多级串联等体积全混流反应器与平推流反应器等效性研究——以二级可逆反应为例

在多级串联全混流反应器中,在等温等容条件下给出了二级可逆反应第Ⅳ级反应器的出口浓度表达式.讨论了在相同操作条件下,达到平推流反应器的转化率所需要的等体积串联全混流反应器的级数Ⅳ;主要考察了正反应速率常数k1、平衡常数K、反应物初始浓度之比M、停留时间τ等因素对N的影响,得出了N与正反应速率常数k1、相平衡常数K以及停留...     

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。     

膜反应器的数学模型

膜反应器是一种新型的反应装置,具有反应功能和分离功能。以化学反应工程的观点,建立了一级可逆反应的膜反应器的数学模型,通过反应速率和分离速率偶合的联立动力学方程求解方法,使用BASIC语言编制程序,采用IBM微机计算,最后得出关于膜反应器的几个基本结论。通过计算,在一定设计和操作条件下,这些关系对于研究膜反应器是有益的。     

由氢、氧直接合成过氧化氢研发新进展

介绍了氢、氧直接合成过氧化氢过程中催化剂、反应介质、反应器(微反应器、膜反应器等)、操作方式等方面近2～3年来的研发新进展。重点介绍了Au-Pd负载催化剂研究应用情况,涉及不同载体、不同Au与Pd质量比等对过氧化氢生成速率、选择性及浓度的影响。还较详细地介绍了无机酸和卤离子在不同条件下对合成反应结果(包括氢转化率、生成过氧化氢选择率及浓度等)的提高所起到的促进作用及其机理。     

生物柴油新反应器及其应用

生物柴油是石化柴油的重要补充.用传统的搅拌釜和管式反应器制备生物柴油,存在反应速率慢、转化率低的问题.从提高反应速率和转化率两方面综述了生物柴油新反应器的研究进展.提高反应速率的反应器包括:微波反应器、空化反应器、旋转床反应器、振荡流反应器、高剪切反应器、静态反应器、微反应器和液液膜反应器.提高转化率的反应器包括:反应/分离器、反应蒸馏反应器和膜反应器.比较了它们的优势和缺陷.提出联合使用几种技术,将强化传质与分离技术进行有效整合,使反应器小型化并缩短工艺流程,以建立适应未来的生产效率高的便携式生物柴油厂.     

膜反应器中5A分子筛负载氢氧化钾催化合成乙二醇单乙醚

以环氧乙烷和无水乙醇为原料,以负载KOH的5A分子筛为催化剂,在连续操作的膜反应器中合成乙二醇单乙醚.考察了反应温度、KOH负载量及空时对乙醇转化率和乙二醇单乙醚选择性的影响.结果表明,以KOH负载质量分数为17.6%的5A分子筛作为催化剂,在110 ℃和空时2 h的条件下反应,乙二醇单乙醚的选择性达到了88.81%.通过膜反应器与间歇釜式反应器对比实验发现,膜反应器中乙二醇单乙醚的选择性明显高于间歇釜式反应器.     

沸石膜反应器苯脱氢反应性能

采用管式沸石膜反应器,研究了乙苯脱氢反应生成苯乙烯的性能。考察了不同渗透分离性能的沸石膜对乙苯脱氢反应的影响和不同沸石膜反应器上乙苯脱氢反应的规律。结果表明,与固定床操作条件下相比,沸石膜反应器乙苯转化率可提高近10％－16％,苯乙烯选择性可提高3％－5％。渗透分离性能是决定沸石膜提高脱氢反应性能的最重要因素,H2渗透量越大、H2／C3H8分离系数越高,对反应越有利。渗透分离性能相近但类型不同的沸石膜对乙苯脱氢反应性能有差异,其中Fe-ZSM-5沸石膜反应性能较好,这是杂原子Fe进入沸石骨架后引起的。反应后膜的渗透分离性能略有变化。     

液固反应-再生循环流化系统连续合成十二烷基苯

在新型液固循环反应-再生流化系统中研究了十二烷基苯的合成。探讨了反应转化率、表观反应速率常数、催化剂活性因子等随接触及操作时间的变化规律。分析了新工艺中的产物分布。预测了具有工业意义转化率的反应器结构尺寸和操作条件。     

微通道反应器内氯苯硝化反应研究

在微通道反应器内对氯苯硝化反应进行了研究,考察了氯苯与硝酸的摩尔比、体积流速、反应温度等对单程转化率及选择性的影响。实验选择了较优工艺参数组合:n(氯苯)∶n(硝酸)=1∶1.3,n(硝酸)∶n(硫酸)=1∶3,氯苯体积流速0.5 mL/min,反应温度80℃,氯苯单程转化率达74.8%,n(邻硝基氯苯)∶n(对硝基氯苯)=0.56∶1,时空转化率(STC)达4.07×109mol/(m3.h)。微通道反应器内,时空转化率是常规反应器的3.08×104倍。     

强酸性树脂催化合成醋酸甲酯动力学

在釜式反应器中研究了Amberlyst-15强酸性离子交换树脂催化合成醋酸甲酯的反应动力学,考察了搅拌速度、反应温度、催化剂用量等影响因素。结果表明,随着温度的升高,反应速率增大,而反应平衡常数减小;催化剂用量与反应速率常数基本成正比关系。分析并计算得到了酯化反应的动力学参数,建立了反应动力学方程。     

膜污染产生机理及解决办法

分析了膜污染形成机理,对导致膜污染的因素进行了深入探讨;因物理的或物理化学的以及浓差极化作用,会使膜的内外表面受到污染,造成膜通量的下降,分离效率降低;膜本身的结构及其材料性能,水体中污染物的性质与活性对膜污染起着重要的作用;操作条件的改变,可以改善膜污染程度;讨论了膜污染控制方法及膜污染后的清洗方法,可以采用物理法、化学法对被污染的膜进行清洗,能够使其恢复功能。     

国外膜催化剂的研究与应用

对当前国外膜催化技术(包括膜催化剂和膜反应器)的研究和应用作了全面的评述。着重考察了无机膜(各种金属膜和合金膜、陶瓷膜、各种氧化物膜、玻璃膜以及复合膜等)的催化作用,分加氢、脱氢、共轭反应、氧化还原、C_1-化学中的膜催化等进行了综述。分析了苏联、日本和美国等国家发展膜催化技术的作法,对我国开展膜催化研究提出了建议。     

A porous carbon membrane reactor for the homogeneous catalytic hydration of propene

A porous carbon membrane contactor was studied to determine whether such a reactor could be used for homogeneous catalytic reactions. The hydration of propene, catalysed by an aqueous solution of phosphoric acid, was selected as a suitable model reaction. Experiments at high pressure and temperature were conducted in a laboratory-scale gas phase continuous reactor equipped with a flat carbon membrane contactor. It was shown that reasonably stable operation of the reactor could be achieved at high operating pressures by tailoring the porous structure of the carbon membrane and coupling the reactor with an on-line feedback pressure controller. The reactor operated in a mass transfer limited regime due to mass transfer resistance in the liquid filled membrane pores. Periodic oscillation of transmembrane pressure was shown to reduce mass transfer resistance and considerably improve the overall reactor performance.A dynamic model of the reactor was developed and the results of simulations compared favourably with experiments and the performance of a commercially operated conventional reactor employing a supported liquid phase (SLP) catalyst.     

Methanol recycling in the production of biodiesel in a membrane reactor

Membrane reactor technology was used to overcome challenges in biodiesel production. The membrane reactor produces a permeate stream which readily phase separates at room temperature into a fatty acid methyl ester (FAME)-rich non-polar phase and a methanol- and glycerol-rich polar phase. To decrease the overall methanol:oil molar ratio in the reaction system, the polar phase was recycled. Three recycle ratios were tested: 100%, 75% and 50%, at the same residence time and operating conditions. The permeate consistently separated to yield a FAME-rich non-polar phase containing a minimum of 85 wt.% FAME (the remainder being methanol) as well as a methanol/glycerol polar phase. At the highest recycle ratio, the FAME concentration ranged from 85.7 to 92.4 wt.% in the FAME-rich non-polar phase. In addition, the overall molar ratio of methanol:oil in the reaction system was significantly decreased to 10:1 while maintaining a FAME production rate of 0.04 kg/min. As a result, a high purity FAME product was produced.     

Pure hydrogen generation in a fluidized bed membrane reactor: Application of the generalized comprehensive reactor model

A generalized comprehensive model was developed to simulate a wide variety of fluidized-bed catalytic reactors. The model characterizes multiple phases and regions (low-density phase, high-density phase, staged membranes, freeboard region) and allows for a seamless introduction of features and/or simplifications depending on the system of interest. The model is implemented here for a fluidized-bed membrane reactor generating hydrogen. A concomitant experimental program was performed to collect detailed experimental data in a pilot scale prototype reactor operated under steam methane reforming (SMR) and auto-thermal reforming (ATR) conditions, without and with membranes of different areas under diverse operating conditions. The results of this program were published in Mahecha-Botero et al. [2008a. Pure hydrogen generation in a fluidized bed membrane reactor: experimental findings. Chem. Eng. Sci. 63(10), pp. 2752-2762]. The reactor model is tested in this second paper of the series by comparing its simulation predictions against axially distributed concentration in the pilot reactor. This leads to a better understanding of phenomena along the reactor including: mass transfer, distributed selective removal of species, interphase cross-flow, flow regime variations, changes in volumetric flow, feed distribution, and fluidization hydrodynamics. The model does not use any adjustable parameters giving reasonably good predictions for the system of study.     

Steam reforming of methanol over a CuO/ZnO/Al2O3 catalyst part II: A carbon membrane reactor

The reaction of methanol steam reforming was studied in a carbon membrane reactor over a commercial CuO/ZnO/Al₂O₃ catalyst (Süd-Chemie, G66 MR). Carbon molecular sieve membranes supplied by Carbon Membranes Ltd. were tested at 150 °C and 200 °C. The carbon membrane reactor was operated at atmospheric pressure and with vacuum at the permeate side, at 200 °C. High methanol conversion and hydrogen recovery were obtained with low carbon monoxide permeate concentrations. A sweep gas configuration was simulated with a one-dimensional model. The experimental mixed-gas permeance values at 200 °C were used in a mathematical model that showed a good agreement with the experimental data. The advantages of using water as sweep gas were investigated in what concerns methanol conversion and hydrogen recovery. The concentration of carbon monoxide at the permeate side was under 20 ppm in all simulation runs. These results indicate that the permeate stream can be used to feed a polymer electrolyte membrane fuel cell.     

酶膜反应器的应用研究

介绍了酶膜反应器的基本概念,主要就酶膜反应器目前存在的突出问题和相应的解决方法进行了讨论,并对酶膜反应器的前景进行了展望。     

MFI型沸石膜的渗透分离性能及应用

综述了ＭＦＩ型沸石分子筛的渗透分离性能，探讨了其可能的分离机理，并介绍了包括膜分离与经在内的前沿进展。     

A study using classical or membrane separation in the biodiesel process

Biodiesel is a clean burning biofuel produced from renewable resources (straight vegetable oil, animal oil/fats, tallow and waste cooking oil), which can be blended at any level with petroleum diesel to create a blend of biodiesel.The EU has adopted a series of directives to promote and to represent some of the most important renewable energy sources out of biofuels also covering biodiesel as well.The main processing stages currently applied for biodiesel technology are represented by transesterification, neutralization of mixture, phase separation, biodiesel and glycerine purifications. The reaction, generally occurring in a two-stage mixer-settler unit, arises some difficulties for clear cut separations.A new alternative technology, using hydrophobic porous membranes, can be used to prevent bulk mixing of the two phases and facilitate contact and mass transfer of species between the two phases.The glycerine side stream (roughly representing 10% of biodiesel) typically contains a mixture of many components, which are generally difficult to separate. Current methods for glycerine purification are complicated and conducted with higher costs.In this case, the new technology provides an economical solution for the purification of crude glycerine stream combining the high efficiency of electro-dialysis and nano-filtration processes.A comparative cost approach based on available information is sketched. Also, some examples sustain the aim of the study.     

Methane steam reforming modeling in a palladium membrane reactor

A mathematical model of a membrane reactor used for methane steam reforming was developed to simulate and compare the maximum yields and operating conditions in the reactor with that in a conventional fixed bed reactor. Results show that the membrane reactor resents higher methane conversion yield and can be operated under milder conditions than the fixed bed reactor, and that membrane thickness is the most important construction parameter for membrane reactor success. Control of the H₂:CO ratio is possible in the membrane reactor making this technology more suitable for production of syngas to be used in gas-to-liquid processes (GTL).