Partial oxidation of methane to syngas in a mixed-conducting oxygen permeable membrane reactor

Mixed-conducting oxygen permeable membranes represent a class of novel ceramic membranes, which exhibit mixed oxygen ionic and electronic conductivities. At high temperatures, oxygen can permeate through the membrane from the high to low oxygen pressure side under an oxygen concentration gradient. Theoretically, the permselectivity of oxygen is 100%. Recently, a novel mixed-conducting membrane—Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ has been developed, which shows extremely high oxygen permeability and promising stability. Furthermore, the reactor made with such membranes was successfully applied to the partial oxidation of methane to syngas reaction using air as the oxygen source, which realized the coupling of the separation of oxygen from air and the partial oxidation of membrane reaction in one process. At 850°C, methane conversion > 88%, CO selectivity > 97% and oxygen permeation rate of about 7.8 mL/(cm² · min) were obtained.     

透氧膜反应器内NiO/MgO催化甲烷重整反应的途径

在透氧膜反应器内对比分析了不加催化剂和添加 1 g 9% Ni/γ -Al2O3 催化剂的甲烷重整反应实验. 结果表明, 不加催化剂时甲烷相对较惰性; 而在催化剂的作用下, 甲烷重整活性得到了较大提高, 但是催化剂易积碳. 推测甲烷重整反应路径如下: 甲烷在催化剂活性组分上发生裂解, 产生氢和碳; 生成的氢与膜表面的氧反应生成 H₂O,从而使得膜表面侧氧分压下降, 透氧量增大. 通过设计不同 Ni 含量 NiO/MgO 催化剂下的甲烷裂解和甲烷重整反应实验, 验证了以上的反应机理模型.     

甲烷氧化偶联催化剂和部分氧化反应机理的原位及非原位谱学表征

采用原痊红外和原位显微Raman光谱技术及XPS、吡啶（Py)吸附的漫反射UV谱、Py-TPD、CO2-TPD等方法对含氟稀土基催化剂上甲烷氧化偶联（OCM）反应活性氧物种、催化剂表面酸碱性进行了考察。在O2预处理和/或工作条件下的SrF2/La2O3,SrF2/Nd2O3,LaOF,BaF2/LaOF和BaF2/CeO2等催化剂上原位观测到超氧物种（O2^-),并在其中前4种催化剂上检测到O2^-物种与CH4反应生成的气相C2H4,CO2和表面碳酸盐等OCM反应主、副产物。这些结果为O2^-是相应催化剂上OCM反应的活性氧物种首次提供了直接的光谱证据。研究结果表明,催化剂的OCM反应性能与其表面酸碱性的强弱并无简单的对应关系。采用原拉时间分辨红外光谱和原位显微Raman光谱技术对SiO2和γ-Al2O3负载的Rh、Ru催化剂上甲烷部分氧化（POM）制合成气反应的研究表明,由CH4直接氧化生成CO和H2是Rh/SiO2上POM反应的主要途径,而燃烧-重整机理是Ru/γ-Al2O3和Ru/SiO2上CO和H2生成的主要途径,反应条件下催化剂表面氧（O^2-)物种浓度的差异很可能是导致这两种催化剂体系上POM反应机理不同的主要原因,其本质可能源于Rh和Ru对氧的亲合力的不同。     

硅气凝胶制备及其作为催化剂载体在甲烷部分氧化反应中的应用

采用超临界干燥(SCD)法和以溶剂置换、表面改性为基础的常压干燥(APD)法分别制得二氧化硅气凝胶.采用N2低温物理吸附脱附法、红外光谱(FT-IR)、X射线衍射(XRD)实验和扫描电子显微镜(SEM)等手段对两种方法制备的气凝胶的理化性能进行了表征.结果表明:SCD法和APD法制备的二氧化硅气凝胶的比表面积分别为1 016和846 m2/g,最可几孔径分别位于孔径大小14.5和11.5 nm处.SCD法制备的二氧化硅气凝胶的孔径分布范围和较大孔的数量均较APD法制备的要宽和多.而以两种方法制备的二氧化硅气凝胶为载体,硝酸镍为镍源,采用浸渍法制备的二氧化硅气凝胶负载镍催化剂中,镍均以极微小的颗粒形式高度分散于二氧化硅气凝胶载体上.对甲烷部分氧化(POM)制合成气反应,用两种方法(SCD和APD)制备的二氧化硅气凝胶载体为基础的负载镍催化剂对产物一氧化碳和氢气的选择性相差不大,但甲烷转化率则呈现明显的差异.     

钴镁固溶体催化剂在混合导体透氧膜反应器中的应用

考察了CoO/MgO 固溶体催化剂在BaCo_0.7Fe_0.2Nb_0.1O_3−σ(BCFNO)透氧膜反应器内, 对焦炉煤气(coke oven gas, COG)中甲烷部分氧化重整(partial oxidation of methane, POM)的催化性能. 首先, 研究了CoO/MgO固溶体催化剂合成的工艺条件; 然后, 考察了焦炉煤气流量和空气流量对重整性能的影响, 并对比分析了NiO/MgO固溶体、CoO/MgO 固溶体催化剂和0.5%RuCoO/MgO 催化剂的重整性能. 实验结果表明, NiO/MgO 固溶体催化剂的重整性能优于CoO/MgO 固溶体催化剂. 但经Ru贵金属修饰后, CoO/MgO 固溶体催化剂的催化活性得到了很大提高.     

In situ time-resolved FTIR investigation on the reaction mechanism of partial oxidation of methane to syngas over supported Rh and Ru catalysts

In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane (POM) to synthesis gas and the reaction of CH4/O2/He (2/1/45, molar ratio) gas mixture with adsorbed CO species over Rh/SiO2, Ru/γ-Al2O3 and Ru/SiO2 catalysts at 500-600℃. It was found that CO is the primary product of POM reaction over reduced and working state Rh/SiO2 catalysts. Direct oxidation of CH4 is the main pathway of synthesis gas formation over Rh/SiO2 catalyst. CO2 is the primary product of POM over Ru/γ-Al2O3 and Ru/SiO2 catalysts. The dominant reaction pathway for synthesis gas formation over Ru/γ-Al2O3 catalyst is via the reforming reactions of CH4 with CO2 and H2O. For the POM reaction over Rh/SiO2 and Ru/γ-Al2O3 catalysts, consecutive oxidation of surface CO species is an important pathway of CO2 formation.     

固体氧化物电解质膜反应器中甲烷氧化偶合反应动力学

研究了固体氧化物电解质膜反应器 ( Ag| YSZ| Ag)中甲烷氧化偶合动力学和外加电流对反应结果的影响 ,提出了该反应系统中甲烷偶合反应网络。用幂指数拟合实验数据 ,得出甲烷总消耗速率、生成 C2 烃和深度氧化速率的动力学方程式 ,并估算了动力学参数。用固体电解质电势分析法监测了反应过程中 Ag催化剂电极表面氧活度 ,结果表明 ,反应室中气相氧与 Ag催化剂电极上的氧并未形成热力学平衡 ,氧的吸附速率小于或接近催化剂电极上氧消耗速率。本实验条件下 ,外加电流 (电压 )并未显著影响甲烷的氧化偶合反应     

Methane Conversion to C2 Hydrocarbons in Solid State Oxide Electrolyte Membrane Reactor

Provskite-type catalysts, Ln0.6Sr0.4FexCo1-x O3 （Ln = Nd, Pr, Gd, Sm, La, 0〈x〈1） and Ln0.8Na0.2CoO3（Ln=La, Gd, Sm） were synthesized, their catalytic properties in the oxidative coupling of methane （OCM） were examined in a fixed-bed reactor. The former group presented higher activity in the OCM, but the main product was carbon dioxide. While the later group showed lower activity but much higher selectivity to C2 hydrocarbons compared with the former. Electrochemical measurements were conducted in a solid oxide membrane reactor with La0.8Na0.2 CoO3 as catalyst. The results showed that methane was oxidized to carbon dioxide and ethane by two parallel reactions. Ethane was oxidized to ethene and carbon dioxide. A fraction of ethene was oxidized deeply to carbon dioxide. The total selectivity to C2 hydrocarbons exceeded 70%. Based on the experimental results, a kinetic model was suggested to describe the reaction results.     

In situ time-resolved FTIR investigation on the reaction mechanism of partial oxidation of methane to syngas over supported Rh and Ru catalysts

In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane (POM) to synthesis gas and the reaction of CH₄/O₂/He (2/1/45, molar ratio) gas mixture with adsorbed CO species over Rh/SiO₂, Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts at 500—600℃. It was found that CO is the primary product of POM reaction over reduced and working state Rh/SiO₂ catalysts. Direct oxidation of CH₄ is the main pathway of synthesis gas formation over Rh/SiO₂ catalyst. CO₂ is the primary product of POM over Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts. The dominant reaction pathway for synthesis gas formation over Ru/γ-Al₂O₃ catalyst is via the reforming reactions of CH₄ with CO₂ and H₂O. For the POM reaction over Rh/SiO₂ and Ru/γ-Al₂O₃ catalysts, consecutive oxidation of surface CO species is an important pathway of CO₂ formation.     

Fluorite Ce0.8Sm0.2O2-δ porous layer coating to enhance the oxygen permeation behavior of a BaCo0.7Fe0.2Nb0.1O3-δ mixed conductor

Fluorite Ce_0.8Sm_0.2O_2-δ (SDC) nanopowder with a crystallite size of 15 nm was synthesized by a co-precipitation method. An SDC porous layer was coated onto a BaCo_0.7Fe_0.2Nb_0.1O_3-δ (BCFN) mixed conductor to improve its oxygen transport behavior. The results show that the SDC-coated BCFN membrane exhibits a remarkably higher oxygen permeation flux (J_O2) than the uncoated BCFN in the partial oxidation of coke oven gas (COG). The maximum (J_O2) value of the SDC-coated BCFN is 18.28 mL·min-1·cm-2 under a COG/air flux of 177 mL·min-1/353 mL·min-1 at 875℃ when the thickness of the BCFN membrane is 1 mm; this (J_O2) value is 23% higher than that of the uncoated BCFN membrane. This enhancement is likely because of the higher oxygen ionic conductivity of SDC, which supplies oxygen vacancies and accelerates oxygen exchange on the membrane/coating layer/gas three-phase boundary.     

甲烷部分氧化制合成气反应中热点位置的研究

将热电偶插入La2 O3 Ni/MgAl2 O4 催化剂反应床层 ,通过移动热电偶详细考察了反应炉温、空速、原料气组成和加入水蒸气对甲烷部分氧化制合成气反应床层温升的影响。结果表明 ,反应热点位于催化剂床层入口处 ,而且热点位置不受上述反应因素的影响。但是 ,其温升值随空速的增大而升高 ,随反应炉温的升高而降低。反应中引入水蒸气可以降低反应热点的温度 ,但同时使产物中CO2 含量增大。根据反应热计算了燃烧重整机理和直接转化机理的绝热温升 ,与实验结果的对比表明 ,反应床层的温升主要来自于部分氧化反应的放热 ,即甲烷部分氧化制合成气可能是按直接转化机理进行的。极高空速时低甲烷转化率下合成气的选择性并未发生明显的变化 ,这也进一步证明了上述结论     

Mo/HZSM-5上甲烷脱氢聚合制苯反应

考察了氧气气氛下 ,活化前后分别用H2 处理 0 5h对Mo/HZSM 5催化剂反应活性的影响 .结果表明 :活化后用H2 处理后催化活性显著降低 .甲烷添加O2 ,CO2 后 ,于 70 0℃时进行氧化反应 ,无苯生成 ;75 0℃时甲烷与O2 反应在进行氧化反应的同时 ,有偶联反应发生 .反应温度的提高使甲烷转化率与苯的选择性均有提高 ,但催化剂稳定性下降 ,可能归结为积炭增加和钼组分的挥发流失 .     

The kinetic studies of direct methane oxidation to methanol in the plasma process

The research outlined here includes a study of methanol production from direct methane conversion by means of thermal and plasma method. The kinetic study, derived from thermal-based approach, was carried out to investigate thoroughly the possible intermediate species likely to be presented in the process. A set of plasma experiments was undertaken by using dielectric barrier discharge （DBD）, classified as non-thermal plasma, done at atmospheric pressure and room temperature. Plasma process yields more methanol than thermal process at the same methane conversion rates and methane to oxygen feed ratios. Oxidation reaction of thermal process resulted CO and CO2 as the most dominant products and the selectivity reached 19% and 68%, respectively. Moreover, more CO and less CO2 were produced in plasma process than in thermal process. The selectivity of CO and CO2 by plasma was 47% and 20%, respectively. Ethane （C2H6）was detected as the only higher hydrocarbon with a significant concentration. The concentration of ethane reached 9% of the total products in plasma process and 17% in thermal process. The maximum selectivity of methanol, the target material of this research, was 12% obtained by plasma method and less than 5% by thermal process. In some certain points, the kinetic model closely matched with the experimental results.     

载体对Au催化剂乙醇部分氧化制氢性能的影响

采用共沉淀制备方法分别制备Au/Al2O3、Au/ZnO、Au/CeO2、Au/Fe2O3催化剂,考察不同载体对乙醇部分氧化制氢性能的影响,并用XRD、H2-TPR、H2-TPD等对各催化剂的晶相结构、表面还原性、吸附性能等进行表征,考察载体对Au催化剂的活性和选择性的影响.结果表明,载体对Au催化剂的催化性能与H2的...     

Aerobic respiration in the Archaean?

The Earth's atmosphere during the Archaean era (3,800-2,500 Myr ago) is generally thought to have been anoxic, with the partial pressure of atmospheric oxygen about 10(-12) times the present value. In the absence of aerobic consumption of oxygen produced by photosynthesis in the ocean, the major sink for this oxygen would have been oxidation of dissolved Fe(II). Atmospheric oxygen would also be removed by the oxidation of biogenic methane. But even very low estimates of global primary productivity, obtained from the amounts of organic carbon preserved in Archaean rocks, seem to require the sedimentation of an unrealistically large amount of iron and the oxidation of too much methane if global anoxia was to be maintained. I therefore suggest that aerobic respiration must have developed early in the Archaean to prevent a build-up of atmospheric oxygen before the Proterozoic. An atmosphere that contained a low (0.2-0.4%) but stable proportion of oxygen is required.     

用于甲烷部分氧化制甲醛反应的超细MoO3／SiO2催化剂

对比研究两种不同载体ＭｏＯ３／ＳｉＯ２催化剂用于甲烷部分氧化反应，结果表明用醇盐法所制ＳｉＯ２做成的催化剂比用所买ＳｉＯ２做成的催化剂反应活性和选择性好；电镜（ＴＥＭ）结果表明前者是超细粒子催化剂，其平均粒径为１２．６５ｎｍ，粒度分布窄；ＢＥＴ及孔结构测定表明前者比表面积大，孔容及孔径小，孔径分布窄；ＴＰＲ结果表明前者ＭｏＯ３与ＳｉＯ２相互作用较弱。     

瓦斯液相催化氧化制甲醇实验研究

以瓦斯为原料制备甲醇的实验研究,可以充分利用瓦斯资源。采用苯酐-尿素法制备了酞菁铜/分子筛复合物CuPc/Y,进一步将金属钯担栽在CuPc/Y上制备了0.5%Pd-CuPc/Y复合物。以0.5%Pd-CuPc/Y为催化剂、醋酸水溶液为溶剂进行了瓦斯液相催化氧化制甲醇的实验研究。结果表明:甲醇的生成量与反应压力、反应温度、催化剂用量、溶剂的酸度、反应时间存在正相关关系,与对苯醌添加量总体上也遵循正相关规律。在瓦斯初始反应压力4 MPa、催化剂用量2 g、溶剂中CH_3COOH与H_2O体积比4:1、对苯醌用量1 000μmol、反应时间3 h、反应温度130℃的条件下,甲醇的生成量为2 754μmol。分析瓦斯液相催化氧化制甲醇的反应机理,认为0.5%Pd-CuPc/Y在醋酸溶液中催化瓦斯选择氧化制甲醇反应同时遵循亲电取代机理和活性氧物种氧化机理。     

新型ZrO_2膜管的研制及其对甲烷部分氧化的催化性能研究

利用ＳＯＬ－ＧＥＬ技术成功地制备了ＺｒＯ_２－ＣａＯ膜管，这种膜管由于能控制氧的扩散速度，并能活化它，因而容易和甲烷反应，表现了高的选择性生成甲醇、甲醛。实验发现最佳的制膜条件为：焙烧温度是７００～９００℃，膜厚４５～６０ｇＺｒ／ｃｍ￣２，ＣａＯ的最佳值为Ｘ＝０．０８～０．１５。实验也考察了最佳的反应条件，常压下反应温度为３５０℃，ＧＨＳＶ＝８０００～１００００ｈ￣（－１）。在这样的条件下获得了９５％的甲醇、甲醛选择性，大约１％转化率。     

High Temperature Corrosion of Fe-25Cr and Fe-17Cr-1.5Si-0.5Al Alloys in Oxidizing and Sulfidizing Enviornments

The simultaneous oxidation and sulfidation of Fe 25Cr and Fe-17Cr-l.5Si-0.5Al alloys was studied at 1023K and 1223K in H2-H2O-H2S gas mixtures. The kinetic boundary which indicates the transition from oxide to sulfide has heen found in these two alloys. The critical oxygen partial pressures of Fel7Crl.5SiO.5Al alloys were systematically lower than those of Fe-25Cr alloy. The reaction kinetics were measured by the stainless steel spring balance, and the reaction products were characterized by X-ray diffraction and scanning electron microscopy. The reaction rate usually decreased with the increase of the oxygen partial pressure at the constant sulfur partial pressure. The exista-nce of silicon plays an important role to suppress the sulfidation of Fel7Cr alloy.     

焦炉煤气在透氧膜反应器中的重整机理

通过实验设计和透氧量测定研究焦炉煤气(coke-oven-gas,COG)或天然气中的甲烷在透氧膜反应器中的部分氧化重整途径,提出反应器内的"重整-透氧"机理模型.在由混合导体和催化床构成的透氧膜反应器中,催化床主要实现甲烷裂解和催化重整的功能,在膜表面处的催化金属微粒完成了还原性气体的"吸附—溢流—氧化"过程,进而强化混合导体内部的氧离子传导.