Influence of alkali metal doping on surface properties and catalytic activity/selectivity of CaO catalysts in oxidative coupling of methane

Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidative coupling of methane （OCM） to higher hydrocarbons at different reaction conditions （viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1） have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties （viz. surface area, basicity/base strength distribution） and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity （strong basic sites） and the C2＋ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO （Na/Ca = 0.1, before calcination） catalyst （calcined at 750 ℃）, showed best performance （C2＋ selectivity of 68.8% with 24.7% methane conversion）, whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.     

Energochemical technologies: energy and bulk/basic chemicals in a single process

The exoergic reactions, which underlie the production of large-scale basic chemicals for organic industry, can be used for one-pot generation of energy and chemical products. Typical examples include methane oxidative conversion to produce synthesis gas and methane oxidative dimerization to give ethylene and ethane.     

Characterization and catalytic behavior of Na-W-Mn-Zr-S-P/SiO2 prepared by different methods in oxidative coupling of methane

Na-W-Mn-Zr-S-P/SiO2 catalysts for oxidative coupling of methane (OCM) were prepared by incipient wetness impregnation, sol-gel and mixture slurry methods. The catalyst prepared by mixture slurry method showed the best catalytic performance among all samples. In addition, the effects of different addition sequences of Na, W, Mn, Zr, S and P on the catalytic performance were studied. The absence of Na before the addition of Mn and Zr in the catalysts preparation depressed the formation of the active phases of Mn2O3 and ZrO2 and decreased the activities of the catalysts significantly.     

Studies on the structure and catalytic performance of S and P promoted Na-W-Mn-Zr/SiO2 catalyst for oxidative coupling of methane

A series of Na-W-Mn-Zr/SiO2 catalysts promoted by different contents of S or/and P were prepared and their catalytic performance for oxidative coupling of methane was investigated to clarify the effect of S and P on the Na-W-Mn-Zr/SiO2 catalyst. The catalysts were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). From the characterization results, it is found that the addition of S and P to the Na-W-Mn-Zr/SiO2 catalyst helps the formation of active phases, such as α-cristo...     

Concerning the dependence of the selectivity of the formation of ethane and ethylene on the degree of methane conversion during its oxidative coupling

The dependences of the maximum selectivity and the limiting yield of C₂ hydrocarbons on the degree of methane conversion during its gas-phase oxidative coupling were calculated by means of kinetic simulation. The correlation between the results of the calculations and the rersults obtained in the experimental studies dealing with catalytic oxidative coupling of methane is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 568–570, March, 1995.     

Effect of group VIII elements on the behavior of Li/CaO catalyst in the oxidative dehydrogenation of ethane

The effect of addition of group VIII elements to Li/CaO on the oxidative dehydrogenation of ethane has been investigated in the range of 550–650°c. Iron, cobalt and nickel promote the reaction. The experiments show that iron and cobalt additives in Li/CaO catalysts mainly increase the catalytic activity. Li/Ni/CaO catalyst gives a high ethane conversion and excellent ethylene selectivity. The results on the catalyst are probably due to coordinative interaction between lithium and nickel. The characteristics of the catalysts revealed by XRD also give evidence that the promotion for both catalytic activity and ethylene selectivity is directly related to the formation of favorable crystal phases.     

CeO2、CaO助剂对甲烷部分氧化制合成气Ni/MgOAl2O3催化剂结构和性能的影响

采用BET、H2 TPR、XRD、TEM和活性评价等表征手段，考察了CeO2、CaO助剂对Ni/MgOAl2O3催化剂物化性质和甲烷部分氧化制合成气反应性能的影响。实验结果表明，单独加入CeO2或CaO助剂可以改善Ni/ MgOAl2O3催化剂中镍物种的还原性能，以CaO尤为明显；CaO作为结构助剂可以降低还原态催化剂中的镍晶粒尺寸，使改性的催化剂具有较好的活性，而CeO2对催化剂的活性未产生显著影响。当CeO2与CaO两种助剂同时对Ni/MgOAl2O3进行改性时，虽然催化剂中镍物种的还原性能没有发生明显变化，但仍具有很好的反应性能，这与CeO2与CaO能够形成CaO-CeO2固溶体有关。CaO-CeO2固溶体不仅与镍物种间存在相互作用，提高了镍物种的分散度、减小了镍晶粒尺寸，还可以提高催化剂的储氧能力和晶格氧的流动性，从而有利于改善其甲烷部分氧化反应性能。     

Li/MgO catalysts. III. Effect of precursor salts on the catalytic activity in methane oxidative coupling

Oxidative coupling of methane has been studied on Li/MgO catalysts prepared from three different MgO precursors and from lithium carbonate or nitrate. In samples prepared from Li₂CO₃, the persistence of this on the support surface favors formation of carbon oxides.

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Li/MgO, MgO . , Li₂CO₃, .

     

Control of the directions of oxidative transformation of methane over nickel-based catalysts by acid-base properties

Two completely different directions of the oxidative transformation of methane (OTM) were performed on nickel-based catalysts due to the different acid-base properties of those catalysts. The relatively acidic LaNiO_x and LiNiLaO_x/Al₂O₃ catalysts exhibit excellent Partial Oxidation of Methane to Syngas (POM) performance. However, the relatively basic LiNiLaO_x catalyst has a good Oxidative Coupling of Methane to C₂ Hydrocarbons (OCM) activity. The basic properties of the catalyst makes it difficult to reduce nickel and keeps it in the oxidized state. Reduced nickel is necessary for POM and oxidized nickel for the OCM reaction.     

La2Zr2O7催化剂结构相变对甲烷氧化偶联反应性能的影响

采用共沉淀法并通过改变焙烧温度制备了一系列具有不同晶相结构的La₂Zr₂O₇催化剂，在微型固定床反应器上评价其甲烷氧化偶联反应性能，并利用XRD、Raman、CO₂-TPD、XPS等表征手段，探究催化剂的物相结构、表面碱性以及表面氧物种的变化规律。结果表明，随着焙烧温度从700℃逐渐升高到1200℃，La₂Zr₂O₇催化剂结晶度不断提高，晶相发生明显变化，从无定形结构逐渐向缺陷萤石结构过渡，最终转变成烧绿石结构。焙烧温度提高促使La₂Zr₂O₇晶相转变过程中，催化剂表面的碱性强度减弱，中等碱性位数量以及具有催化活性的表面氧物种O₂^2-和O₂^-的相对含量不断减少，致使催化剂的CH₄转化率和C₂₊选择性不断降低。其中，无定形LZO-CP-700催化剂表现出最佳的甲烷氧化偶联反应性能。     

Formation of hydrogen in oxidative coupling of methane over BaCO3 and MgO catalysts

Hydrogen formed in oxidative coupling of methane （OCM） over BaCO3 and MgO catalysts was measured since the data of H2 selectivity were missing almost in all articles published heretofore. It was found that H2 selectivity achieved about 18%, when C2 hydrocarbon＇s selectivity was maintained at 48%-45% over BaCO3 catalyst at the feed molar ratio of CH4/O2 = 4 in temperature range of 780 °C-820 °C. Under similar conditions, H2 selectivity was about 14%-16% over MgO catalyst, with C2 selectivity maintained at 41%-42%. Possible routes for hydrogen formation in OCM reaction were discussed. Effect of addition of alkali metallic ions was also investigated.     

Interaction of Methane and Oxygen with the Surface of Manganese Oxide-Containing Catalysts

We used pulsed reduction and temperature programmed oxidation to study the interaction of methane and oxygen with the surface of manganese oxide-containing catalysts. We hypothesized that during oxidative dimerization of methane, the phase supplying strongly bound oxygen for selective methane coupling is an acceptor for weakly bound oxygen of the phase catalyzing exhaustive oxidation.     

Effect of CeO2 and CaO Promoters on Ignition Performance for Partial Oxidation of Methane over Ni/MgO-Al2O3 Catalyst

The effect of CeO2 and CaO promoters on the ignition performance over Ni/MgO-Al2O3 catalyst for the partial oxidation of methane （POM） to synthesis gas was investigated. It was found that the POM reaction could not be ignited over lwt%Ni/MgO-Al2O3 catalyst without the promoters in the temperature range from 773 K to 1073 K. CeO2 and CaO promoters enhanced the ignition performance and the POM reactivity of lwt%Ni/MgO-Al2O3 catalyst remarkably. Moreover, the improving effect became greater with the increase of the promoter content under the investigated reactiorrconditions. The modification effects of CeO2 and CaO promoters were closely related to the concentration and reducibility of the surface and bulk oxygen species.     

Kinetic studies of the oxidative coupling of methane over the Mn/Na2WO4/SiO2 catalyst

Oxidative coupling of methane is a direct way to obtain C2 hydrocarbon,and Mn-Na-W/SiO2 catalyst is the most promising among all the catalysts.The 2%Mn/5%Na2WO4/SiO2 catalyst was prepared by the incipient wetness impregnation method.A 7-step heterogeneous reaction model of the oxidative coupling of methane to C2 hydrocarbons was conducted by co-feeding methane and oxygen at a total pressure of 1 bar over the catalyst.The kinetic measurements were carried out in a micro-catalytic fixed bed reactor.The kinetic data were obtained at the appropriate range of reaction conditions (4 kPa＜Po2 ＜20 kPa,20 kPa＜PCZH4 ＜80 kPa,800℃＜T＜900℃).The proposed reaction kinetic scheme consists of three primary and four consecutive reaction steps.The conversions of hydrocarbons and carbon oxides were evaluated by applying Langrnuir-Hinshelwood type rate equations.Power-law rate equation was applied only for the water-gas shift reaction.In addition,the effects of operating conditions on the reaction rate were studied.The proposed kinetic model can predict the conversion of methane and oxygen as well as the yield of C2 hydrocarbons and carbon oxides with an average accuracy of ±15%.     

Influence of the composition of perovskites based on SrMnO<Subscript>3</Subscript> on their catalytic properties in the oxidative coupling of methane

The oxidative coupling of methane (OCM) in a periodic regime over the SrMnO₃ and its derivatives has been investigated. It has been established that partial replacement of the strontium ion by alkali metal ions leads to an increase in both catalytic activity and in selectivity with respect to higher hydrocarbons. Comparison of the results obtained in the present work with those obtained earlier for catalysts based on SrCoO₃ led to the conclusion that the Co-containing catalysts were preferable to the Mn-containing catalysts for carrying out oxidative coupling of methane in a periodic regime.__________Translated from Teoreticheskaya i Éksperimentalnaya Khimiya, Vol. 41, No. 1, pp. 30–34, January–February, 2005.     

镧、锆改性的氧化铝载体对钯催化氧化甲烷活性的影响

研究了镧、锆改性的氧化铝载体对钯催化氧化甲烷活性的影响,结果表明,nLa∶nZr=2∶1时,所得的改性氧化铝载体在1 050℃焙烧后具有较大的比表面积和孔容;nLa∶nZr=1∶2时,所得的改性氧化铝载体经过1 050℃焙烧后具有较大的储氧量;Pd/Al2O3高温下的烧结情况较为严重,而加入La与Zr后烧结现象得到明显改善;改性后的Pd/La0.13Zr0.065-Al对甲烷氧化的活性最高,Pd/La0.065Zr0.13-Al次之,未改性的Pd/Al2O3活性最低.     

Suppressed formation of CO2 and H2O in the oxidative coupling of methane over La2O3/MgO catalyst by surface modification

Oxidative coupling of methane (OCM) is a promising way to convert methane into C_2 hydrocarbons. However, CO_2 and H_2O are by-products of the reaction. To utilize the higher activity of lanthanum oxide and save its usage, MgO supported La_2O_3 catalyst was prepared. Surface modification of the catalyst with nitric acid was made to suppress the formation of the by-products. Experimental results indicated that the addition of nitric acid increased the surface oxygen species with binding energy of ca. 531.7 eV and at the same time reduced the pore volume of the catalyst. These effects of nitric acid finally led to the increase of C_2 selectivity and the decrease of the by-products formation. Hydrogen selectivity was found about 14%- 18% over the catalysts adopted in this work.     

Oxidative coupling of methane over La-promoted CaO catalysts： Influence of precursors and catalyst preparation method

The oxidative coupling of methane to C2 hydrocarbons has been studied over a series of La-promoted CaO (La/Ca = 0.05) catalysts, prepared using different precursor salts for CaO and La2O3 (viz. acetates, carbonates, nitrates and hydroxides) and catalyst preparation methods (viz. physical mixing of precursors, co-precipitation using ammonium carbonate/sodium carbonate as a precipitating agent), under different reaction conditions (temperature: 700-850℃, CH4/O2 ratio: 4.0 and 8.0, and GHSV: 51360 cm3 g-1 h-1)...     

Product oriented oxidative bromination of methane over Rh/SiO2 catalysts

Rh/SiO2 was prepared for the oxidative bromination of methane. The catalyst was prepared by calcination at different temperatures and for different times to obtain catalysts with different specific surface areas for the purposes of producing either CH3Br or CH3Br and CO. It was found that the catalyst having a low specific surface area (calcined at relatively high temperature) favors the selective oxidation of methane to prepare CH3Br, while the catalyst having a high specific surface area favors the deeper partial oxidation of methane, which is good for CH3Br and CO preparation. The 650 h on stream life-time test revealed that the catalytic performance of the 0.4Rh/SiO2--900-10 catalyst was excellent. Both methane conversion and CH3Br selectivity kept increasing trends during the life-time test. No matter how serious was the Rh leaching during the reaction, the 0.4Rh/SiO2--900-10 catalyst did not deactivate at all.