Comparison of Alkali Metal Promoted MgO Catalysts for Their Surface Acidity/Basicity and Catalytic Activity/Selectivity in the Oxidative Coupling of Methane

Alkali metal (viz. Li, Na, K, Rb and Cs) promoted MgO catalysts (with an alkali metal/Mg ratio of 0·1) calcined at 750°C have been compared for their surface properties (viz. surface area, morphology, acidity and acid strength distribution, basicity and base strength distribution, etc.) and catalytic activity/selectivity in the oxidative coupling of methane (OCM) to C₂-hydrocarbons at different temperatures (700–750°C), CH₄/O₂ ratios (4·0 and 8·0) in feed, and space velocities (10320 cm³ g⁻¹ h⁻¹). The surface and catalytic properties of alkali metal promoted MgO catalysts are found to be strongly influenced by the alkali metal promoter and the calcination temperature of the catalysts. A close relationship between the surface density of strong basic sites and the rate of C₂-hydrocarbons formation per unit surface area of the catalysts has been observed. Among the catalysts calcined at 750°C, the best performance in the OCM is shown by Li–MgO (at 750°C). © 1997 SCI.     

甲烷氧化偶联制乙烯工艺研究进展

甲烷氧化偶联(OCM)途径是通过一步法获取乙烯,是现有乙烯生产中最为简捷的工艺。本文综述了该工艺催化剂系统、反应机理、工艺开发研究的新进展,并探讨了OCM过程面临的关键问题有催化剂的选择、反应器和反应流程的设计和反应温度的控制。     

SrTiO3体系上甲烷氧化偶联催化性能及XPS表征

用X-光电子能谱（XPS）研究SrTiO2体系上不同Sr/Ti比、B位不同价态掺杂元素和掺杂量的催化剂组成、表面吸附氧含量与甲烷氧化偶联（OCM）催化性能.结果表明Sr/Ti比增加、B位掺杂元素（Zr,Al,Mg）价态降低和B位Mg2＋掺杂量增加会导致催化剂表面吸附氧含量的增加,并与催化剂的C2产物选择性有顺变关系,但表面吸附氧含量过高会导致甲烷的深度氧化.     

甲烷氧化偶联催化剂制备和表面性能的研究

通过对共浸渍法、层浸渍法和分浸渍法制得的甲烷氧化偶联（OCM）催化剂的比表面积（BET）和扫描电镜（SEM）表征,共浸溃法制得催化剂的比表面积最大。采用共浸渍法,制备OCM催化剂并考评,以考察制备条件对催化剂性能的影响．得后处理方法和浸渍温度是主要影响因素,BET和SEM表征结果表明：浸渍温度能调控催化剂比表面积,在50℃时制得的催化剂比表面最大,反应收率最高。     

Combined Single-Pass Conversion of Methane Via Oxidative Coupling and Dehydroaromatization

A new reaction mode, i.e., the combined single-pass conversion of methane via oxidative coupling (OCM) over mixed metal oxide (SLC) catalysts and dehydroaromatization (MDA) over Mo/HZSM-5 catalysts, is reported. With the assistance of an OCM reaction over SLC catalysts in the top layer of the reactor, the deactivation resistance of Mo/HZSM-5 catalysts is remarkably enhanced. Under the selected reaction conditions, the CH₄ conversion decreased from 18 to 1% and the aromatics yield decreased from 12.8 to 0.1%, respectively, after running the reaction for 960min on both 6Mo/HZSM-5 and SLC-6Mo/HZSM-5 catalyst system without O₂ in the feed. On the other hand, for the SLC-6Mo/HZSM-5 catalyst system with O₂ in the feed, the deactivation was improved greatly, and after 960min onstream the CH₄ conversion and aromatics yield were still as high as 12.0 and 8.0%, respectively. The promotion effect mainly appears to be associated with in situ formation of CO₂ in the OCM layer, which reacts with coke via the reverse Boudouard reaction.     

Critical Influence of Mn on Low-Temperature Catalytic Activity of Mn/Na2WO4/SiO2 Catalyst for Oxidative Coupling of Methane

Oxidative coupling of methane (OCM) was investigated in the temperature range 370-775 °C over Mn/Na₂WO₄/SiO₂ catalysts with different loadings of manganese in integral-mode conditions. Na₂WO₄/SiO₂ shows no activity at low temperature (370 °C), whereas Mn-doped catalyst exhibits 14% C²⁺ yield under similar reaction conditions, indicating that manganese plays a critical role in low-temperature methane coupling reaction. Partial pressure of oxygen in the feed also influences the low-temperature OCM activity of the catalysts.     

Combined Single-pass Conversion of Methane Via Oxidative Coupling and Dehydro-aromatization

A single-pass process with the combination of oxidative coupling (OCM) and dehydro-aromatization (MDA) for the direct conversion of methane is carried out. With the assistance of the OCM reaction over the SrO–La₂O₃/CaO catalyst loaded on top of the catalyst bed, the duration of the dehydro-aromatization reaction catalyzed by a 6Mo/HMCM-49 catalyst shows a significant improvement, and. the initial deactivation rate constant of the overall process revealed about 1.5×10⁻⁶ s⁻¹. Up to 72 h on stream, the yield of aromatics was still maintained at 5.0% with a methane conversion of 9.6%, which is obviously higher than that reported for the conventional MDA process with single catalyst. Upon the TPR results, this wonderful enhancement would be attributed to an in-situ formation of CO₂ and H₂O through the OCM reaction, which serves as a scavenger for actively removing the coke formed during the MDA reaction via a reverse Boudouard reaction and the water gas reaction as well.     

Effect of Electronic Properties of Catalysts for the Oxidative Coupling of Methane on Their Selectivity and Activity

The oxidative coupling of methane (OCM) to higher hydrocarbons may eventually become an interesting alternative for the chemical utilization of natural gas. Extensive studies have been conducted since the works of Keller and Bhasin [l] and of Hinsen and Baerns [2].     

Effect of Electronic Properties of Catalysts for the Oxidative Coupling of Methane on Their Selectivity and Activity

The oxidative coupling of methane (OCM) to higher hydrocarbons may eventually become an interesting alternative for the chemical utilization of natural gas. Extensive studies have been conducted since the works of Keller and Bhasin [l] and of Hinsen and Baerns [2].     

甲烷氧化偶联制C2烃催化剂及催化反应机理研究进展

综述了甲烧氧化偶联制乙烷、乙烯催化剂及催化机理研究概况。重点介绍1989年以来对碱及碱土金属化合物、烯土氧化物、复合氧化物等各类催化剂的研究进展。对目前催化剂上甲烷活化途径、甲基自由基在反应过程中的作用机理、不同氧化物种及表面酸、碱位与催化性能的关系等方面的研究抉况及不同观点也作了简介。     

Thermal Reaction Analysis of Oxidative Coupling of Methane

For more than three decades, the oxidative coupling of methane (OCM) process has been investigated as a promising alternative approach for ethylene production. Simulations of different sets of surface mechanisms over the Na₂WO₄/Mn/SiO₂ catalyst and the gas phase reactions that come along with the OCM reaction were analyzed in a fixed‐bed, membrane, and fluidized‐bed reactor. The results were compared with the experimental data generated in an OCM mini‐plant. It was observed that the gas phase reactions are crucial in reducing the overall selectivity, especially in the fluidized‐bed reactor.     

Autothermal Methane Oxidative Coupling Process over La2O3/MgO Catalysts

Some essential conditions necessary to reach an autothermal regime in methane oxidative coupling on La₂O₃/MgO catalysts were investigated. The following three ways can be suggested to transfer the process into the autothermal regime: (1) higher initial concentrations of reagents; (2) larger reactor diameter; (3) optimization of the flow rate and the preheating temperature. It was found that the optimal temperature of the autothermal regime of methane oxidative coupling is governed by the nature of the catalyst.     

LiCl/MnO_2-H_3BO_3体系甲烷氧化偶联催化剂的研究

由于石油资源的日见枯竭 ,天然气在化工原料中的地位日益突出。对天然气的主要成分甲烷、氧化偶联 (OCM)制备乙烯的催化剂—— Li Cl/Mn O2 - H3 BO3 进行了系统研究并探讨了其组分及外界反应条件对该催化剂性能的影响 ,发现了可能的活性组分 :立方晶型的 Li4 B7O12 Cl。     

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     

Higher Hydrocarbon Production through Oxidative Coupling of Methane Combined with Hydrogenation of Carbon Oxides

In the production of higher hydrocarbons, combining oxidative coupling of methane (OCM) with hydrogenation of the formed carbon oxides in a separate reactor provides an alternative to the currently applied methane conversion to syngas followed by Fischer‐Tropsch synthesis. The effects of CH₄:O₂ feed ratio in the OCM reactor and partial pressures of H₂ or/and H₂O in the hydrogenation reactor were analyzed to maximize production of C₂₊ hydrocarbons and reduce CO_x formation. The highest C₂₊ yield was achieved with low CH₄:O₂ feed ratio for OCM and removal of the formed water before entering the hydrogenation reactor.     

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.     

Li~+/MgO上交叉偶联作用的研究

采用Li+/MgO催化剂研究了Li含量、反应温度、原料气组成对甲烷和甲苯催化氧化交叉偶联成乙苯或苯乙烯 (即C8)反应的影响 ,对几种Li含量催化剂上各影响因素引起的差异进行了考察。结果表明 ,其活性中心也主要是Li+O- ,合适的L酸点是本交叉偶联反应中反应物的吸附中心 ,Li+O- 和L酸点是决定偶联反应产物C2 和C8的主要因素。偶联可能主要按游离基机理进行     

A Critical Assessment of Li/MgO-Based Catalysts for the Oxidative Coupling of Methane

Li/MgO is one of the most frequently investigated catalysts for the oxidative coupling of methane. Besides catalytic testing, it is also a suitable system to perform surface science experiments and quantum chemical calculations, which is not possible for many other active catalysts. However, the real structure of Li/MgO, the nature of the active center and the structure - activity relationship remain unclear, despite all the research that has been done. The aim of this review is to summarize the available knowledge on Li/MgO to structure and accelerate and improve the ongoing work on this catalytic system.     

Deactivation of NaCl/B2O3/Fe2O3 catalysts and their improvement for the oxidative coupling of methane

In the present work, the deactivation of the NaCl/B₂O₃/Fe₂O₃ catalysts was studied for the oxidative coupling of methane. Several techniques, such as XPS, XRD, SEM, H₂-TPR, and flow-reaction, were employed to examine the function of each catalyst component, and its change during the catalytic reaction. NaCl and B₂O₃ show a synergistic effect on the Fe₂O₃ surface. B₂O₃ modifies the oxidative activity of Fe₂O₃ and makes the first reduction peak of Fe₂O₃ shift from 490 to 750°C. The NaCl modified B₂O₃/Fe₂O₃ catalyst has high reduction rate, high activity and selectivity at about 750°C. It is demonstrated that the deactivation of the NaCl/B₂O₃/Fe₂O₃ catalysts is a complicated process, consisting of chloride loss, sodium change, B₂O₃ loss, silica deposition and catalyst sintering. The chloride loss enhances the surface basicity, which causes the silica deposition and sodium change, and aggravates the catalyst sintering. The silica deposition and catalyst sintering cause permanent deactivation. The B₂O₃ loss is not a direct reason for catalyst deactivation. NaCl crystal diluted NaCl/B₂O₃/Fe₂O₃ catalysts have a better stability. The deactivated catalyst has a more stable structure. When it is regenerated by impregnating with NaCl again, a more stable catalyst can be obtained.     

SrTiO3超细微粒的制备与甲烷氧化偶联催化性能

采用溶胶－凝胶法合成钙钛矿型立方相SrTiO3超细微粒,探讨了成胶温度,配体,溶剂以及干凝胶热处理条件对生成SrTiO3微粒粒度,均匀性及比表面积的影响,用TGA－DTA,IR,TEM,XRD,XPS,BET表面积测试等手段对SrTiO3超细微粒的形成机制,结构及形貌和甲烷氧化偶联催化性能进行了研究,发现SrTiO3超细微粒对于甲烷低温（~650℃）氧化偶联催化性能明显优于固相反应法制备的大粒子SrTiO3催化剂。