钯膜反应器柴油重整制氢模拟与验证

为了研究钯膜反应器柴油重整制氢工艺的反应规律,对其进行热力学和动力学建模,并通过实验验证模型的准确性。采用顺序模块法将钯膜反应器分为连续的子反应器和子分离器,模拟钯膜反应器的反应分离耦合过程,通过灵敏度分析,研究钯膜反应器中各反应因素等对氢气收率的影响规律。结果表明,钯膜反应器较无膜反应器可突破热力学平衡的限制,减小反应体积,在低温下可获得较高的氢气产率。在一定条件下模拟结果与实验值误差为8.9%,证明该仿真模型可对实验研究起到预测和指导作用。     

钯膜及钯膜反应器的研究进展

钯基膜具有很高的透氢速率和透氢选择性以及良好的化学和热稳定性,一直是膜技术领域的研究热点。文章综述了钯膜的透氢原理、钯膜制备方法及钯膜反应器的研究进展。重点介绍了钯膜反应器在加氢、脱氢等反应中的应用,并对钯膜反应器的发展趋势进行了展望。     

钯膜及钯膜反应器的研究进展

钯基膜具有很高的透氢速率和透氢选择性以及良好的化学和热稳定性,一直是膜技术领域的研究热点。文章综述了钯膜的透氢原理、钯膜制备方法及钯膜反应器的研究进展。重点介绍了钯膜反应器在加氢、脱氢等反应中的应用,并对钯膜反应器的发展趋势进行了展望。     

氢气燃烧对自热透氢膜反应器的影响

设计了一种新型的钯膜自热反应器体系,利用钯膜的透氢和换热的作用,燃烧部分氢气来提供热量。通过建立一维拟均相管壳式结构的膜反应器模型,将反应器控制方程、动力学数据、膜渗透数据,以及组分的物理化学性质通过Matlab编程计算,比较了氢气均相燃烧和催化燃烧2种动力学对反应器的影响。结果表明,在没有燃烧催化剂的情况下,反应器易发生爆炸,而有催化剂可以避免爆炸,并且能够提高反应器的处理量。指出催化燃烧加快氢气燃烧速率、避免氢气在燃烧一侧的积累是反应器安全操作的关键。     

管状钯膜反应器中的脱氢反应与氢气分离

讨论了钯膜反应器的实验装置及环己烷的脱氢反应实验方法。对环己烷的脱氢反应及氢气通过钯膜的渗透建立了扩散模型，使用状态－变量法求解偏微分方程组，得出反应物和生成物的组分浓度分布，进而求出反应转化率。同实验结果对比表明，扩散模型能较好地计算脱氢反应及氢气的分离过程。     

流化床膜反应器的应用研究进展

流化床膜反应器中所采用的膜主要有2类,一类为钯(及其合金)膜,另外一类为透氧膜.介绍了近十几年来流化床膜反应器的新型应用研究,主要集中在反应器概念设计、膜及其透过性能、以及流化床流体特性.提出未来有必要对流化床膜反应器中化学反应与膜分离过程的耦合这一关键科学问题进行深入的研究,揭示膜对流化床流体力学特性的影响和流化床对膜透过性能的影响机理,以及这两个过程的耦合机制.     

超薄钯膜的制备

超薄钯膜的制备具有超薄、稠密的或表层的合成膜能够把氢从混合气体中分离出来，并被用于氢化作用、脱氢作用的反应器膜。这项研究包含陶器底物的减轻、基于ＡＩ。Ｏ。或ＳＩＯ。薄层上的具有超薄钯表层的膜的制备以及渗透实验。在不同的温度下，Ｎ２、Ｈ２混合气体对合成...     

钯膜的应用

介绍了钯膜在制取烯烃和氢气的反应系统中的应用。由于使用了钯膜,在甲烷、甲醇蒸气重整反应中降低了反应温度,在丙烷、异丁烷、乙苯脱氢中均提高了反应物的转化率以及目的产物的选择性。在氨催化分解、水煤气转化、除去水中硝酸盐的反应中使用钯膜也得到了令人满意的效果。     

钯膜反应器制氢研究进展

钯膜与水蒸汽重整反应器集成使反应与分离一体化,在降低装置投资成本和节能降耗方面具有明显优势和发展前景,受到研究者的青睐。综述了固定床和流化床钯膜反应器规模验证方面的研究进展,并指出钯膜反应器制氢工业化进程中可能会遇到的问题和需要解决的问题。     

钯复合膜反应器中异丁烷催化脱氢反应

引　言异丁烷脱氢反应是一个受热力学平衡限制的反应 ,平衡转化率很低 ,若将膜反应器用于该反应 ,则可以通过膜不断地从反应区选择性分离出氢气 ,克服了反应受热力学平衡制约的缺点 ,这样就可降低反应温度和减压程度的要求 ,改善反应的工艺条件 ,从而达到高效和节能的目的 .文献中已分别对钯 /陶瓷复合膜[1,2 ]和钯 -钌 (钌的质量分数为 2 % )合金膜[3]反应器中的异丁烷脱氢反应进行了初步研究 .前文[4 ]已对用改进的化学镀新工艺制备的钯和钯 -银 /陶瓷复合膜进行了表征 ,本文将用钯-银 /陶瓷复合膜反应器进行异丁烷脱氢反应的研究 .本工作…     

多孔膜反应器中丙烷催化脱氢制丙烯的模拟研究

针对丙烷高效脱氢制丙烯的多孔膜反应器构建了无量纲数学模型并进行了模拟研究,考察了催化剂活性、透氢膜性能、操作条件对多孔膜反应器中丙烷脱氢的转化率、丙烯收率、氢气收率和纯度的影响。结果表明,移走产物氢气可以有效提升膜反应器的性能,其性能的提升程度由不同温压条件下催化剂和透氢膜性能共同决定。高活性催化剂是丙烷高效转化的基础,催化剂活性越高,膜反应器内的产氢速率越快;其次,膜的选择性和渗透通量越高,氢气的移除效率越高,可在最大程度上打破热力学平衡的限制,使反应向生成丙烯的方向移动。当多孔透氢膜的氢气渗透率在10^-7~10^-6 mol·m^-2·s^-1·Pa^-1,H₂/C₃H₈选择性达到100时,其丙烷转化率可以与Pd膜反应器内的转化率相当,但分离的氢气纯度低于Pd膜反应器。与传统的固定床反应器相比,膜反应器由于促进了化学平衡的移动,可以在较低的反应温度下获得相当高的丙烷转化率,且丙烷转化率随着反应压力的增加呈现出一个最大值。该模拟研究可为实际生产过程中膜反应器用于PDH反应的高效强化提供有益的技术指导。     

Advances on methane steam reforming to produce hydrogen through membrane reactors technology: A review

Methane steam reforming is the most common industrial process used for almost the 50% of the world’s hydrogen production. Commonly, this reaction is performed in fixed bed reactors and several stages are needed for separating hydrogen with the desired purity. The membrane reactors represent a valid alternative to the fixed bed reactors, by combining the reforming reaction for producing hydrogen and its separation in only one stage. This article deals with the recent progress on methane steam reforming reaction, giving a short overview on catalysts utilization as well as on the fundamentals of membrane reactors, also summarizing the relevant advancements in this field.     

A novel dynamic membrane reactor concept with radial‐flow pattern for reacting material and axial‐flow pattern for sweeping gas in catalytic naphtha reformers

Naphtha reforming units are of high interest for hydrogen production in refineries. In this regard, the application of membrane concept in radial‐flow tubular naphtha reactors for hydrogen production is proposed. Because of the importance of the pressure drop problem in catalytic naphtha reforming units, the radial‐flow reactors are proposed. A radial‐flow tubular membrane reactor (RF‐TMR) with the radial‐flow pattern of the naphtha feed and the axial‐flow pattern of the sweeping gas is proposed as an alternative configuration for conventional axial‐flow tubular reactors (AF‐TR). The cross‐sectional area of the tubular reactor is divided into some subsections in which walls of the gaps between subsections are coated with the Pd‐Ag membrane layer. A dynamic mathematical model considering radial and axial coordinates ((r, z)‐coordinates) has been developed to investigate the performance of the new configuration. Results show ～300 and 11 kg/h increase in aromatic and hydrogen production rates in RF‐TMR compared with AF‐TR, respectively. Furthermore, smaller catalyst particles with higher efficiency can be used in RF‐TMR due to a slight pressure drop. The enhancement in aromatics (octane number) and hydrogen productions owing to applying simultaneously the membrane concept and radial‐flow pattern in naphtha reactors motivates the application of RF‐TMR in refineries. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Optimal conditions of isobutane dehydrogenation in radial flow moving bed hydrogen-permselective membrane reactors to enhance isobutene and hydrogen production

In the isobutane dehydrogenation process, coupling reaction and separation and optimization of the intensified process can improve the isobutane conversion and selectivity, reduce operational costs and lets to produce pure hydrogen. In this research, the radial flow moving bed reactors in the Olefex technology have been supported by Pd–Ag membrane plate to remove hydrogen from the reaction zone. The reactions occur in the tube side and the hydrogen is permeated from the reaction zone to the sweep gas stream. The proposed configuration has been modeled heterogeneously based on the mass and energy conservation laws considering reaction networks. To prove the accuracy of the considered model, the simulation results of the conventional process have been compared against available plant data. The Genetic algorithm as an effective method in the global optimization has been considered to optimize the operating condition of membrane reactors to enhance isobutene productivity. In this optimal configuration, the isobutene production has been enhanced about 3.7%.     

Oxidation by electrogenerated mediator: influence of perfluorosulfonic separator on process performance

The electrogenerated mediator oxidation process is capable of oxidizing organic compounds to the final step, producing CO2. It requires the use of separate compartments for the anode and cathode. A considerable electric charge is necessary to decompose long carbon chains and high-intensity electrochemical reactors are needed for use at industrial scale. A variety of porous and microporous ceramic separators (frits) have been used in industrial-scale electrochemical cells, for example, hollow cylinders made of various porous ceramics have been used to build annular cells. However, these separators exhibit a high electric resistance and one alternative is to use a perfluorosulfonic ion-exchange membrane. It is, therefore, essential to determine the flows through this membrane in order to optimize process operation. The authors describe the ion and water flows through the membrane, and their influence on the process.     

Hydrogen production from methanol by oxidative steam reforming carried out in a membrane reactor

The aim of this work is to study from an experimental point of view the oxidative steam reforming of methanol by investigating the behaviour of a dense Pd/Ag membrane reactor (MR) in terms of methanol conversion as well as hydrogen production. The main parameters considered are the operating temperature and the O₂/CH₃OH feed ratio. This is a pioneer work in the application of MR to this kind of reaction, whose goal should be to produce a CO-free hydrogen stream suitable for hydrogen fuel cell applications. The experimental results show that the MR gives methanol conversions higher than traditional reactors (TRs) at each temperature investigated, confirming the good potential of the membrane reactor device for this interesting reaction system.     

Pd-Decorated Tungsten as Pt-Free Bimetallic Catalysts for Hydrogen Oxidation Reaction in Alkaline Electrolyte

Developing Pt-free catalysts for hydrogen oxidation reaction (HOR) in alkaline solution is becoming a key challenge in the development of anion exchange membrane fuel cells and electrochemical reactors. Herein, we present the preparation, HOR activity, and stability of Pd-decorated tungsten (Pd-d-W) catalysts. The Pd-d-W catalysts were prepared by the chemically activated surface of tungsten nanoparticles by Pd ions. The resultant bimetallic catalysts consisted of crystalline phases of both Pd and W nanoparticles. The CO stripping voltammograms and H-desorption (H_des) peak potential of hydrogen desorption in Pd suggests that the enhancement of HOR catalytic activity observed in Pd-d-W catalyst can be ascribed to the modification of electronic property of Pd and availability of OH_ad near-surface Pd atoms.     

Facile surface modification of porous stainless steel substrate with TiO2 intermediate layer for fabrication of H2-permeable composite palladium membranes

The increasing demand in compact hydrogen separators greatly stimulated the investigation and utilization of composite palladium membranes. Porous stainless steel (PSS) tubes were chosen as substrate material in this study, and a novel process of carbon-assisted solid-state sintering was introduced to modify the PSS surface with a TiO₂ layer. A Pd/TiO₂/PSS membrane with a Pd thickness of 6 µm was successfully fabricated via electroless plating. Scanning electron microscopy (SEM), metallographic microscopy, X-ray diffraction and pore-size analyses were performed for material characterizations. As measured by H₂/N₂ single-gas testing, the fabricated Pd/TiO₂/PSS membrane is permeable and selective to hydrogen, and it was stable during a time-on-stream of 100 h under 450°C.     

A hybrid adsorbent-membrane reactor (HAMR) system for hydrogen production

Design characteristics and performance of a novel reactor system, termed a hybrid adsorbent-membrane reactor (HAMR), have been investigated for hydrogen production. The recently proposed HAMR concept couples reactions and membrane separation steps with adsorption on the membrane feed-side or permeate-side. Performance of conventional reactors has been significantly improved by this integrated system. In this paper, an HAMR system has been studied involving a hybrid-type packed-bed catalytic membrane reactor undergoing methane steam reforming through a porous ceramic membrane with a CO₂ adsorption system. This HAMR system is of potential interest to pure hydrogen production for fuel cells for various mobile and stationary applications. Reactor behaviors have been investigated for a range of temperature and pressure conditions. The HAMR system shows enhanced methane conversion, hydrogen yield, and product purity, and provides good promise for reducing the hostile operating conditions of conventional reformers, and for meeting the product purity requirements.     

High purity hydrogen production by low temperature catalytic ammonia decomposition in a multifunctional membrane reactor

Catalytic ammonia decomposition for the generation of high purity CO_x free hydrogen has been performed in a multifunctional membrane reactor with Pd membrane walls for the hydrogen separation and a high performance Ru-carbon catalyst. By adjusting the experimental conditions an enhancement of the efficiency of the system for the hydrogen production has been achieved. The chemical thermodynamic equilibrium conversion has been exceeded using an improved catalyst, at temperatures lower than those reported in the literature. In addition, both the membrane and the catalyst components were very stable. The system showed no loss of performance after having been operated for several cycles.