of CO, H₂, and CO₂, and CH₄ conversion were maintained in high values, even increasing the space velocity of feed gas over Ir–Ni/La₂O₃ catalyst, indicating that rapid reaction takes place. As a by-product, a small amount of carbon deposition was observed, but carbon formation decreased with increasing the space velocity. On the other hand, with reduced monometallic Ni(10 wt%)/La₂O₃ catalyst, yield of synthesis gas and carbon decreased with increasing the space velocity.     

Novel utilization of mesoporous molecular sieves as supports of cobalt catalysts in Fischer–Tropsch synthesis

Mesoporous molecular sieves (MCM-41 and SBA-15) with different pore diameters have been studied as supports of high loading of Co catalysts, and the performances in FT synthesis have been examined with a fixed bed stainless steel reactor at 2.0 MPa for the purpose of efficient production of C₁₀–C₂₀ fraction as the main component of diesel fuel. The method of exchanging template ions in uncalcined MCM-41 with Co²⁺ ions is effective for holding 10–20% Co within the mesopores while keeping the structure regularity of MCM-41 to some extent, compared with the conventional impregnation method using calcined MCM-41. At 523 K, CO conversion and selectivity to C₁₀–C₂₀ hydrocarbons are both higher at larger loading of 20% Co for the exchanged catalysts with pore diameters of 2.7–2.9 nm. When four kinds of 20% Co/SBA-15 with the diameters of 3.5–13 nm, prepared by the impregnation method using an ethanol solution of Co acetate, are used in FT synthesis at 523 K, the catalyst with the diameter of 8.3 nm shows the largest CO conversion, which is higher than those over MCM-41 supported Co catalysts. At a lower temperature of 503 K, however, the acetate-derived Co is almost inactive. In contrast, the use of Co nitrate alone or an equimolar mixture of the acetate and nitrate as Co precursor drastically enhances the reaction rate and consequently provides high space–time yield (260–270 g C/kg_cat h) of C₁₀–C₂₀ hydrocarbons. The X-ray diffraction and temperature-programmed reduction measurements show that the dependency of the catalytic performance of 20% Co/SBA-15 on its precursor originates probably from the differences in not only the reducibility of the calcined catalyst but also the dispersion of metallic Co. Catalyst characterization after FT synthesis strongly suggests the high stability of the most effective Co/SBA-15 in the dispersion and reducibility of the oxide species and in the mesoporous structure.     

Surface properties and reactivity of Cu/γ-Al2O3 catalysts for NO reduction by C3H6: Influences of calcination temperatures and additives

The influences of calcination temperatures and additives for 10 wt.% Cu/γ-Al₂O₃ catalysts on the surface properties and reactivity for NO reduction by C₃H₆ in the presence of excess oxygen were investigated. The results of XRD and XPS show that the 10 wt.% Cu/γ-Al₂O₃ catalysts calcined below 973 K possess highly dispersed surface and bulk CuO phases. The 10 wt.% Cu/γ-Al₂O₃ and 10 wt.% Mn–10 wt.% Cu/γ-Al₂O₃ catalysts calcined at 1073 K possess a CuAl₂O₄ phase with a spinel-type structure. In addition, the 10 wt.% La–10 wt.% Cu/γ-Al₂O₃ catalyst calcined at 1073 K possesses a bulk CuO phase. The result of NO reduction by C₃H₆ shows that the CuAl₂O₄ is a more active phase than the highly dispersed and bulk CuO phase. However, the 10 wt.% Mn–10 wt.% Cu/γ-Al₂O₃ catalyst calcined at 1073 K possesses significantly lower reactivity for NO reduction than the 10 wt.% Cu/γ-Al₂O₃ catalyst calcined at 1073 K, although these catalysts possess the same CuAl₂O₄ phase. The low reactivity for NO reduction for 10 wt.% Mn–10 wt.% Cu/γ-Al₂O₃ catalyst calcined at 1073 K is attributed to the formation of less active CuAl₂O₄ phase with high aggregation and preferential promotion of C₃H₆ combustion to CO_x by MnO₂. The engine dynamometer test for NO reduction shows that the C₃H₆ is a more effective reducing agent for NO reduction than the C₂H₅OH. The maximum reactivity for NO reduction by C₃H₆ is reached when the NO/C₃H₆ ratio is one.     

Catalytic performance of quaternary ammonium salts in the reaction of butyl glycidyl ether and carbon dioxide

The synthesis of cyclic carbonate from butyl glycidyl ether (BGE) and carbon dioxide was performed in the presence of quaternary ammonium salt catalysts. Quaternary ammonium salts of different alkyl group (C₃, C₄, C₆ and C₈) and anions (Cl⁻, Br⁻ and I⁻) were used for this reaction carried out in a batch autoclave reactor at 60–120 °C. The catalytic activity increased with increasing alkyl chain length in the order of C₃ < C₄ < C₆. But, the quaternary ammonium salt with longer alkyl chain length (C₈) decreased the conversion of BGE because it is too bulky to form an intermediate with BGE. For the counter anion of the tetrabutyl ammonium salt catalysts, the BGE conversion decreased in the order Cl⁻ > Br⁻ > I⁻. The effects of carbon dioxide pressure and reaction temperature on this reaction were also studied to better understand the reaction mechanism.