撞击流反应器用于甲醇合成反应

撞击流反应器用于气液固三相甲醇合成反应可以充分发挥其优良的传热、传质性能。在撞击流反应器内,催化剂浆料经喷嘴雾化后成微米尺度的液滴,气液相间接触面积远大于其他三相合成反应器。考察了温度、压力、气体流量、浆料循环量以及喷嘴个数对甲醇合成反应的影响,结果表明,当压力从3.8 MPa上升到5 MPa时,反应器的时空产率增长了近1倍,气体流量达22.4 L·min^-1后时空产率几乎不再变化,增加浆料循环量以及在同一循环量下采用多喷嘴对置都可以增加催化剂时空产率。同时,与固定床、搅拌釜和浆态鼓泡床甲醇合成进行了对比,结果表明,在低空速下撞击流反应器与其他反应器时空产率相当,而在高空速下要优于其他反应器。     

浆态床甲醇合成反应过程数学模拟

在固定床等温积分反应器中回归了LP201催化剂上的甲醇合成反应动力学参数,在液固拟均相、全混流、气相流动形式分别为全混流、平推流的基础上建立了浆态床搅拌反应器中甲醇合成反应的数学模型. 模拟结果显示,根据所得动力学参数,计算结果与实验结果吻合良好;气相甲醇合成过程中气相流动形式明显影响反应效率;在液相甲醇合成过程中,气相的流动形式对反应影响不大;气液传质阻力对反应有较显著的影响,必须与反应过程同时加以考虑.     

浆态床中二氧化碳加氢合成甲醇

研究了浆态床中自行开发的LP201甲醇合成催化剂上二氧化碳加氢合成甲醇的过程。探讨了不同操作条件,如温度、压力、气体空速、原料气配比等对反应的影响;考察了该催化剂在浆态床二氧化碳加氢合成甲醇过程中的稳定性。实验结果表明,浆态床二氧化碳加氢合成甲醇过程中主要产物为甲醇、CO和水;随温度的增加,CO2的转化率和甲醇产率呈现上升的趋势,但甲醇的选择性明显下降;压力的升高有利于CO2的转化率、甲醇产率以及甲醇的选择性提高;原料气空速的提高会增大甲醇产率,但同时降低CO2的转化率以及甲醇的选择性;CO2的转化率、甲醇收率以及甲醇的选择性在氢碳摩尔比4～5获得极大值。LP201催化剂的寿命考察结果表明,该催化剂具有较好的催化活性和稳定性。     

三相床甲醇合成新工艺工程开发研究

在大量的基础数据测定及实验室小试的基础上 ,建立了一套三相床甲醇合成的热模试验装置。在直径 0 .2 0 3m、高 8.2m的鼓泡淤浆反应器内 ,以医用液体石蜡为惰性液相介质 ,在温度 2 10～2 5 5℃、压力 2 .5～ 3.1MPa的条件下 ,在C30 2铜基催化剂上进行三相甲醇合成。试验中着重考察了全套试验装置的运行情况与催化剂活性。结果表明 ,所建立的一套工业侧线试验装置具有良好的操作性和稳定性 ,达到了设计的要求。文中分析了导致催化剂失活的原因及其他工程问题     

合成气制二甲醚三相淤浆床反应器的数学模型研究

A mathematical model for a bubble column slurry reactor is presented for dimethyl ether synthesis from syngas. Methanol synthesis from carbon monoxide and carbon dioxide by hydrogenation and the methanol dehydration are considered as independent reactions, in which methanol, dimethyl ether and carbon dioxide are the key components. In this model, the gas phase is considered to be in plug flow and the liquid phase to be in partly back mixing with axial distribution of solid catalyst. The simulation results show that the axial dispersion of solid catalysts, the operational height of the slurry phase in the bubble column slurry reactor, and the reaction results are influenced by the reaction temperature and pressure, which are the basic data for the scale-up of reactor.     

对撞流反应器甲醇合成实验研究

液相法甲醇合成由于有惰性液体介质的存在,气液相间传质对反应起到了一定的阻碍作用,对撞流反应器使用喷嘴将催化剂浆料雾化从而强化了气液相间传质。文中在对撞流反应器内对甲醇合成温度、合成气比例、气流量、浆料循环量以及喷嘴个数进行了考察,结果表明,温度控制在230℃左右操作比较适宜,二氧化碳参与反应对甲醇合成较为有利,合成气流量在22.4 L/min以后时空产率几乎不再增加,增加浆料循环量和采用对置式二喷嘴或四喷嘴比单喷嘴时空产率和出口甲醇体积分数都有所增加。由结果可知,利用喷嘴雾化和液体对撞可以显著地增强气液传质从而达到增加液相甲醇合成时空产率的目的。     

A Novel Fluidized‐Bed Membrane Dual‐Type Reactor Concept for Methanol Synthesis

A novel fluidized‐bed membrane dual‐type methanol reactor (FBMDMR) concept is proposed in this paper. In this proposed reactor, the cold feed synthesis gas is fed to the tubes of the gas‐cooled reactor and flows in counter‐current mode with a reacting gas mixture in the shell side of the reactor, which is a novel membrane‐assisted fluidized bed. In this way, the synthesis gas is heated by heat of reaction which is produced in the reaction side. Hydrogen can penetrate from the feed synthesis gas side into the reaction side as a result of a hydrogen partial pressure difference between both sides. The outlet synthesis gas from this reactor is fed to tubes of the water‐cooled packed bed reactor and the chemical reaction is initiated by the catalyst. The partially converted gas leaving this reactor is directed into the shell of the gas‐cooled reactor and the reactions are completed in this fluidized‐bed side. This reactor configuration solves some drawbacks observed from the new conventional dual‐type methanol reactor, such as pressure drop, internal mass transfer limitations, radial gradient of concentration, and temperature in the gas‐cooled reactor. The two‐phase theory of fluidization is used to model and simulate the proposed reactor. An industrial dual‐type methanol reactor (IDMR) and a fluidized‐bed dual‐type methanol reactor (FBDMR) are used as a basis for comparison. This comparison shows enhancement in the yield of methanol production in the fluidized‐bed membrane dual‐type methanol reactor (FBMDMR).     

Dynamic Simulation and Optimization of a Dual‐Type Methanol Reactor Using Genetic Algorithms

In this investigation, a dynamic simulation and optimization for an auto‐thermal dual‐type methanol synthesis reactor was developed in the presence of catalyst deactivation. Theoretical investigation was performed in order to evaluate the performance, optimal operating conditions, and enhancement of methanol production in an auto‐thermal dual‐type methanol reactor. The proposed reactor model was used to simulate, optimize, and compare the performance of a dual‐type methanol reactor with a conventional methanol reactor. An auto‐thermal dual‐type methanol reactor is a shell‐and‐tube heat exchanger reactor in which the first reactor is cooled with cooling water and the second one is cooled with synthesis gas. The proposed model was validated against daily process data measured of a methanol plant recorded for a period of 4 years. Good agreement was achieved. The optimization was achieve by use of genetic algorithms in two steps and the results show there is a favorable profile of methanol production rate along the dual‐type reactor relative to the conventional‐type reactor. Initially, the optimal ratio of reactor lengths and temperature profiles along the reactor were obtained. Then, the approach was followed to get an optimal temperature profile at three periods of operation to maximize production rate. These optimization approaches increased by 4.7 % and 5.8 % additional yield, respectively, throughout 4 years, as catalyst lifetime. Therefore, the performance of the methanol reactor system improves using optimized dual‐type methanol reactor.     

Neues Verfahren zur Methanol- und Ammoniak-Synthese. Der Gas/Feststoff/Feststoff-Rieselströmungsreaktor – ein neuer Reaktortyp zur Führung chemischer Gleichgewichtsprozesse

New process for the production of methanol and ammonia. The gas/solids/solids thrickle flow reactor – a new kind of reactor for chemical equilibrium processes . A new process for the production of ammonia or methanol has been developed in the high pressure laboratory of Twente Technical University. The reactants can be made to react completely in a single reactor pass, thus avoiding expensive recirculation. Complete reaction without recirculation is accomplished by a combination of two reversible processes: a chemical reaction and a selective adsorption of the reaction product on a solid in constant flow. On introduction of an inert-gas free stoichiometric mixture of reactants into the reactor, the exhaust gas outlet can be closed. If there is an excess of one of the reactants or of inert gas, it can leave from the top of the reactor. Such a process has been accomplished in a new gas/solids/solids trickle flow reactor in which a granulated adsorbent ?rains”? through a fixed bed of catalyst. The present article describes the use of this kind of reactor for methanol synthesis. Considerable savings in production costs are expected relative to the modern Lurgi low pressure process. A pilot plant is to be built to characterize and evaluate the new process. Royal Dutch Shell has registered a patent application.     

Operability of an Industrial Methanol Synthesis Reactor with Mixtures of Fresh and Partially Deactivated Catalyst

Disposal of spent catalyst is a common practice in industrial methanol synthesis. However, the spent catalyst has, generally, a good level of activity and can be used if mixed with fresh catalyst. In this work the operation of an industrial methanol synthesis reactor with mixtures of fresh and partially deactivated catalyst was investigated using a one‐dimensional transient model. Analysis of the deactivation behavior of low‐pressure methanol synthesis catalyst shows there is an extremely sharp rate of deactivation in a small part of the catalyst life‐time, which is followed by a relatively slow rate of deactivation in the remaining catalyst cycle‐time. Different configurations were studied for catalyst recycling, and two limiting cases are discussed in detail in this paper, namely layered and homogeneous (mixed) bed models. In the first one, the catalyst was segregated into two alternate layers of fresh and partially deactivated catalyst, while in the second homogeneity of the catalyst bed was simulated by segregating a large number of alternate layers of fresh and partially deactivated catalyst. It was observed in both cases that when catalyst recycling is used, the process does not depart significantly from the standard operating conditions, and also that the mixed bed had less influence on the reactor performance than layered one.     

Improved Design of the Lurgi Reactor for Methanol Synthesis Industry

Current studies are devoted to promote the production yield of the methanol synthesis process for treating large feed capacities in Algerian methanol manufacture industry by designing new reactor technologies. In order to achieve a high yield of methanol, the performance of methanol synthesis is improved by substituting the quench reactor by a new Lurgi reactor. The design of operating parameters of the Lurgi reactor involves the effect of CO₂ injection on methanol production yield and the catalyst deactivation. The simulation results demonstrate that under the same industrial operating conditions the conversion rate of reactants increases from 23 % in the quench reactor to 37 % in the Lurgi reactor and the methanol yield can be increased by 33 % when substituting the quench reactor by the Lurgi reactor     

Neue Konvertersysteme für die Methanol-Synthese

New converter systems for methanol synthesis. Far-reaching energy savings in equilibrium reactions requires development not only of better catalysts but also processes with higher conversions in the reactor; wherever possible, so high that recirculation of residual gases is unnecessary. With this aim in mind, two new processes have been developed for methanol production and this paper represents the first report about the second of these processes. The two new reactor concepts are based on the gas/solid/solid-trickling film reactor GSSTFR and the reactor with intermediate product removal RSIPR. In the case of the GSSTFR, the product formed at the catalyst is removed directly from the reactor with a solid adsorbent which moves down through the catalyst bed. Conversions of 100% are achieved in the simplest way – recirculation becomes unnecessary. Savings in investment costs, energy, and raw materials are discussed and compared with the Lurgi process. With the RISPR, high conversions are achieved by selective absorption of the methanol at the temperature of reaction. Tetraethylene glycoldimethylether, TEGDME, is selected as solvent for this purpose. A possible flow scheme is also shown for this process and savings are estimated. Possible savings are so promising that further development on a semi-industrial scale is recommended.     

Synthesis of Dimethyl Carbonate from Methyl Carbamate and Methanol Using a Fixed‐Bed Reactor

Several mixed oxide catalysts were prepared by coprecipitation for dimethyl carbonate (DMC) synthesis from methyl carbamate and methanol. During the batch process, the DMC yield was below 35 %. In order to minimize the unfavorable thermodynamic equilibrium and side reactions for the DMC synthesis, a fixed‐bed reactor was designed. A maximum DMC yield of ～ 73 % could be realized over a ZnO‐Al₂O₃ catalyst. The effects of reaction conditions for this type of reactor were investigated in detail.     

A Novel Radial‐Flow,Spherical‐Bed Reactor Concept for Methanol Synthesis in the Presence of Catalyst Deactivation

A radial‐flow, spherical‐bed reactor concept for methanol synthesis in the presence of catalyst deactivation, has been proposed. This reactor configuration visualizes the concentration and temperature distribution inside a radial‐flow packed bed with a novel design for improving reactor performance with lower pressure drop. The dynamic simulation of spherical multi‐stage reactors has been studied in the presence of long‐term catalyst deactivation. Model equations were solved by the orthogonal collocation method. The performance of the spherical multi‐stage reactors was compared with a conventional single‐type tubular reactor. The results show that for this case study and with similar reactor specifications and operating conditions, the two‐stage spherical reactor is better than other alternatives such as single‐stage spherical, three‐stage spherical and conventional tubular reactors. By increasing the number of stages of a spherical reactor, one increases the quality of production and decreases the quantity of production.     

低温液相甲醇合成鼓泡浆态反应器数学模拟

建立了经由甲酸甲酯的低温液相甲醇合成鼓泡浆态反应器的数学模型 ,模拟了实验室鼓泡浆态反应器的行为 ,并利用模型考察了工艺参数如表观气速、催化剂浓度对反应的影响 ,对改进和提高低温液相浆态床反应器甲醇合成提供了信息 ,以便对开发低温甲醇合成工艺提供参考和指导     

Liquid phase methanol and dimethyl ether synthesis from syngas

The Liquid Phase Methanol Synthesis (LPMeOH^TM) process has been investigated in our laboratories since 1982The reaction chemistry of liquid phase methanol synthesis over commercial Cu/ZnO/Al₂O₃ catalysts, established for diverse feed gas conditions including H₂-rich, CO-rich, CO₂-rich, and CO-free environments, is predominantly based on the CO₂ hydrogenation reaction and the forward water-gas shift reactionImportant aspects of the liquid phase methanol synthesis investigated in this in-depth study include global kinetic rate expressions, external mass transfer mechanisms and rates, correlation for the overall gas-to-liquid mass transfer rate coefficient, computation of the multicomponent phase equilibrium and prediction of the ultimate and isolated chemical equilibrium compositions, thermal stability analysis of the liquid phase methanol synthesis reactor, investigation of pore diffusion in the methanol catalyst, and elucidation of catalyst deactivation/regenerationThese studies were conducted in a mechanically agitated slurry reactor as well as in a liquid entrained reactorA novel liquid phase process for co-production of dimethyl ether (DME) and methanol has also been developedThe process is based on dual-catalytic synthesis in a single reactor stage, where the methanol synthesis and water gas shift reactions takes place over Cu/ZnO/Al₂O₃ catalysts and the in-situ methanol dehydration reaction takes place over -Al₂O₃ catalystCo-production of DME and methanol can increase the single-stage reactor productivity by as much as 80%. By varying the mass ratios of methanol synthesis catalyst to methanol dehydration catalyst, it is possible to co-produce DME and methanol in any fixed proportion, from 5% DME to 95% DMEAlso, dual catalysts exhibit higher activity, and more importantly these activities are sustained for a longer catalyst on-stream life by alleviating catalyst deactivation.     

Hydrodynamics of slurry bubble column during dimethyl ether (DME) synthesis: Gas-liquid recirculation model and radioactive tracer studies

Radioactive tracer measurements, using impulse injections of Ar⁴¹, powdered oxide of Mn⁵⁶ and real catalyst particles doped with an oxide of Mn⁵⁶, conducted at the Advance Fuels Development Unit (AFDU) slurry bubble column (BC) reactor during dimethyl ether (DME) synthesis (reactor pressure of 5.27 MPa, reactor temperature of , inlet superficial gas velocity of 17.1 cm/s, and a catalyst loading of 36 wt%) at LaPorte, Texas, are interpreted. The differences in the responses obtained by the catalyst and fine powdered Mn₂O₃ tracer injections are minimal indicating the validity of the pseudo-homogeneous assumption for the liquid plus solid (catalyst) phase mixtures. The gas-liquid recirculation model [Gupta et al., 2001a. Comparison of single- and two-bubble class gas-liquid recirculation models—application to pilot-plant radioactive tracer studies during methanol synthesis. Chemical Engineering Science 56(3), 1117-1125. 2001b. Hydrodynamics of churn turbulent bubble columns: gas-liquid recirculation and mechanistic modeling. Catalysis Today 64(3-4), 253-269], based on a constant bubble size, describing gas-liquid mass transfer superimposed on turbulent mixing of the gas and liquid phases, is used to simulate the gas, liquid and catalyst tracer responses acquired at the AFDU. The model is able to predict the characteristic features of the experimental responses observed for gas, slurry powder and catalyst tracers at different reactor elevations. The fact, that the same model was previously shown capable of predicting both gas and liquid radioactive tracer responses during methanol and Fischer-Tropsch (FT) synthesis, indicates that this model offers a relatively simple tool for assessing mixing and transport in bubble (BCs) for a variety of gas conversion processes and provides a phenomenologically based framework for BC reactor modeling.     

Modeling of a Reverse Flow Reactor for Methanol Synthesis Modeling of a Reverse Flow Reactor for Methanol Synthesis

An accurate one-dimensional, heterogeneous model taking account of axial dispersion and heat transfer to the reactor wall, and heat conduction through the reactor wall for methanol synthesis in a bench scale reactor under periodic reversal of flow direction is presented. Adjustable parameters in this model are the effectiveness factors for each of the three reactions occurring in the synthesis and a factor for the bed to wall heat transfer coefficient correlation. Experimental data were used to evaluate these parameters and reasonable values of these parameters were obtained. The model was found to closely predict the reactor performance under a wide range of operating conditions, such as carbon oxide concentrations, volumetric flow rate, and cyclic period.     

Optimization of Methanol Yield from a Lurgi Reactor

Methanol is an important chemical with the potential to become an alternative fuel. An optimization study was performed for a Lurgi methanol synthesis reactor using the commercial process simulator Aspen Plus. The optimization routine is coupled with a steady‐state model of the methanol synthesis reactor. Syngas inlet temperature, steam drum pressure, and cooling water volumetric flow rate were optimized so that methanol production in the reactor outlet was maximized. The methanol yield increased by 7.04 %.     

Enhancement of Methanol Production in a Membrane Dual‐Type Reactor

In this study, a dynamic model for a membrane dual‐type methanol reactor was developed in the presence of long term catalyst deactivation. The proposed model is used to compare the performance of a membrane dual‐type methanol reactor with a conventional dual‐type methanol reactor. A conventional dual‐type methanol reactor is a shell and tube heat exchanger reactor in which the first reactor is cooled with cooling water and the second one is cooled with synthesis gas. In a membrane dual‐type reactor, the wall of the tubes in the gas‐cooled conventional reactor is covered with a palladium‐silver membrane, which is only permeable to hydrogen. Hydrogen can penetrate from the feed synthesis gas side into the reaction side due to the hydrogen partial pressure driving force. Hydrogen permeation through the membrane shifts the reaction towards the product side according to the thermodynamic equilibrium. The proposed dynamic model was validated against measured daily process data of a methanol plant recorded for a period of four years and a good agreement was achieved. The simulation results show that there is a favorable profile of temperature and activity of the membrane dual‐type reactor relative to single and conventional dual‐type reactor systems. Therefore, the performance of methanol reactor systems improves when a membrane is used in a conventional dual‐type methanol reactor.