致密透氧膜用于甲烷部分氧化制合成气的实验研究

引　言钙钛矿型致密透氧膜在高温下具有氧离子、电子混合导电性 .当膜两侧存在氧分压梯度时 ,高压侧的氧在膜表面经化学吸附解离成氧离子、电子 ,于膜主体内扩散至另一侧 ,并重新结合、脱附至低氧压体系 .将致密透氧膜反应器用于甲烷部分氧化制合成气反应为天然气利用开辟了一条崭新的路径 ,近年来受到普遍关注 .该过程集空分与反应于一体 ,降低了大量的操作成本 ,通过膜壁控制氧气的进料有效控制了反应进程 .提高膜的透氧量 ,解决还原性气氛下膜的稳定性等问题 ,是该过程实现工业化的关键 .Ｂａｌａｃｈａｎｄｒａｎｄ[1] 、Ｔｓａｉ[2 ] …     

钙钛矿型透氧膜及其在甲烷部分氧化中的应用

钙钛矿型透氧陶瓷膜是同时具有氧离子和电子导电性的功能无机膜,在纯氧分离和甲烷部分氧化膜反应器中具有重要的潜在应用.介绍了钙钛矿型透氧陶瓷膜的氧渗透原理、膜材料的结构性能及其在甲烷部分氧化制合成气中的应用研究进展,并对透氧膜所面临的挑战进行了论述.     

SrFe0.6Cu0.3Ti0.1O3-δ透氧膜反应器中甲烷部分氧化反应工艺及膜稳定性考察

采用SrFe_0.6Cu_0.3Ti_0.1O_3-δ混合导体透氧膜组装成膜催化反应器,进行甲烷部分氧化制合成气反应,考察了反应温度、空速、催化剂粒径等条件的影响,并分析了反应气氛引起的透氧膜结构变化情况。结果表明,在膜反应器内,催化反应与透氧过程存在相互制约和相互促进的关系。在膜反应器内进行甲烷部分氧化反应后,透氧膜的两侧表面均发生蚀刻现象,结晶度显著降低,反应侧蚀刻现象较为严重,膜表面形成了疏松的多孔层,反应气氛使膜表面晶体结构发生了较大改变,Sr容易从钙钛矿结构中析出并与CO₂结合形成SrCO₃,Sr的析出导致组成不平衡,促进了钙钛矿结构分解及其他物相的产生。     

管式致密透氧膜用于甲烷部分氧化制合成气的研究

采用钙钛矿型管式致密透氧膜反应器,在Ｎｉ／Ａｌ２Ｏ３催化剂上进行了甲烷部分氧化制合成气的实验研究,考察了进料气中甲烷的摩尔分数和反应温度对反应结果的影响,并对膜在反应条件下的稳定性作了分析     

SrFe_(0.6)Cu_(0.3)Ti_(0.1)O_(3-δ)透氧膜反应器中甲烷部分氧化反应工艺及膜稳定性考察

采用SrFe0.6Cu0.3Ti0.1O3?δ混合导体透氧膜组装成膜催化反应器,进行甲烷部分氧化制合成气反应,考察了反应温度、空速、催化剂粒径等条件的影响,并分析了反应气氛引起的透氧膜结构变化情况。结果表明,在膜反应器内,催化反应与透氧过程存在相互制约和相互促进的关系。在膜反应器内进行甲烷部分氧化反应后,透氧膜的两侧表面均发生蚀刻现象,结晶度显著降低,反应侧蚀刻现象较为严重,膜表面形成了疏松的多孔层,反应气氛使膜表面晶体结构发生了较大改变,Sr容易从钙钛矿结构中析出并与CO2结合形成SrCO3,Sr的析出导致组成不平衡,促进了钙钛矿结构分解及其他物相的产生。     

甲烷部分氧化制合成气膜反应实验与模拟

采用钙钛矿型致密透氧膜对甲烷部分氧化制合成气进行了膜反应实验研究,并建立了该膜反应的数学模型。模拟计算结果与实验结果吻合较好：通过该模型考察了绝热条件下的反应床层温度分布,以及恒温反应体系中温度、流量、反应器长度等因素对膜反应结果的影响。     

富甲烷部分氧化制氢气混合导体材料的研究进展

综述了混合导体透氧膜材料用于富甲烷气体部分氧化制氢气的研究状况。介绍了混合导体材料用于富甲烷气体部分氧化制氢气的工作原理,BaCoO3基单相混合导体材料、及体相掺杂或使用催化剂对此类材料的改性研究,双相混合导体透氧膜材料。并对混合导体膜材料的应用前景和改进方向进行了展望。     

氧泵型催化膜反应器中甲烷氧化偶联反应(Ⅱ)——动力学研究

在1％Sr/La_2O_3-Bi_2O_3-Ag-YSZ氧泵型催化膜反应器中,进行了甲烷氧化偶联反应动力学研究,提出了反应途径及机理,并建立了速率方程。结果表明,在该氧泵型催化膜反应器中,甲烷氧化偶联反应满足Rideal-Rdox机理。采用固体电解质电位测定技术进行了内扩散影响的考察。     

甲烷部分氧化反应的稳态模拟

甲烷部分氧化制合成气是天然气资源开发利用的主要方面。而通过甲烷部分氧化反应的模拟能够使研究者在探索反应本质的基础上有效地指导其工艺操作。本文综述了近年来国内外甲烷部分氧化反应的反应机理和模拟研究进展。同时也展望了将来甲烷部分氧化模拟的发展方向。     

膜反应器中甲苯部分氧化制苯甲醛

研究了负载及装填铁－钼经剂的氧化铝膜管应用于甲苯膜催化氧化制苯甲醛的反应,考察了三种进料方式：（１）甲苯从管侧面渗入,空气从管口进入;（２）甲苯从管口进入,空气从管侧面渗入;９３甲苯空气混合从管口进入,并考察耻温度、空气甲苯进料比、甲苯空速的变化以及不同催化剂对反应的影响。结果表明,在采用（１）进料方式,温度６００℃时苯甲醛产率和选择性最高;在一定范围内随甲苯空速和空气甲苯进料比的增大,苯珠产率也     

Failure mechanisms of ceramic membrane reactors in partial oxidation of methane to synthesis gas

In the course of generating synthesis gas (H₂, CO) from methane, we have observed two types of fractures occurring on the Sr(Co, Fe)O_x-type oxygen membrane reactors. The first type occurred shortly after the reaction started and the second type often occurred days after the reaction. To determine the causes of these fractures, we have examined the starting material and fractured membranes using a combination of X-ray diffraction and thermogravimetric analyses. We found that the first type of fracture was the consequence of an oxygen gradient in the membrane, pointing from the reaction side to the air side. This causes a lattice mismatch inside the membrane, leading to fracture. The second type of fracture, however, was the result of a chemical decomposition. We found that the Sr(Co, Fe)O_x-type membrane had been reduced to SrCO₃, and elemental Co and Fe by the synthesis gas generated in the reaction. The decomposition causes enormous expansion leading to a large crack along the axis of tube.     

Partial oxidation of methane in hollow‐fiber membrane reactors based on alkaline‐earth metal‐free CO2‐tolerant oxide

The U‐shaped alkaline‐earth metal‐free CO₂‐stable oxide hollow‐fiber membranes based on (Pr_0.9La_0.1)₂(Ni_0.74Cu_0.21Ga_0.05)O_4+δ (PLNCG) are prepared by a phase‐inversion spinning process and applied successfully in the partial oxidation of methane (POM) to syngas. The effects of temperature, CH₄ concentration and flow rate of the feed air on CH₄ conversion, CO selectivity, H₂/CO ratio, and oxygen permeation flux through the PLNCG hollow‐fiber membrane are investigated in detail. The oxygen permeation flux arrives at approximately 10.5 mL/min cm² and the CO selectivity is higher than 99.5% with a CH₄ conversion of 97.0% and a H₂/CO ratio of 1.8 during 140 h steady operation. The spent hollow‐fiber membrane still maintains a dense microstructure and the Ruddlesden‐Popper K₂NiF₄‐type structure, which indicates that the U‐shaped alkaline‐earth metal‐free CO₂‐tolerant PLNCG hollow‐fiber membrane reactor can be steadily operated for POM to syngas with good performance. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3587–3595, 2014     

Catalytic partial oxidation of methane to synthesis gas in a ceramic membrane reactor

Methane has been selectively converted to synthesis gas using a two-zone fixed bed of a Ni/Al₂O₃ catalyst inside a modified ceramic membrane. The first zone of the reactor was surrounded by an impervious wall, and therefore behaved as a conventional fixed bed reactor. In the second zone, some of the reaction products could preferentially diffuse out of the reactor, which yielded higher than equilibrium methane conversions. The influence of the different operating conditions has been studied, and the performance of the membrane reactor has been compared to that of a fixed bed reactor. The membrane reactor has also been used at pressures above atmospheric (2 bar), with good conversions and selectivities.     

Partial oxidation of methane to syngas in BaCe0.15Fe0.85O3−δ membrane reactors

Dense planar Ba_0.15Ce_0.85FeO_3−δ (BCF1585) membrane reactors were investigated to produce syngas from methane. Firstly, the membrane itself catalytic activity to methane was investigated using a blank BCF1585 without any catalysts. Then a LiLaNi/γ-Al₂O₃ catalyst was packed on the BCF1585 membrane surface to test the synergetic effects of the membrane and catalyst. It was found that the membrane itself has a poor catalytic activity to methane. The main products are CO₂ and C₂, and methane conversion is low due to the low oxygen permeation flux. However, after the catalyst was packed on the membrane surface, both methane conversion and oxygen permeation flux were greatly improved by the synergetic effect between the membrane and catalyst. Carbon monoxide selectivity reached at 96% with methane conversion of up to 96%. The oxygen permeation flux reached at 3.0 mL/cm² min at 850 °C for a 1.5 mm disk membrane and can effectively be increased by reducing the thickness of the membranes. After operation for 140 h at 850 °C, the used membrane was examined with SEM and EDXS. The results revealed that the decomposition of the membrane materials could not be avoided under such conditions. Oxygen partial pressure gradient across the membranes is suggested as a critical factor to accelerate the kinetic decomposition of the materials.     

Design of mixed conducting ceramic membranes/reactors for the partial oxidation of methane to syngas

The performance of mixed conducting ceramic membrane reactors for the partial oxidation of methane (POM) to syngas has been analyzed through a two‐dimensional mathematical model, in which the material balance, the heat balance and the momentum balance for both the shell and the tube phase are taken into account. The modeling results indicate that the membrane reactors have many advantages over the conventional fixed bed reactors such as the higher CO selectivity and yield, the lower heating point and the lower pressure drop as well. When the methane feed is converted completely into product in the membrane reactors, temperature flying can take place, which may be restrained by increasing the feed flow rate or by lowering the operation temperature. The reaction capacity of the membrane reactor is mainly determined by the oxygen permeation rate rather than by the POM reaction rate on the catalyst. In order to improve the membrane reactor performance, reduction of mass transfer resistance in the catalyst bed is necessary. Using the smaller membrane tubes is an effective way to achieve a higher reaction capacity, but the pressure drop is a severe problem to be faced. The methane feed velocity for the operation of mixed conducting membrane reactors should be carefully regulated so as to obtain the maximum syngas yield, which can be estimated from their oxygen permeability. The mathematical model and the kinetic parameters have been validated by comparing modeling results with the experimental data for the La_0.6Sr_0.4Co_0.2Fe_0.8O_3‐α (LSCF) membrane reactor. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Improving selectivity during methane partial oxidation by use of a membrane reactor

A reactant-swept catalytic membrane reactor for partial oxidation of methane to formaldehyde has been modeled. Kinetic parameters were taken from the literature for a V₂O₅/Sio₂ methane partial oxidation catalyst, and membrane parameters characteristic of commercially available materials were used. The models show that the selectivity for formaldehyde can be significantly improved by using a membrane reactor.     

Partial oxidation of methane over platinum metal gauze

The partial oxidation of methane to synthesis gas has been studied over a platinum gauze catalyst. The experiments were carried out at atmospheric pressure with a single gauze in a quartz reactor heated in an electric furnace. The furnace temperature was varied in the range 200–900°C and the space time in the range 0.00021–0.00042 s. The feed consisted of a mixture of CH₄O₂Ar2110 and carbon oxides and water were the main products. Oxygen was only partly consumed and relatively small amounts of hydrogen were formed.     

Simulations of the effect of hydrodynamic conditions and properties of membranes on the catalytic performance of a fluidized-bed membrane reactor for partial oxidation of methane

In a fluidized-bed membrane reactor the selectivity of separation can be controlled by influencing the hydrodynamics of the fluidized bed. In this reactor type, with the mass transport limitation between bubbles and the emulsion phase, even with the non-selective membranes, high selectivity of separation can be achieved. This opens the possibility for applications of membrane reactors for reaction systems for which selective membranes do not exist, e.g. when Knudsen-type membranes or form-selective separation can not be applied. This paper is aimed at explaining the interaction between the selectivity of separation and the hydrodynamics of the fluidized bed by means of simulations that were performed for a fluidized-bed membrane reactor for catalytic partial oxidation of methane.     

Partial oxidation of methane to synthesis gas over Rh-hexaaluminate-based catalysts

The partial oxidation of methane to synthesis gas over catalysts consisting of Rh supported on hexaaluminates (BaAl₁₂O₁₉, CaAl₁₂O₁₉ and SrAl₁₂O₁₉) was investigated at atmospheric pressure and high reactant dilution in order to compare their performances within the kinetic-controlling regime. Comparison with the results obtained over a commercial Rh/-Al₂O₃ system indicates that hexaaluminate catalysts are active and selective in this reaction. Despite of the higher surface area of the support, hexaaluminate-supported catalysts were found less stable, active and selective than an -Al₂O₃-supported catalyst.