Influence of precursors of Li2O and MgO on surface and catalytic properties of Li‐promoted MgO in oxidative coupling of methane

The influence of the catalyst precursors (for Li₂O and MgO) used in the preparation of Li‐doped MgO (Li/Mg = 0.1) on its surface properties (viz basicity, CO₂ content and surface area) and activity/selectivity in the oxidative coupling of methane (OCM) process at 650–750 °C (CH₄/O₂ feed ratio = 3.0–8.0 and space velocity = 5140–20550 cm³ g⁻¹ h⁻¹) has been investigated. The surface and catalytic properties are found to be strongly affected by the precursor for Li₂O (viz lithium nitrate, lithium ethanoate and lithium carbonate) and MgO (viz magnesium nitrate, magnesium hydroxide prepared by different methods, magnesium carbonate, magnesium oxide and magnesium ethanoate). Among the Li–MgO (Li/MgO = 0.1) catalysts, the Li–MgO catalyst prepared using lithium carbonate and magnesium hydroxide (prepared by the precipitation from magnesium sulfate by ammonia solution) and lithium ethanoate and magnesium acetate shows high surface area and basicity, respectively. The catalysts prepared using lithium ethanoate and magnesium ethanoate, and lithium nitrate and magnesium nitrate have very high and almost no CO₂ contents, respectively. The catalysts prepared using lithium ethanoate or carbonate as precursor for Li₂O, and magnesium carbonate or ethanoate, as precursor for MgO, showed a good and comparable performance in the OCM process. The performance of the other catalysts was inferior. No direct relationship between the basicity of Li‐doped MgO or surface area and its catalytic activity/selectivity in the OCM process was, however, observed. © 2000 Society of Chemical Industry     

Surface Properties of CaO (or BaO)–La2O3–MgO Catalysts and Their Performance in Oxidative Coupling of Methane

CaO–La₂O₃–MgO and BaO–La₂O₃–MgO catalysts with different compositions have been studied for their bulk and surface properties (viz. crystal phases, surface area, acidity/acid strength distribution, basicity/base strength distribution, etc.) and catalytic activity/selectivity in the oxidative coupling of methane (OCM) at different processing conditions (reaction temperature, 700–850°C; CH₄/O₂ ratio in feed, 3·0, 4·0 and 8·0 and GHSV, 102000 and 204000 cm³ g⁻¹ h⁻¹). The surface acidity and strong basicity of La₂O₃–MgO are found to be increased due to the addition of a third component (CaO or BaO), depending upon its concentration in the catalyst. The addition of CaO or BaO to La₂O₃–MgO OCM catalyst causes a significant improvement in its performance. Both the CaO- and BaO-containing catalysts show a high activity and selectivity at 800°C, whereas, the activity and selectivity of BaO-containing catalysts at 700°C is lower than that of CaO-containing catalysts. © 1997 SCI.     

Oxidative coupling of methane to C2-hydrocarbons over lithium–cerium-promoted MgO and MgO–CaO catalysts

The oxidative coupling of methane to ethylene and ethane was studied over lithium–cerium-promoted MgO and MgO–CaO catalysts in the presence of molecular oxygen at 730°C and at atmospheric pressure in a continuous flow, fixed bed quartz reactor. The catalysts were prepared by an impregnation method and finally calcined at 900°C. The surface area, pore size distribution and pore volume of the catalysts were determined. The feed consisted of only methane and oxygen in the molar ratio of 2:1. The results obtained over the catalyst systems, viz. (i) lithium–cerium-promoted MgO and (ii) lithium–cerium-promoted MgO–CaO, have been compared. A relatively high C₂-selectivity has been obtained with Li–Ce-promoted MgO–CaO catalysts. The optimum yield and selectivity for C₂-hydrocarbons were found to be 21·5% and 76·8% respectively at a methane conversion of 28% over Li (7 wt%)–Ce (2 wt%)-doped MgO–CaO (3:1 wt ratio) catalyst. The various factors governing the activity and the selectivity of the catalyst systems have been discussed.     

Oxidative coupling of methane over Sm-promoted MgO: Influence of composition and preparation conditions

Influences of promoter concentration (or Sm/Mg ratio), precursor for MgO (viz. Mg-acetate, Mg-carbonate and Mg-hydroxide), calcination temperature of Sm-promoted MgO catalyst on the catalytic activity/selectivity in the oxidative coupling of methane (OCM) at different temperatures (650–850°C) and CH₄/O₂ ratios in feed (2·0–8·0) at a high space velocity (51600 cm³ g⁻¹ h⁻¹) have been investigated. The catalytic activity/selectivity of Sm–MgO catalysts in the OCM are found to be strongly influenced by the Sm/Mg ratio, precursor used for MgO and catalyst calcination temperature. The catalyst with Sm/Mg ratio of 0·11, prepared using magnesium acetate and magnesium carbonate as a source of MgO and calcining at 950°C, is found to be highly active and selective in the OCM process. A drastic reduction in catalytic activity/selectivity is observed when the catalyst is supported on low surface area porous catalyst carriers, indicating strong catalyst–support interactions. ©1997 SCI     

High-temperature in situ FTIR spectroscopy study of LaOF and BaF2/LaOF catalysts for methane oxidative coupling

In situ FTIR spectroscopy was used to characterize the oxygen adspecies and its reactivity with CH₄ over LaOF and 15 mol% BaF₂/LaOF catalysts at OCM temperature (750-800°C). It was found that gas-phase oxygen was activated on the surface of LaOF and 15 mol% BaF₂/LaOF, which had been pretreated under vacuum at 750 or 800°C, forming O ₂ ^- species at high temperature (750-800°C). At 750°C, the adsorbed O ₂ ^- species can react with pure CH₄ accompanied by formation of gas-phase C₂H₄ and CO₂, and there is a good correlation between the rate of disappearance of surface O₂and the rate of formation of gas-phase C₂H₄. The O ₂ ^- species was also observed over the catalysts under working condition, and it reacted with CH₄ in a manner that was consistent with its role in a catalytic cycle. These results suggest that O ₂ ^- may be the active oxygen species for OCM reaction over these catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

Oxidative coupling of methane and oxidative dehydrogenation of ethane over strontium-promoted rare earth oxide catalysts

Sr-promoted rare earth (viz. La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er and Yb) oxide catalysts (Sr/rare earth ratio = 0·1) are compared for their performance in the oxidative coupling of methane (OCM) to C₂ hydrocarbons and oxidative dehydrogenation of ethane (ODE) to ethylene at different temperatures (700 and 800°C) and CH₄ (or C₂H₆)/O₂ ratios (4–8), at low contact time (space velocity = 102000 cm³ g⁻¹ h⁻¹). For the OCM process, the Sr–La₂O₃ catalyst shows the best performance. The Sr-promoted Nd₂O₃, Sm₂O₃, Eu₂O₃ and Er₂O₃ catalysts also show good methane conversion and selectivity for C₂ hydrocarbons but the Sr–CeO₂ and Sr–Dy₂O₃ catalysts show very poor performance. However, for the ODE process, the best performance is shown by the Sr–Nd₂O₃ catalyst. The other catalysts also show good ethane conversion and selectivity for ethylene; their performance is comparable at higher temperatures (≥800°C), but at lower temperature (700°C) the Sr–CeO₂ and Sr–Pr₆O₁₁ catalysts show poor selectivity. © 1998 SCI.     

The effect of Nb2O5 and ZrO2 additions on the behaviour of Li/MgO and Li/Na/MgO catalysts for the oxidative coupling of methane

Incorporation of Nb₂O₅ or ZrO₂ into both Li/MgO and Li/Na/MgO systems produced ternary and quaternary catalysts, respectively, capable of attaining optimal C₂ yields and selectivities at lower temperatures relative to the unpromoted materials. The degree of enhancement effected by these metal oxide additives was compared to that produced by Li/MgO and Li/Na/MgO catalysts promoted with SnO₂ or Co₃O₄. At reaction temperatures < 700°C, the Li/Co/MgO ternary system showed marked differences in behaviour compared to the other ternary catalysts tested. This was particularly evident in the variation in C₂ selectivity with time on stream during ageing studies of (i) untreated materials, (ii) materials pretreated in CO₂, and (iii) materials dosed periodically with CHCI₃.     

Effect of MgO calcination temperature on the reaction products and kinetics of MgO–SiO2–H2O system

MgO-based binders have been widely studied for decades. Recently, the MgO–SiO₂–H₂O system was developed as a novel construction material, however, its reaction mechanism remains unclear. This paper investigated the reaction products and kinetics of MgO/silica fume (SF) pastes with MgO calcinated at different temperatures. The results indicate that MgO presented larger grain size after calcination at higher temperature. Mg(OH)₂ and magnesium silicate hydrate (M–S–H) gel were formed when using MgO calcined at 850, 950, and 1050°C. However, only M–S–H gel was formed when using MgO calcined at 1450°C. The reaction kinetics of MgO could be described using α = 1 − e^−k*t. The reaction rate of MgO increased with decreasing calcination temperature, increasing SF dosage, and the addition of sodium hexametaphosphate. Only M–S–H gel was formed when the reaction rate of MgO was below the demarcation line (about 0.250 × 10⁻⁶ s⁻¹), and the corresponding demarcation area was around 14 days.     

Synthesis and characterization of new Mg–O–F system and its application as catalytic support

The Mg–O–F system (MgF₂–MgO) with different contents of MgF₂ (100–0%) and MgO is tested as support of iridium catalysts in the hydrogenation of toluene as a function of the MgF₂/MgO ratio. Mg–O–F samples have been prepared by the reaction of magnesium carbonate with hydrofluoric acid. The MgF₂–MgO supports, after calcination at 500 °C, are classified as mesoporous of surface area (34–135 m²·g^− 1) depending on the amount of MgO introduced. The Ir/Mg–O–F catalysts have been tested in the hydrogenation of toluene. The highest activity, expressed as TOF, min^− 1, was obtained for the catalyst supported on Mg–O–F containing 75 mol%MgF₂.     

Simultaneous oxidative conversion and CO2 or steam reforming of methane to syngas over CoO–NiO–MgO catalyst

CO₂ reforming, oxidative conversion and simultaneous oxidative conversion and CO₂ or steam reforming of methane to syngas (CO and H₂) over NiO–CoO–MgO (Co: Ni: Mg=0·5: 0·5:1·0) solid solution at 700–850°C and high space velocity (5·1×10⁵ cm³ g⁻¹ h⁻¹ for oxidative conversion and 4·5×10⁴ cm³ g⁻¹ h⁻¹ for oxy-steam or oxy-CO₂ reforming) for different CH₄/O₂ (1·8–8·0) and CH₄/CO₂ or H₂O (1·5–8·4) ratios have been thoroughly investigated. Because of the replacement of 50 mol% of the NiO by CoO in NiO–MgO (Ni/Mg=1·0), the performance of the catalyst in the methane to syngas conversion process is improved; the carbon formation on the catalyst is drastically reduced. The CoO–NiO–MgO catalyst shows high methane conversion activity (methane conversion >80%) and high selectivity for both CO and H₂ in the oxy-CO₂ reforming and oxy-steam reforming processes at ⩾800°C. The oxy-steam or CO₂ reforming process involves the coupling of the exothermic oxidative conversion and endothermic CO₂ or steam reforming reactions, making these processes highly energy efficient and also safe to operate. These processes can be made thermoneutral or mildly exothermic or mildly endothermic by manipulating the process conditions (viz. temperature and/or CH₄/O₂ ratio in the feed). © 1998 Society of Chemistry Industry     

Synthesis of Biodiesel from Canola Oil Using Heterogeneous Base Catalyst

A series of alkali metal (Li, Na, K) promoted alkali earth oxides (CaO, BaO, MgO), as well as K₂CO₃ supported on alumina (Al₂O₃), were prepared and used as catalysts for transesterification of canola oil with methanol. Four catalysts such as K₂CO₃/Al₂O₃ and alkali metal (Li, Na, K) promoted BaO were effective for transesterification with >85 wt% of methyl esters. ICP-MS analysis revealed that leaching of barium in ester phase was too high (~1,000 ppm) when BaO based catalysts were used. As barium is highly toxic, these catalysts were not used further for transesterification of canola oil. Optimization of reaction conditions such as molar ratio of alcohol to oil (6:1–12:1), reaction temperature (40–60 °C) and catalyst loading (1–3 wt%) was performed for most efficient and environmentally friendly K₂CO₃/Al₂O₃ catalyst to maximize ester yield using response surface methodology (RSM). The RSM suggested that a molar ratio of alcohol to oil 11.48:1, a reaction temperature of 60 °C, and catalyst loading 3.16 wt% were optimum for the production of ester from canola oil. The predicted value of ester yield was 96.3 wt% in 2 h, which was in agreement with the experimental results within 1.28%.     

Properties of Magnesium Oxo-Fluoride Supports for Metal Catalysts

A mixed MgF₂–MgO system has been tested as a potential support of iridium catalysts in the hydrodesulfurization of thiophene. Samples of MgF₂–MgO with different contents of MgO (0–100%) have been prepared by one-step sol–gel method in the reaction of magnesium methoxide dissolved in methanol with hydrofluoric acid. They have been used as supports for the synthesis of iridium (1 wt% Ir) catalysts. The supports have been characterized by XRD, low temperature nitrogen adsorption and thermogravimetric measurements. The one-step method of MgF₂–MgO synthesis has been shown to permit the control of MgO content in the mixed system. The MgF₂–MgO samples are classified as mesoporous, of large surface area (100–450 m² g^?1) depending on the amount of MgO introduced, with the maximum for 71 mol% MgO. The presence of two phases in the mixture delays the process of both MgF₂ and MgO crystallization and increases the resistance of the MgF₂–MgO texture to treatment at temperatures up to 800 °C. The catalysts obtained by deposition of the iridium phase on MgF₂, MgO and MgF₂–MgO (62 mol% MgO) calcined at 400–700 °C, have been tested in the reaction of hydrodesulfurization of thiophene. The most active has been the iridium catalyst supported on MgF₂–MgO.     

The effect of the calcination temperature of LaFeO3 precursors on the properties and catalytic activity of perovskite in methane oxidation

In the synthesis of perovskite-type LaFeO₃ oxides iron and lanthanum nitrates were used as a precursors. The nitrates were dissolved in water, evaporated, crushed and calcined in temperature range of 650–850?°C. The obtained perovskites were applied as an active layer on monolithic catalysts for the oxidation of methane. The increase in the calcination temperature of the perovskite precursors from 650° to 850°C results in a reduction in the surface area of the powders from 10.1 to 4.2?m²/g. XRD studies revealed that calcination at 800–850?°C caused the formation of an almost homogeneous LaFeO₃ perovskite phase. A decrease in the La/Fe surface ratio from 12 to 5.2 with the rise in calcination temperature from 650° to 800°C was detected by XPS. EDX results confirmed that at 750–850?°C, the La/Fe ratio in the perovskite layer is close to the stoichiometric and amount to 1.01–1.03. The highest activity in methane oxidation was achieved when the LaFeO₃ perovskite was calcined at 700?°C. A further slight increase in the activity was noticed after H₂ treatment. As the calcination temperature of the perovskites is increased, the catalyst activity decreases due to a reduction in the specific surface area, despite the more complete LaFeO₃ perovskite phase formation.     

Coating metal oxide particles via the combustion of deposited polymer precursors

Water-swellable chelated polymers were synthesized, starting either from (1) In(III) or In(III) and Sn(II) as central ions and N-trimethoxysilylpropylethylenediamine or ethylenediamine each together with ethylenediaminetetraacetic acid (EDTA) as coordination ligands, or from (2) Ag(I) as the central ion and ethylene glycol (EG) and EDTA as coordination ligands, as follows: The nitrate(s) of the above metal ions together with the corresponding ligands were dissolved in water, and the solution was concentrated by heating to carry out the chelating polymerization. After cooling, the polymer was dried and ground to a fine powder, which was then mixed with a metal oxide powder by grinding in the presence of a small amount of water. A paste was thus obtained, which, after drying, was calcined at 200°C and subsequently at 750°C. The polymer became a sticky gel at 200°C, which adhered to the surface of the metal oxide particles; it was converted to an inorganic coating, In₂O₃—SnO₂—SiO₂, In₂O₃—SnO₂, SnO₂, or Ag, during the subsequent calcination at 750°C. Two metal oxide powders, namely, the electrically conductive In₂O₃ and the nonconductive SnO₂, were used as substrates. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) indicated that the substrate particles were coated after calcination by a multicomponent oxide or silver layer. Temperature-resistant electrically antistatic film could be prepared by using the metal oxide coated In₂O₃ particles as pigments and polypropylsiloxane as the binder. The Ag-coated SnO₂ powder had a conductivity σ = 1.0 × 10⁻³ S cm⁻¹ at 8.6 vol % Ag, while the mechanically mixed powders of Ag and SnO₂ exhibited a conductivity of 2.0 × 10⁻⁷ S cm⁻¹ at 16 vol %. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1891–1903, 1998     

Visible light-irradiated degradation of alachlor on Fe-TiO<Subscript>2</Subscript> with assistance of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

0.1 Fe/Ti mole ratio of Fe-TiO₂ catalysts were synthesized via solvothermal method and calcined at various temperatures: 300, 400, and 500 °C. The calcined catalysts were characterized by XRD, N₂-adsorption-desorption, UV-DRS, XRF, and Zeta potential and tested for photocatalytic degradation of alachlor under visible light. The calcined catalysts consisted only of anatase phase. The BET specific surface area decreased with the calcination temperatures. The doping Fe ion induced a red shift of absorption capacity from UV to the visible region. The Fe-TiO₂ calcined at 400 °C showed the highest photocatalytic activity on degradation of alachlor with assistance of 30 mM H₂O₂ at pH 3 under visible light irradiation. The degradation fitted well with Langmuir-Hinshelwood model that gave adsorption coefficient and the reaction rate constant of 0.683 L mg⁻¹ and 0.136 mg/L·min, respectively.     

Influence of support on surface basicity and catalytic activity in oxidative coupling of methane of Li–MgO deposited on different commercial catalyst carriers

Deposition of Li–MgO catalyst on commonly used supports (containing SiO₂, Al₂O₃, SiC, ZrO₂, HfO₂, etc.) causes a drastic reduction in the catalytic activity/selectivity for the oxidative methane coupling reaction and also in both the total and strong surface basicity. The decrease in the catalytic activity/selectivity and basicity is attributed to strong chemical interactions between the catalyst and support which occur during the high temperature (750°C) calcination/pretreatment of the catalyst. The chemical interactions result in catalytically less active binary and ternary metal oxides containing Li and/or Mg, thus deactivating the Li–MgO catalyst by consuming its active components. © 1998 SCI     

A new nano‐(2Li2O/MgO) catalyst/porous alpha‐alumina composite for the oxidative coupling of methane reaction

The present work discloses a new methodology for the production of detached nanorods of 2Li₂O/MgO catalyst particles on the internal surface of α‐Al₂O₃ porous supports to be used as efficient catalysts for the oxidative coupling of methane reaction (OCM). The peculiarity of our preparatory recipe is the success in producing “detached” nanosized entities on the support surface. The performance of the new catalyst/support system for the OCM reaction has been evaluated using a special reactor assembly with cross flow of methane and oxygen gas streams. Under the optimum process conditions, the yield of C product is 25% at an average reaction temperature of 750°C. Under the optimum conditions, the yield of ethylene reaches 8%. It is shown that the enhanced catalytic properties of the new catalyst/support composite may be attributed to nanoeffects. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

福建无烟煤CO2气化过程纸浆黑液和钙混合物的催化活性

CO2 gasification of Fuijian high-metamorphous anthracite with black liquor （BL） and/or mixture of BL and calcium stuff （BL＋Ca） as catalyst was studied by using a thermogravimetry under 750-950℃ at ambient pressure. When the coal was impregnated with an appropriate quantity of Ca and BL mixture, the catalytic activity of CO2 gasification was enhanced obviously. With a loading of 8%Na-BL＋2%Ca, the carbon conversion of three coal samples tested reaches up to 92.9%-99.3% at 950℃ within 30min. The continuous formation of alkali surface compounds such as （[-COM], [-CO2M]） and the presence of exchanged Ca, such as calcium phenolate and calcium carboxylates （COO）2Ca, contribute to the increase in catalytic efficiency, and using BL＋Ca is more efficient than that adding BL only, The homogeneous model and shrinking-core model were applied to correlate the data of conversion with time and to estimate the reaction rate constants under different temperature. The corresponding reaction activation energy （Ea） and pre-exponential factor of three anthracites were estimated. It is found that Ea is in the range from 73.6 to 121.4kJ·mol^-1 in the case of BL＋Ca, and 74.3 to 104.2kJ·mol^-1 when only BL was used as the catalyst, both of which are much less than that from 143.5 to 181.4kJ·mol^-1 if no catalyst used. It is clearly demonstrated that both of BL＋Ca mixture and BL could be the source of cheap and effective catalyst for coal gasification.     

Sol–gel synthesis of Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte

The effect of calcination on Li ion conductivity of Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) solid electrolyte prepared by a sol–gel method is examined. The Li ion conductivity of LAGP increases with calcination temperature. After reaching maximum conductivity at 850 °C, the conductivity decreases with increase of the calcination temperature. The calcination holding time also strongly affects Li ion conductivity of LAGP. The conductivity increases with holding time until 12 h and then decreases. It is found that the control of crystallization rate is critical to obtain bulk LAGP with high Li ion conductivity. The highest bulk and total conductivities at 30 °C are 9.5×10⁻⁴ and 1.8×10⁻⁴ S cm⁻¹, respectively, obtained for the bulk LAGP calcined at 850 °C for 12 h.     

Corrosive and mechanical resistance of MgO ceramics under metallizing and mild chlorination of spent nuclear fuel in molten salts

The present work is aimed at the study of the unirradiated and irradiated MgO ceramics corrosion and mechanical properties in the molten LiCl at 650–750 °C with addition of UCl₃ and Li₂O(LiCl + nLi₂O and LiCl + mUCl₃ molten salts with n = 1.0 and 2.0 mol. % and m = 0.25, 0.5 and 1.0 mol. %). MgO ceramics is suggested to be used as one of materials for pyrochemical technology for recycling of spent nuclear fuel.The gravimetric method with the exposure time during 100 h was the primary method of investigation. The investigation of surface and bulk corrosion of MgO samples by scanning electron microscopy (SEM) and X-ray spectroscopy (MRSA) was performed using scanning electron microscope equipped with a x-Act 6 energy-dispersive analytic system for X-rays characteristic (XRС). Determination of corrosion losses and average corrosion rates of MgO samples was based on the assumption that the ejection of the radionuclides ⁹⁵Zr, ¹⁷⁵Hf and ¹⁸¹Hf from the MgO samples.Incorporation of Li₂O and UCl₃ in molten LiCl result in increase in the rate of MgO ceramic corrosion both at 650 °C and 750 °C and acts on MgO compressive strength (σ_cs) and on the elemental composition of MgO surface layers. Besides the increasing of UCl₃ concentration led to the bulk corrosion of MgO sample grains.Short-term mechanical tests demonstrated the transition of MgO sample destruction pattern depending on the concentration of Li₂O and UCl₃ additions in LiCl melt.Doping of molten LiCl by 0.5 mol. % of UCl₃ at 650 °C and by 0.25 mol. % of UCl₃ at 750 °C had no influence on the ultimate compression strength of irradiated and unirradiated MgO samples. Increased UCl₃ concentration totaling 0.5 mol. % in the LiCl melts at 750 °C reduced the ultimate compression strength of irradiated MgO ceramic samples by ~15%.