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应用组成为Ba0.5Sr0.5Co0.8Fe0.2O3-(的钙钛矿型混合导体陶瓷膜制成膜反应器。该膜在进行氧分离的同时具有活化甲烷氧化偶联的催化功能。随着温度升高和膜的富氧端氧分压的增大,透氧量有所增加。在空气、氦气的氧分压梯度下,850(C,膜厚度为1.5 mm时,JO2可达到1.2 mL/(cm3(min)。同时在800(C~900(C温度范围内,该膜对于甲烷转化为乙烷和乙烯一般只具有0.5%~3.5%的低转化率,而选择性可达40%~70%。在反应尾气中发现了大量的未反应的分子氧,说明过量的氧与甲烷未经催化反应的气相反应导致了C2的选择性相对较低。OCM膜反应模式情况下的透氧量与空气、氦气梯度情况下的透氧量相比只有微小增加,这与POM膜反应模式情况下透氧量大量增加显著不同。 相似文献
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混合导体透氧膜反应器 总被引:4,自引:0,他引:4
综述了混合导体透氧膜反应器中的催化反应.介绍了混合导体透氧膜的氧渗透原理、膜材料的结构、组成以及无机膜反应器的种类和优势.详细讨论了混合导体透氧膜反应器中的甲烷部分氧化反应以及用于该反应的膜材料的发展历程,总结了甲烷氧化偶联和乙烷氧化脱氢等膜反应器中的催化反应,以及混合导体透氧膜用于水分解和二氧化碳分解等受热力学平衡限制的反应. 相似文献
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Ba0.5Sr0.5Co0.8Fe0.2O3-δ透氧膜反应器在丙烷氧化脱氢反应中的应用 总被引:1,自引:0,他引:1
工业上一般采用丙烷热裂解脱氢反应生产丙烯. 该反应通常在高温(>700 ℃)下进行,催化剂容易积碳. 而且,由于反应受到热力学平衡的限制,丙烯的选择性也不很高. 近年来,以廉价空气和丙烷为原料的丙烷氧化脱氢(PODH)反应为丙烯的生产提供了另外一条途径,且已引起广泛的关注. 在PODH反应中,一般认为晶格氧(O2-)参与丙烷的选择氧化,而其它氧物种(O-,O-2等)导致丙烷的完全氧化[1]. 钙钛矿结构的混合导体透氧膜是同时具有氧离子导电性和电子导电性的一类材料. 在高温下,当膜两侧存在氧浓度梯度时,氧以氧离子的形式通过氧缺陷进行传导,同时以电子的反向传输来完成传输回路[2]. 这种透氧机理使得混合导体透氧膜在理论上对烷烃氧化反应具有一定的催化活性. 作为膜反应器材料,这类混合导体透氧膜已成功地应用于甲烷部分氧化(POM)反应[3]. 但迄今为止,还没有文献报道这种膜反应器在PODH反应中的应用. 组成为Ba0.5Sr0.5Co0.8Fe0.2O3-δ的钙钛矿膜材料是本研究组开发的一类具有高透氧量、高稳定性的新型透氧膜材料. 本文尝试将该材料制备的膜反应器用于PODH反应,同时研究了PODH反应对膜透氧量的影响. 相似文献
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BaCo0.7Fe0.2Nb0.1O3-δ膜反应器还原侧表面反应机理 总被引:1,自引:0,他引:1
研究了BaCo0.7Fe0.2Nb0.1O3-δ(BCFN)透氧膜反应器还原侧表面反应机理, 分析了表面催化微粒及催化床对膜反应器的作用. 提出了“催化解离机制”是构成甲烷重整BCFN膜反应器透氧量上升的主要原因; CH4, H2及CO在BCFN膜表面的反应活性依次为H2>CO>CH4; 当CH4气氛中加入H2或CO时, BCFN膜表面的主要发生由CH4直接氧化转变H2或CO的氧化反应, 同时极大提升了BCFN膜反应器的透氧量; BCFN膜表面氧化反应为“晶格氧”氧化反应模式主导. 相似文献
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制备了金属陶瓷双柏Ni-BaCe0.6Zr0.2Nd0.2O3-δ膜,并将其用丁从含氢混合气巾分离氧气,研究了该膜在不同条件下的透氢性能以及膜片在CO2与H2O存在条什卜的透氢稳定性.结果表明,膜片的透氧最随着温度的升高而提高.当使用含3%H2O的原料气时,膜片透氢量是其在干燥气氛时的2~5倍;在900℃,原料气为潮湿80%H2/He的条件卜,膜片的透氢量达到0.073cm3/(min cm2).膜片在含有30%CO2的混合气巾,经100 h寿命实验后,仍然保持较高的渗透稳定性.这些结果表明该双相膜在分离CO2和H2混合气中具有很好的应用前景. 相似文献
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利用固相合成法制备了A位La掺杂Ba Co0.88Nb0.12O3-δ[BLCN-x,x为La的掺杂量(摩尔分数)]钙钛矿透氧膜材料,采用X射线衍射(XRD)、扫描电子显微镜(SEM)、热重分析(TG)及程序升温脱附-质谱(TPD-MS)等方法研究了CO2气氛静态处理及动态透氧条件BLCN-x系列材料的结构稳定性.研究结果表明,随着La掺杂量的增加,BLCN-x膜片材料抗CO2腐蚀的性能明显提高.当La含量高于0.5时,在850℃纯CO2气氛静态处理或透氧条件下均未观察到碳酸盐衍射峰.尽管La掺杂会降低BLCN-x膜片的初始透氧量,但在CO2气氛吹扫时透氧量的降低速率明显减慢,其中BLCN-0.5膜片在纯CO2气氛下10 h后的透氧量仍可达到0.46 m L·cm-2·min-1.通过容差因子和平均金属-氧键能计算可知,良好的结构稳定性和增强的金属-氧键能是导致La掺杂样品抗CO2腐蚀的主要因素. 相似文献
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在透氧膜反应器中进行甲烷氧化偶联反应的研究 总被引:2,自引:0,他引:2
混合导体透氧膜是一类同时具有电子和氧离子两类导电性的陶瓷膜.在高温下,氧会以氧离子的形式透过透氧膜,因此在膜表面存在丰富的氧物种(O-,O-2,O2-2和O2-),这些氧物种能够提高甲烷氧化偶联(OCM)反应的C2选择性.采用挤压的方法制备出致密的Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCFO)透氧膜管,并考察了此透氧膜管对OCM反应的催化性能.发现BSCFO的C2生成速率比La0.6Sr0.4Co0.8Fe0.2O3-δ(LSCFO)和La-Ba-Co-Fe-O(LBCFO)要高得多,其原因主要是由于BSCFO中的氧空缺浓度比较高.高的氧空缺浓度不仅能够加速氧离子的传输,而且能够提高甲烷分子的活化速度,所以BSCFO具有比LSCFO和LBCFO更好的催化性能.C2生成速率随着反应温度及原料气中甲烷浓度的升高而升高,C2选择性取决于氧离子结合与OCM反应竞争的结果,高的氧离子结合速率会降低C2选择性.甲烷转化率随着富氧侧氧分压的升高而升高,但C2选择性则随着氧分压的升高而降低.这说\r\n明在OCM过程中气相反应起着重要的作用. 相似文献
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铁掺杂浓度对Ba0.5Sr0.5CoxFe1-xO3-δ混合导体膜性质的影响 总被引:3,自引:0,他引:3
用湿化学法合成了Ba0.5Sr0.5CoxFe1-xO3-δ系列混合导体透氧膜材料,并用XRD,O2-TPD,H2-TPR和透氧测定等手段考察了铁离子掺杂浓度对导体膜相结构及其稳定性、氧脱附性能和透氧能力等的影响.在氧浓度为2.13×104~0.1 Pa的范围内,x=0.2~0.8时材料保持为立方钙钛矿结构.铁含量的增加有利于材料钙钛矿结构在低温的稳定化,并提高了材料的热化学稳定性.然而,导体膜的透氧量却随着铁含量的增加而减小.这可能是由于导体膜表面的氧交换动力学过程在透氧速率控制步骤中的分量随铁含量的增加而变大之故. 相似文献
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荷电膜的膜电位研究进展 总被引:1,自引:0,他引:1
膜电位的测定是表征荷电膜的传递现象的重要参数之一。本文简要介绍了膜电位理论基础,包括T. M. S.理论和不可逆热力学理论。分别阐述了关于离子交换膜、双极膜、两性膜以及复合膜的膜电位的最新进展,并提出今后的发展方向。 相似文献
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Zeolite X membranes were investigated by in-situ hydrothermal synthesis on porous ceramic tubes precoated with zeolite X seeds or precursor amorphous aluminosilicate, and porous α-Al2O3 ceramic tubes with a pore size of 50 200 nm were employed as supports. Zeolite X crystals were synthesized by the classic method and mixed into deionized water as a slurry with a concentration of 0.2 0.5wt%, having a range of crystal sizes from 0.2 to 2μm. Crystal seeds were pressed into the pores near the inner surface of the ceramic tubes, and crystallization took place at 95℃ for 24-96 h. It was also investigated that Boehmite sol added with zeolite X seeds was precoated on ceramic supports to form a layer of γ-Al2O3 by heating, and hydrothermal crystallization could then take place to prepare the zeolite membranes on the composite ceramic tubes. The crystal species were characterized by XRD, and the morphology of the supports subjected to crystallization was characterized by SEM. The composite zeolite membranes have zeolitic top-layers with a thickness of 10-25 μm, and zeolite crystals can be intruded into pores of the supports as deeply as 100μm. The experimental results indicate that the precoating of zeolitic seeds on supports is beneficial to crystallization by shortening the synthesis time and improving the membrane strength. The resulting zeolite X membrane shows permselectivity to tri-n-butylamine((C4H9)3N) over perfluro-tributyl-amine ((C4Fg)3N), and a permeance ratio of 57 for ((C4Hg)3N to (C4F9)3N could be reached at 350℃. Permeances of BZ, EB and TIPB through the zeolite membrane were also measured and were found to slightly increase with temperature. 相似文献
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A model of the composite membrane consisting of the catalytic layer (CL) and the nanofiltration layer (NFL) is presented. It has been found that applying NFL on the permeate side of CL it is possible to enhance substantially the conversion of substrate into the product. The best performance is obtained for high retention of substrate and low of product. At higher values of volume flow and/or longer catalytic path the retention degree of product becomes negligible. The presence of NFL enhances the influence of distribution of the reaction rate constant, k, on the conversion ratio. Comparing to k = constant the positive effect is obtained if k increases along the catalytic pore, whereas negative—if k decreases. 相似文献
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Zhongqiang Xu Qingling Chen Guanzhong LuShanghai Research Institute of Petrochemical Technology Shanghai ChinaInstitute of Industrial Catalysis East China University of Science Technology Shanghai China 《天然气化学杂志》2002,(Z2)
Zeolite X membranes were investigated by in-situ hydrothermal synthesis on porous ceramic tubes precoated with zeolite X seeds or precursor amorphous aluminosilicate, and porous α-Al2O3 ceramic tubes with a pore size of 50-200 nm were employed as supports. Zeolite X crystals were synthesized by the classic method and mixed into deionized water as a slurry with a concentration of 0.2-0.5wt%, having a range of crystal sizes from 0.2 to 2μm. Crystal seeds were pressed into the pores near the inner surface of the ceramic tubes, and crystallization took place at 95℃ for 24-96 h. It was also investigated that Boehmite sol added with zeolite X seeds was precoated on ceramic supports to form a layer of r-Al2O3 by heating, and hydrothermal crystallization could then take place to prepare the zeolite membranes on the composite ceramic tubes. The crystal species were characterized by XRD, and the morphology of the supports subjected to crystallization was characterized by SEM. The composite zeolite membranes hav 相似文献
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