煤制甲醇项目原料气深度净化精脱硫工艺方案和催化剂选型研究

介绍了煤制甲醇项目合成气深度净化脱硫催化剂和CO_2原料气脱硫催化剂的应用情况,以神华宁煤100万t/a煤制甲醇装置为例,研究将合成气和CO_2原料气中硫脱除的工艺设计和催化剂选型。结果表明,CO_2原料气设置COS水解反应器,选用K、Na金属负载催化剂将CO_2中的COS转化为H_2S,合成气和CO_2原料气混合后再设置深度净化精脱硫反应器,选用ZnO型催化剂将硫脱除至5μg/m~3以下,满足甲醇合成催化剂要求的入口总硫控制在30μg/m~3以下的要求。     

上流式反应器气液相间传质特性的实验研究

上流式反应器设置在固定床渣油加氢反应器前有利于提高渣油原料适用性,延长装置运行时间。实验研究了上流式反应器气液相间传质,采用五齿柱形氧化铝催化剂模拟工业催化剂颗粒,水溶液模拟渣油,空气模拟氢气,采用无氧水物理吸收和亚硫酸钠化学吸收的方法,测定了在高气液比的条件下上流式反应器床层气液相间传质特性实验。考察了表观气速、表观液速、填料粒径、内构件、催化剂级配和床层高径比对液相体积传质系数和气液相界比表面积的影响规律。实验数据表明,液相体积传质系数随着气、液速的增大而增大;随填料颗粒增大而减小;在床层内安装合适的内构件或增大反应器高径比,能够促进气液相间传质。基于实验数据拟合了适合上流式反应器液相体积传质系数和气液相界比表面积的经验关联式,拟合误差最大分别为12%和24%;表明所建气液相间传质的经验关联式能更好地预测上流式反应器中的气液相间传质特性。     

上流式反应器气液相间传质特性的实验研究

上流式反应器设置在固定床渣油加氢反应器前有利于提高渣油原料适用性,延长装置运行时间。实验研究了上流式反应器气液相间传质,采用五齿柱形氧化铝催化剂模拟工业催化剂颗粒,水溶液模拟渣油,空气模拟氢气,采用无氧水物理吸收和亚硫酸钠化学吸收的方法,测定了在高气液比的条件下上流式反应器床层气液相间传质特性实验。考察了表观气速、表观液速、填料粒径、内构件、催化剂级配和床层高径比对液相体积传质系数和气液相界比表面积的影响规律。实验数据表明,液相体积传质系数随着气、液速的增大而增大;随填料颗粒增大而减小;在床层内安装合适的内构件或增大反应器高径比,能够促进气液相间传质。基于实验数据拟合了适合上流式反应器液相体积传质系数和气液相界比表面积的经验关联式,拟合误差最大分别为12%和24%;表明所建气液相间传质的经验关联式能更好地预测上流式反应器中的气液相间传质特性。     

多室气升式环流反应器传质特性

以Higbie的渗透理论为基础,建立了多室气升式环流反应器体积传质系数的模型方程．用亚硫酸钠空气氧化法测定反应器的比表面积和体积传质系数,讨论了表观气速和催化剂浓度对它们的影响,并验证了模型的适用性。     

基于CFX的规整催化剂甲烷化反应器流场模拟与结构优化

煤制天然气可有效解决天然气消耗量持续增加、环保等问题。甲烷化反应是煤制天然气重要环节。在众多甲烷化催化剂中,规整催化剂由于传热、传质、反应特性、压降性能良好,受到广泛关注。而规整结构催化剂的孔道独立,与反应器轴线垂直截面的流场均匀度对产物产率影响很大。基于CFX以反应器内流场均匀度为目标,对规整催化剂固定床甲烷化反应器进行冷态数值模拟,获得最优反应器结构。     

具有内循环管的鼓泡塔液体轴向的循环速度

<正> 一、引言 气液反应是相当复杂的反应,其产品收率不仅取决于催化剂和化学反应动力学的特性,而且与工业反应器内热和质的传递关系密切,很多反应受传质控制。因此,选择并设计合理的反应器结构,就成为液相反应十分重要的问题。 随着近代化学反应工程的发展,已开发了各种各样的气液反应器,鼓泡塔是其中较     

气固两相流内中空多孔催化剂性能的数值模拟

气固流态化过程中流体和颗粒分别聚集,形成稀密两相,严重限制其传质效率和反应速率的提高。针对此问题,本工作设计了一种中空多孔结构的催化剂颗粒,通过模拟方法研究该颗粒对稀密两相气相传质与反应的影响,及其在稀密相间转换的时间尺度。结果表明,一定的流动强度时,在颗粒稀密相转换的时间尺度内,中空多孔结构的颗粒能够有效地在稀相存储反应气体,并在密相释放,为密相提供额外的反应气体,增强体系的整体反应效率。当催化反应速率高于传质速率时,在所研究的流动条件下中空多孔颗粒体系的反应效率比实心球形颗粒体系高出26.92%~29.55%。可以预见在稀密相分布更广的大型气固流化床反应器中,中空多孔结构的催化剂颗粒能够更为有效地提高反应器的整体效率。     

面向催化剂快速表征的串联微反应器系统设计

探讨了一种串联微反应器的设计。此串联微反应器由上下2层各自可以实现独立温控的微反应器组成。上层微反应器(微反应器1)用于预热气体、蒸发液体或使有机固体热分解形成一个气相样品。装满催化剂的催化剂反应管放置于下层微反应器(微反应器2)。气化物从上层微反应器流入下层微反应器的反应管,与其中催化剂进行反应。质量流量控制器控制1/3上层微反应器流出的反应气化物作为气相样品,进入下层微反应器催化剂床。从下层微反应器流出反应产物直接进入气相色谱仪进行分析。通过质谱检测评估催化剂的化合物组成及相对分布。通过对纤维素、甘油和麻风树"压饼"的转化,说明了此串联微反应器快速表征一种催化剂或一系列的催化剂的便捷和价值。     

逆向涓流床中稀乙烯液相烷基化制乙苯的研究

在逆向涓流床中考察了稀乙烯液相法反应精馏制乙苯反应器的传质和反应特性,获得了气液膜无因次传质准数ShL的关联式,并对FX-02沸石原颗粒催化剂进行宏观动力学的研究。     

内循环光催化反应器降解甲基橙废水的研究

利用自行研制的内循环光催化反应器，以紫外灯光为光源、二氧化钛为催化剂，降解甲基橙废水。试验表明，催化剂、传质、废水色度对光催化降解效率影响显著。本反应器具有良好的气－液－固传质。在最佳实验条件下废水色度去除率≥90％，取得了较好的处理效果。光催化技术对废水的深度处理有广阔的应用前景。     

Mass transfer in the spinning catalyst basket reactor

A mathematical model is derived for the evaluation of the relative velocity between the gas and the pellets in two configurations of the spinning catalyst basket reactor. This slip velocity is then used to calculate the particle Reynolds number and hence mass transfer coefficients from well known correlations for mass transfer in packed beds. Experimentally determined mass transfer coefficients were found to be in good agreement with the model. The effect on mass transfer rates of the position of the pellet and rotor dimensions for the cruciform spinning catalyst basket reactor is seen to be well predicted from the model. The performance of a typical spinning catalyst basket reactor is calculated when a catalytic oxidation reaction takes place at various jacket temperatures and rotational speeds.     

Measurement and enhancement of gas-liquid mass transfer in milliliter-scale slurry reactors

Due to the limited availability of chemical reactants in the early process development of pharmaceuticals and fine chemicals, and sometimes the high-cost of catalyst, it is increasingly popular to use milliliter-scale slurry reactors with reaction volumes of 20 ml or less to screen catalyst candidates for three-phase reactions. To ensure the success of catalyst screening, it is advantageous to run reactions under kinetically controlled conditions so that the activities of different catalysts can be compared. Because catalysts with small particle sizes are used in slurry reactors, the reactions are susceptible to gas-liquid mass transfer limitations. This work presents an efficient way of enhancing gas-liquid mass transfer in milliliter-scale reactors through the use of magnetically driven agitation with complex motion. In the reactor described here, gas-liquid mass transfer coefficients can be doubled over those obtained with the agitation technique used in commercial milliliter-scale units. In addition, the reactor can achieve the top range of mass transfer coefficients obtained in a full-scale reactor. This work also presents the first measurements of gas-liquid mass transfer coefficients in milliliter-scale reactors, which are two orders-of-magnitude smaller than systems for which mass transfer coefficients have been reported earlier. Both physical and chemical absorption techniques are used.     

Characterizing the catalyst fluidization with field synergy to improve the amine absorption for CO_2 capture

There are great interests to capture the CO_2 to control the greenhouse gas emission. Amine absorption of CO_2 is being taken as an effective way to capture CO_2 in industry. However, the amine absorption of CO_2 is cost-ineffective due to great energy consumption and solution consumption. In order to reduce the capture cost, catalyst fluidization is proposed here to intensify the mass transfer and heat transfer. Catalyst fluidization with field synergy and DFT model is developed by incorporating the effects of catalyst reaction kinetics, drag force and multi-field into the mass transfer, heat transfer, fluid flow and catalyst collision. Experiments with an improved distributor are performed well to validate the model. The reaction kinetics is determined by the DFT simulation and experiment. The mass transfer coefficient in the fluidized reactor is identified as 17% higher than the conventional packed reactor. With the field synergy of catalyst fluidization, the energy consumption for CO_2 desorption is reduced by 9%. Stepwise operation and inclination reactor are used to improve catalyst fluidization process.     

Characteristics of the reactive distillation column with a novel internal

A new catalyst loading method, in which catalyst particles are packed in a reactor with a novel internal, has been studied by measuring pressure drop, RTD, liquid holdup and mass transfer. It can be inferred from experimental results that the internal changes the conventional gas and liquid counter-current flow into a new cross-current flow, so the problems of excessive pressure drop and “flooding” are avoided. When pressure drop, liquid holdup, RTD and mass transfer coefficient are similar, the catalyst loading fraction of the new method is much higher than that of conventional methods. Furthermore, the reactive distillation reactor with the novel internal has advantages such as simple structure, low operating cost, and convenience for installation and removal of the catalyst.     

Hydrodynamik und Stofftransport in einem Perlschnurreaktor für Gas/Flüssig/Fest‐Reaktionen

In this work, a pellet string reactor was characterized with respect to hydrodynamics and mass transfer. The catalyst packing consists of a cylindrical channel with a diameter of 1.41 mm, which was filled with spherical catalyst particles, having an outer diameter of 0.8 mm. Under reaction conditions (liquid phase hydrogenation of α‐methylstyrene) overall (gas‐liquid‐solid) volumetric mass transfer coefficients for hydrogen between 0.8 and 5.5 s^–1 were computed. Due to high mass transfer rates and simple reactor geometry, pellet string reactors can be applied in industry as highly efficient reaction units.     

Oxidation of ethyl alcohol in trickle bed reactors: Analysis of the conversion rate

The interpretation of results of a chemical reaction carried out in a trickle bed reactor is not immediate when the key reactants are volatile; in fact some authors state that the overall conversion rate increases at very low liquid flow rates, i.e. when the catalyst is unevenly wetted. In these conditions, the reactants may penetrate inside the catalyst pellets directly through the “dry” zones; therefore the mass transfer resistance is diminished and the conversion rate can be increased. To investigate this phenomenon tests on the catalytic oxidation of ethyl alcohol dissolved in water were performed at different operating conditions in a trickle bed reactor. An interpretation of the results was tried by using two different models based on partially wetted particles. This approach considers both the cases in which “dry” zones are active or not for mass transfer and mass transfer rates are affected or not by the chemical reaction.     

在微结构反应器中制备双酚A环氧丙烯酸树脂

为了解决釜式反应器制备双酚A环氧丙烯酸树脂(EA)过程中存在温度控制难、反应周期长和稳定性差等问题,采用具有高效传热和传质能力的微结构反应器来合成EA。研究了反应温度、流速、停留时间、催化剂种类及用量、管径对反应的影响,优化出最佳制备工艺。采用傅里叶红外光谱(FT-IR)对产物EA结构进行了表征。结果表明:应用微结构反应器可以成功制备EA。最佳制备条件如下:反应温度140 ℃,流速3.05 mL/min,停留时间4 min,管径1 mm,催化剂选用三苯基膦且用量为双酚A环氧树脂(EP)质量的2%。在最佳制备条件下,丙烯酸和环氧基的转化率分别为99.1%和96.3%。固化涂膜的附着力、铅笔硬度和耐磨性等,均达到了使用要求。     

Comparison of different reactor types for low temperature Fischer-Tropsch synthesis: A simulation study

The commercially established slurry bubble column and fixed-bed reactors for low temperature Fischer-Tropsch synthesis were compared with novel micro- and monolith-reactors by mathematical modeling. Special attention was paid to the influence of catalytic activity on the reactor efficiency and the losses by mass and heat transfer resistances. The simulation results show that a micro-structured reactor exhibits the highest productivity per unit of catalyst volume followed by slurry bubble column reactor and monolith reactor. The fixed-bed reactor that was assumed to operate in the trickle-flow regime has a particularly low catalyst specific productivity due to severe mass transfer resistances. However, caused by a very low ratio of catalyst and reactor volume the micro-reactor has only a similarly low productivity per unit of reactor volume as the fixed-bed reactor. In contrast, the reactor specific productivity of slurry bubble column reactor and monolith reactor is up to one order of magnitude higher.     

The gas–liquid contacting effect on the operation of small scale upflow hydrotreaters

The effect of reactor geometry and bed dilution on the extent of gas oil hydrodesulfurization was tested by conducting hydrodesulfurization experiments in two laboratory reactors of different scale with non-diluted and diluted beds in ascending flow. The superficial gas and liquid velocities and the catalyst bed height were kept constant while the main difference between the two reactor scales was the reactor diameter. The diluted bed of the mini-reactor showed the best performance and its results were identical in upflow and downflow mode. The differences between the performance of the mini- and the bench-scale reactor operating in upflow mode have been investigated. Reactor performance simulation was attempted by a mathematical model that takes into account axial dispersion of the liquid phase and gas–liquid mass transfer. Bench-scale reactor operation was characterized by lower mass transfer rates than the corresponding mini-scale one. Combining model predictions and mock up operation it is concluded that the stronger mass transfer resistances calculated for the bench-scale reactor are associated with poorer gas distribution through the catalyst bed. Reduction of the bed diameter results in better gas–liquid contact by forcing the gas bubbles to distribute more effectively into the liquid phase.     

Design of novel Pt-structured catalyst on anodic aluminum support for VOC’s catalytic combustion

Emission control of volatile organic compounds (VOCs) is one of the priorities for environmental catalysis. Catalytic combustion is one of promising technologies for elimination of VOCs. A novel platinum-structured catalyst was designed and is presented in this work. Aluminum was used as support for the catalyst after anodic oxidation treatment and in a shifted arrangement bent, short channels are applied in the design of the structured catalyst. The simulation results show that the novel design of the structured catalyst brings in the higher catalytic activity, compared with the traditional structured catalyst which has long, straight channels. Lastly, the novel structured catalyst was manufactured and its catalytic activity was evaluated with the catalytic combustion of VOC. The results show that the conversion obtained from the reactor with the structured catalyst is almost identical to that obtained from the tube reactor packed with the plate catalyst in which the reaction rate is controlled by surface reactions. Hence, it can be concluded that the mass transfer can be improved by the novel design of the structured catalyst and that the mass transfer in gas phase is not the rate-determining step for the catalytic combustion of VOC.