掺杂电活性离子聚吡咯膜内的电荷传输

用循环伏安法和计时库仑法研究了掺杂亚铁氰化钾离子的聚哟咯膜内的电荷传输问题。实验结果表明，聚吡咯膜内的电荷传递可以处理成电子在膜内的扩散模型，电荷传递速度可以 用电子表观扩散系数（Ｄａｐｐ）来表征。Ｄａｐｐ的大小由聚合物膜的结构、电活怀离子之间的过及对离了在膜中的运动决定。     

N_(235)二甲苯-醋酸铵-液膜体系萃取Cd(Ⅱ)的研究

本文研究了反萃剂、料液 HCl浓度、温度、 N_(235)浓度对 N_(235)二甲苯醋酸铵大块液膜体系迁移 Cd~(2＋)的影响。当膜相添加不同浓度的表面活性剂 Span 80时，测定了膜料液界面的萃取反应表观速率常数 k_1和膜反萃相界面的反萃取表观速率常数 k_2，并进行了相应的动力学分析。实验证明， Cd~(2＋)的迁移可用两个连续单向不可逆的一级反应来描述。在本文的液膜体系中， Cd2＋的跨膜迁移和 H＋的同向迁移耦合。     

气体在玻璃态高分子膜中的溶解-扩散行为

本文建立了纯气体-膜体系以及混合气体-膜体系的溶解和扩散行为的通用模型,经采用玻璃态及橡胶态高分子膜在不同温度及压力下得到的实验数据证明,该模型可以只用纯气体实验得到的模型参数来预测混合气体在膜中的行为,计算值与实验结果吻合良好。     

厚体液膜拆分克伦特罗外消旋体及其动力学研究

以D-( )-二苯甲酰酒石酸(D-( )-DBTA)为流动载体,研究了克伦特罗(clenbuterol,Cle)对映体的厚体液膜法拆分,建立了手性拆分条件和动力学拆分模型。考察了D-( )-DBTA浓度、缓冲液pH值对手性拆分性能的影响,进行了动力学分析,并测定了膜-料液界面的萃取反应表观速率常数k1和膜-反萃相界面的反萃取表观速率常数k2。结果表明:在优化的实验条件下(pH为7,手性载体与Cle浓度比为1∶4),Cle外消旋体能被含有手性载体D-( )-DBTA的厚体液膜有效拆分,分离因子大于1.08;Cle单体的跨膜迁移过程可以用两个串联的准一级不可逆过程进行描述。     

N235二甲苯-醋酸铵-液膜体系萃取Cd(Ⅱ)的研究

本文研究了反萃剂,料液ＨＣｌ浓度、温度、Ｎ２３５浓度对Ｎ２３５－二甲苯－醋酸铵大块液膜体系迁移Ｃｄ＾２＋的影响,当膜相添加不同浓度的表面活性剂Ｓｐａｎ－８０时,测定了膜－料液界面的萃取反应表观速率常数ｋ１和膜－反萃相界面的反萃取表观速率常数ｋ２,并进行了相应的动力学分析。实验证明,Ｃｄ＾２＋的迁称可用两个连续单不可逆的一级反应来描述,在本文的液膜体系中,Ｃｄ＾２＋的跨膜迁移和Ｈ＾＋的同向迁移耦合。     

单臂液晶冠醚LB膜的研究

首次研究了４种单液晶冠醚（１～４）的ＬＢ膜成膜特性，实验发现它们在气－液界面均可形成单分子膜，但４的稳定性较差，３易转移到玻璃基片上形成Ｙ型膜。４种化合物与硬脂酸以１：１混合形成稳定的Ｙ型ＬＢ膜。小角Ｘ射线衍射证实了膜的有序结构。用ＣＰＫ原子模型对成膜分子构型和面积进行了估算，其结果与实验一致。并讨论了分子结构对成膜性能的影响。     

壳聚糖-丝心蛋白合金膜的研究(Ⅰ)——合金膜的结构及其对丝心蛋白吸水性和机械性能的改善

通过ＦＴＩＲ、Ｘ射线衍射、ＴＧＡ和ＤＳＣ等手段对壳聚糖－丝心蛋白合金膜的结构进行了表征．结果表明，合金膜中壳聚糖和丝心蛋白之间存在着较强的氢键相互作用，根据Ｘ射线衍射结果并结合合金膜表观均匀透明、扫描电镜观察未发现明显宏观相分离，认为合金膜是基本相容的．同时发现，在丝心蛋白中共混一定量的壳聚糖可以改善其吸水性和机械性能．     

聚1-三甲基硅基丙炔膜渗透汽化分离乙醇-水溶液的研究Ⅰ.PTMSP膜渗透汽化分离乙醇-水传质的基本特征

研究了聚１－三甲基硅基丙炔膜渗透汽化分离乙醇－水溶液传质的主要特点。发现膜对乙醇优先吸附、溶解，对水优先扩散。但因吸附液中水含量很低，总的结果表现为优先透醇。在３１３Ｋ，膜厚２０～２５μｍ，料液浓度１０ｗｔ％时，α＝１８．５，Ｊ＝０．９６９ｋｇ·ｍ－２·ｈ－１。透过膜的渗透液及其中的水和乙醇渗透汽化表观活化能分别为２８．８７、３１．３０和２７．６６ｋＪ／ｍｏｌ，并随料液浓度下降而增加。对实验数据进行非线性回归，建立了该膜传递乙醇的经验关联式：Ｊｅ＝－５．５６４Ｃ２Ｅ０＋１３．３４ＣＥ０－０．１５７３（ｋｇ·ｍ－２·ｈ－１），计算值与实验值相吻合。     

磺化聚乙烯离子交换膜渗透汽化分离二氧六环／水混合物研究

本文用非均相光化学氯磷化反应制得了亲水的耐有机溶剂耐酸碱的磺化聚乙烯离子交换膜．膜截面离子基因密度与反应程度有关．该膜对近恒沸组成的二氧六环／水混合液显示出很高的渗透汽化分离系数和透过速率．研究了对离子、离子交换容量、料液浓度和温度对分离性能的影响．通过膜内水合离子形成“水通道”模型讨论了渗透机理．膜内离子基团密度估计及水的表观渗透活化能的大小支持“水通道”的存在．     

膜反应器中乙苯脱氢反应的理论分析

本文从化工角度对化学反应与膜分离的动态过程进行了关联，对连续流式膜反应器建立了一维数学模型，并以乙苯氢反应为例，对膜反应器的诸多影响因素进行了综合分析，对该反应而言，低水／油比进高Ｄａ值操作，都有利于膜反应器效果的提高。膜的选择分离性能好，转化率也随之增加，对膜反应器的结构进行了重点分析，发现催化剂床层高度与膜长及膜放置位置之间存在着一个最佳匹配关系，从理论上说明了前期工作的实验结果。     

Ionic liquid silver salt complexes for propene/propane separation

Properties of the room-temperature liquid complex salt [Ag(propene)(x)][Tf(2)N] have been studied to probe its suitability for acting as active separation layer in immobilised liquid membrane (ILM) concepts for propane/propene separation. The pressure/temperature range of complex formation has been determined and the thermal properties of Ag[Tf(2)N] and [Ag(propene)(x)][Tf(2)N] have been studied by DSC (differential scanning calorimetry) and TGA (thermogravimetric analysis) measurements. Pressure dependent measurements of solubility and diffusivity showed that the observed membrane selectivity is dominated by the solubility selectivity. The self-diffusion coefficient of propene is always smaller compared to propane as propene is temporarily bound to the silver ion in the [Ag(propene)(x)][Tf(2)N] ionic liquid.     

Transient and steady state investigation of selective and non-selective reaction pathways in the oxidative dehydrogenation of propane over supported vanadia catalysts

Mechanistic aspects of the formation of C3H6, CO and CO2 in the oxidative dehydrogenation of propane over VOx/gamma-Al2O3 materials have been investigated by means of steady state and transient isotopic tests. The materials possessed highly dispersed and polymerised VOx species as well as bulk-like V2O5. Propene was primarily formed via oxidative dehydrogenation of propane by lattice oxygen of VOx species. It was suggested that non-selective consecutive propene oxidation is initiated by the breaking of the C-C bond in the molecule by the lattice oxygen, forming formaldehyde as a side product, which is further oxidised to CO and CO2. The following order of initial steady state propene selectivity (at a zero degree of propane conversion) as a function of the nature of VOx species was established: a mixture of bulk-like V2O5 and polymerised VOx>polymerised VOx>highly dispersed VOx species. The low propene selectivity over highly dispersed VOx species was explained by the fact that these species do not fully cover the bare acidic surface of gamma-Al2O3 where propene adsorption and further oxidation take place. Thus, two different locations of COx formation were considered: (i) in the vicinity of acidic sites of the support and (ii) on VOx species. The propene selectivity over samples possessing polymerised VOx species and bulk-like V2O5 strongly decreased with an increasing degree of propane conversion. Contrarily, highly dispersed VOx species showed the lowest ability for consecutive propene oxidation.     

FTIR matrix-isolation study of the reaction products of vanadium atoms with propene: observation of allylvanadium hydride as a precursor to sacrificial hydrogenation of propene

Vanadium atoms have been reacted with different partial pressures of propene in Ar under matrix-isolation conditions, and the products have been observed using Fourier transform infrared (FTIR) spectroscopy. Under dilute propene in Ar conditions, new features are observed in the IR spectra corresponding to a C-H insertion product, identified here as H-V-(η(3)-allyl). Use of d(3)-propene (CD(3)-CH═CH(2)) demonstrates that the initial V-atom insertion occurs at the methyl group of the propene molecule, and DFT calculations have been used to support the identity of the initial product. Upon increasing the partial pressure of propene, additional features corresponding to propane (C(3)H(8)) are observed, with the hydrogen-atom source for the observed hydrogenation demonstrated to be additional propene units. Analysis of a systematic increase in the partial pressure of propene in the system demonstrates that the yield of propane correlates with the decrease of the allyl product, demonstrating the H-V(allyl) species as a reactive intermediate in the overall hydrogenation process. An overall mechanism is proposed to rationalize the formation of the insertion product and ultimately the products of hydrogenation, which agrees with previous gas-phase and matrix-isolation work involving propene and the related system, ethene.     

P-modified cobalt oxide：A novel and effective catalyst for oxidative dehydrogenation of propane

A series of nanosized cobalt oxide catalysts modified with phosphorus have been synthesized by the sol–gel method and investigated in the oxidative dehydrogenation of propane to propene.With the addition of phosphorus,the crystallite size of the catalyst was largely decreased,while the P species in the catalyst were highly dispersed.Compared to pure cobalt oxide,the P-modified samples showed higher propane conversion and enhanced propene selectivity.Over the PCoO catalyst with a P/Co atomic ratio of 0.05,the maximal propene yields of 15.7%with a propane conversion of 28.3%were obtained at 520℃.     

The destruction of atmospheric pressure propane and propene using a surface discharge plasma reactor

Surface discharge plasma reactors (SDRs) have been shown to be effective in removing a wide range of pollutants. In this study, the effectiveness of a SDR for the removal of propane and propene from an atmospheric pressure air stream was investigated. For an input energy of 100 J L-1, the conversions were found to be 16% and 68% for propane and propene, respectively. The total carbon recovery was found to increase with increasing specific input energy (SIE) for both hydrocarbons. FTIR analysis showed that CO and CO2 are the major end-products, and GC-MS identified formic acid as a significant byproduct. The effect of initial propane concentration was also investigated. The reaction chemistry involved in the oxidative plasma conversion of propane and propene is discussed.     

VMgO催化剂上丙烷和异丁烷临氧催化转化机理

用程序升温反应 -红外光谱技术研究 2 0VMgO和 6 0VMgO催化剂上丙烷和异丁烷临氧催化转化的机理 .结果表明 ,临氧条件下的反应性是异丁烷 >丙烷 ,与其分子中最弱C -H键键能从弱到强顺序相同 ,这意味着临氧活化的第一步可能是断裂分子中强度最弱的C -H键、且为速率控制步骤 ;丙烷临氧反应的深度氧化产物COx 与氧化脱氢产物丙烯的生成是平行和 (或 )连续反应关系 ,而裂解产物乙烯和甲烷的生成则是平行反应 ;异丁烷氧化脱氢反应中C -C键的断裂比丙烷的容易 .     

Thermal activation of typical oxidative dehydrogenation catalyst precursors belonging to the Ni−Mo−O system

NiMoO₄ obtained by calcination of precursors has been shown to be a very effective catalyst for oxidative dehydrogenation of propane into propene. Preparation conditions and thermal decomposition of two precursors have been studied by TG-DTA, HTXRD, FFT-IR, and thermo-desorption coupled to mass spectroscopy in order to determine their composition and to define the best treatment to favour the oxidative dehydrogenation process. The selectivity and activity for propane transformation into propene are very different depending on the nature of the precursor and of the active phases obtained after thermal activation. The more selective high-temperature β phase of NiMoO₄ has been obtained at a lower temperature (500°C) than previously reported (700°C).     

丙烷脱氢制丙烯研究进展

介绍了丙烷脱氢制丙烯的研究现状。包括丙烷催化脱氢的热力学、脱氢技术丙烷在膜反应器中脱氢及以氧气和二氧化碳作氧化剂的丙烷氧化脱氢。     

Oxidative dehydrogenation of ethane and propane on CuTh oxide catalysts

CuThO oxides prepared with different atomic ratios Cu/Th have been tested in the oxidative dehydrogenation of ethane and propane. These catalysts are active and selective in the formation of ethene and propene, but the activity and selectivity change with the nature of the alkane.     

Enhanced Propene/Propane Separation by Directional Decoration of the 12‐Membered Rings of Mordenite with ZIF Fragments

Propene/propane separation is challenging due to the very small difference in molecular sizes, boiling points and condensabilities between these molecules. Herein, we report a strategy of introducing ZIF fragments into traditional mordenite (MOR) zeolite to decorate the 12‐membered ring of MOR. After decoration, the originally ineffective zeolite MOR exhibited high kinetic propene/propane selectivities (139 at 25 °C) and achieved efficient propene/propane separation. The propene/propane separation potentials of the resulting adsorbents were further confirmed by breakthrough experiments with equimolar propene/propane (50/50) mixtures.