悬浮催化蒸馏合成甲基叔丁基醚的模拟

建立了悬浮催化蒸馏合成甲基叔丁基醚过程的平衡级模型。利用模型模拟研究了特征参数,特别是固液分离器分率φ和塔底流量B对塔性能的影响。结果表明：参数φ对应的多重定态区域的上界非常小,在实际操作条件下,塔内仅存一个高转化率定态。极限点曲线将参数平面“φ-B”按定态解数目划分成3个子域,其中右上角子域是具有唯一定态且异丁烯转化率高和产物纯度高的操作域。     

Synthesis of High‐Purity Methylal via Extractive Catalytic Distillation

An integrated continuous process, which combines catalytic distillation and extractive distillation in one column, is investigated for the synthesis of high‐purity methylal from methanol and formalin in the presence of a cation‐exchange resin catalyst. A feed with methanol:formaldehyde 2:1 molar ratio is chosen to evaluate the effects of operating parameters, such as extractant feeding position, ratio of extractant to feed, reflux ratio, and reboiler temperature, on the continuous synthesis of methylal. Under the optimum operating conditions and with water as extractant, the extractive catalytic distillation process operated continuously, producing a methylal purity of 98.7 % (H₂O: < 1.30 %) with 98.0 % formaldehyde conversion.     

悬浮床催化蒸馏新工艺合成异丙苯

以丙烯与苯烷基化合成异丙苯作为模型反应 ,对悬浮床催化蒸馏新工艺进行了初步探索 .结果表明 ,只要选择合适的催化剂 ,新工艺不仅能够稳定运转 ,而且可在常压、低温和低苯烯比的条件下取得高转化率、高选择性的较好反应结果 .     

Activity evaluation of a catalytic distillation packing for MTBE production

The octane enhancer methyl tertiary butyl ether (MTBE) can be produced very efficiently from methanol and isobutene in a reactive distillation column where the heterogeneous catalyst also acts as distillation packing. Some mathematical models have been published for the simulation of such a process but they focus on the physical transport processes between the vapour and liquid phases. However, the aim of this paper is to analyze the importance of the internal and external multicomponent mass and heat transfer phenomena on the catalyst under boiling conditions. Therefore, experiments were carried out in a reactive distillation column at different compositions of feed, column pressures and reflux ratios using a Raschig ring shaped acidic ion exchange resin as the catalyst. The temperature and composition of the liquid phase entering and leaving the catalytic column section were measured. These data were used to evaluate the effectiveness factor of the catalyst with a rigorous macrokinetic model. It is shown that the effectiveness factor varies significantly along the column length. Under certain operating conditions, decomposition of MTBE can occur accompanied by boiling processes inside the catalyst macropores.     

Gas-liquid and gas-liquid-solid reactors for the alkylation of benzene with propylene

This work deals with the mathematic models and improvement of four kinds of gas-liquid and gas-liquid-solid reactors for producing cumene by catalytic reaction, i.e., fixed-bed reactor, fixed-bed catalytic distillation (FCD) column, suspension catalytic distillation (SCD) column and ionic-liquid catalytic distillation (ICD) column. The fixed-bed reactor was improved by changing the particle diameter of catalyst and no extra equipment was needed. The FCD and SCD columns were, respectively, improved by carrying out alkylation and transalkylation simultaneously in a column, which also may hold for the ICD column, in which, however, the conductor-like screening model for real solvents (COSMO-RS) was used to take into account the influence of ionic liquid on vapor-liquid equilibrium (VLE).     

On the multiple solutions of the reactive distillation column for production of fuel ethers

A systematic study of the operating conditions and parameter sensibility of multiple steady states in a reactive distillation column for production of fuel ethers is presented. The multiplicity analysis is performed using bifurcation diagrams for several scenarios using the process simulator Aspen One Aspen Plus. Our results indicate that the main variables that affect both the presence and behavior of multiple solutions in the reactive distillation column are the reflux ratio, the reboiler duty and the thermal condition in the feed stream. In particular, we have determined that the vapor–liquid stream in the feed has a major influence on the occurrence of this phenomenon and this parameter especially establishes the type of multiplicity that can occur in the reactive distillation column for production of fuel ethers.     

STUDY ON A CATALYTIC DISTILLATION COLUMN WITH A NOVEL INTERNAL

A novel internal for holding a catalyst in a catalytic distillation column was studied and its feasibility was verified by a model reaction, which is the alkylation of benzene with propylene over Hβ zeolite catalyst. The novel internal enlarges the void of the catalyst bed and provides the gas and liquid flow channels. It was proved that the catalytic distillation column with the novel internal has such advantages as simple structure, low operating cost, convenience for loading and unloading catalyst, and large catalyst loading fraction. It was found that the operational capability of the column with the novel internal whose volume fraction is about 30% is similar to that of a column filled with catalysts mixed with Cannon rings whose volume fraction is about 80%. It was also found that compared with the fixed-bed bubble reactor, the selectivity of cumene and the conversion of benzene are significantly improved in the CD (Catalytic Distillation) column with the internal.     

连续萃取催化精馏制备高纯度甲缩醛

研究了以甲醇和甲醛为原料,大孔径阳离子交换树脂为催化剂,通过将萃取精馏和催化精馏相耦合的方法制备高纯度甲缩醛,证明了这种工艺的可行性。在内径为35 mm、高为2700 mm的玻璃反应精馏塔内进行实验,考察了总进料量、萃取剂进料位置、醇醛摩尔比、回流比以及用甲醛溶液作为萃取剂对甲醛转化率和甲缩醛纯度的影响。在选定的实验条件下,甲醛的转化率可达到97.82%以上,甲缩醛纯度可达到97.64%（含甲醛0.79%、水1.41%、甲醇0.20%）。     

Study on a catalytic distillation column with a novel internal

A novel internal for holding a catalyst in a catalytic distillation column was studied and its feasibility was verified by a model reaction, which is the alkylation of benzene with propylene over Hβ zeolite catalyst. The novel internal enlarges the void of the catalyst bed and provides the gas and liquid flow channels. It was proved that the catalytic distillation column with the novel internal has such advantages as simple structure, low operating cost, convenience for loading and unloading catalyst, and large catalyst loading fraction. It was found that the operational capability of the column with the novel internal whose volume fraction is about 30% is similar to that of a column filled with catalysts mixed with Cannon rings whose volume fraction is about 80%. It was also found that compared with the fixed-bed bubble reactor, the selectivity of cumene and the conversion of benzene are significantly improved in the CD (Catalytic Distillation) column with the internal.     

混合离子液体催化反应精馏合成乙酸正己酯

离子液体催化反应精馏是提高酯交换平衡反应转化率的一种绿色有效方法。以离子液体1-丙基磺酸-3-甲基咪唑三氟甲烷磺酸盐（［PSO₃HMIm］［OTf］）和离子液体1-辛基-2,3-二甲基咪唑双（三氟甲烷磺酰）亚胺盐（［OMMIm］［Tf₂N］）的混合物作为乙酸甲酯和正己醇进行酯交换反应合成乙酸正己酯的催化剂,测定了酯交换反应动力学。探讨了混合比、反应温度、反应物初始摩尔比、催化剂浓度对反应速率和乙酸甲酯转化率的影响,考察了催化剂的回收性能。利用实验数据回归得出混合离子液体催化酯交换反应动力学方程。在反应动力学的基础上进行了乙酸甲酯和正己醇的酯交换反应精馏流程模拟,分析了理论板数、回流比、进料位置及反应段塔板数、催化剂用量、持液量等参数对反应精馏塔的影响。在优化的操作条件下,获得纯度为0.9993的乙酸正己酯产品。     

Hydrolysis of methyl acetate via catalytic distillation: Simulation and design of new technological process

An equilibrium stage model was developed for the simulation of the catalytic distillation process of methyl acetate (MeOAc) hydrolysis. In the model, the influences of the reactive kinetics, residence-time, liquid holdup, and separation efficiency of the catalytic packing were considered. The model predicted the conversion of MeOAc and the mass ratio of acetic acid to water in the hydrolysis mixture. The predictions were in good agreement with experimental data. A novel process was designed based on the results of theoretic analysis and the simulation research. This new process had a higher conversion of MeOAc compared with the results in previous research and was found to be energy efficient. Optimal effect parameters and design factors of new technology on energy consumption and conversion were also determined and summarized as the following: the position of side draw is 18th to 19th stages, the catalytic distillation (CD) column pressure is at 350 kPa, the volume ratio of reflux to feed is 6–8, mole ratio of feed water to MeOAc is 3.5–4.5, and the mass ratio of side withdrawal to feed is 0.32–0.34.     

Synthesis of methylal by catalytic distillation

Methylal is an important raw material and an excellent solvent in industry. The conventional methods for the synthesis of methylal have drawbacks such as corrosion to the equipments, catalyst isolation, high molar ratio of methanol to formaldehyde and high cost of equipments. To overcome these drawbacks, the synthesis of methylal was investigated in a pilot scale catalytic distillation column using Sulzer BX and the structured catalytic packing Katapak-SP 12 in the present study. The reaction was catalyzed by polystyrene based macroporous cation exchange resin (D72) which was filled in the catalystic layers of the structured packings. The effects of operating parameters such as reflux ratio, total feed rate, molar ratio of methanol to formaldehyde, catalyst weight, aqueous formaldehyde concentration were studied experimentally. The appropriate operating parameters obtained in the present study include: reflux ratio is 5; total feed rate is 3.10 kg/h; molar ratio of methanol to formaldehyde is 2.5, catalyst weight is 0.51 kg, aqueous formaldehyde concentration is 35.3%. Under the above operating conditions the average conversion of formaldehyde is 99.6% while the average methylal purity is 92.1%. In order to achieve higher purity of methylal at the top of the column, two different configurations: feeding aqueous formaldehyde and feeding water at mid-way of rectifying section, was tried in the experiments. The experimental results show that the former configuration surpasses the latter, under which the average conversion of formaldehyde is 99.8% and the average methylal purity is 99.1%.     

离子液体催化反应精馏合成乙酸乙酯工艺模拟

为研究离子液体在反应精馏中的作用,采用离子液体1-丁基-3-甲基咪唑硫酸氢盐（[BMIM]HSO₄）作为催化剂,对乙酸和乙醇合成乙酸乙酯的反应精馏流程进行了计算模拟。在确定了参数的酯化反应动力学的基础上,用Aspen Plus软件建立了反应精馏流程,研究了催化剂用量、精馏段理论板数、反应段理论板数、乙醇进料位置、进料摩尔比、持液量及回流比等参数对反应精馏过程的影响。研究结果表明,塔顶乙酸乙酯的质量分数随催化剂用量、精馏段理论板数、反应段理论板数和持液量增大而增大,工艺流程存在最佳回流比以及最佳进料酸醇摩尔比。得到的优化条件如下：离子液体与乙酸摩尔比为1：2.5,进料酸醇摩尔比为4：1,理论塔板数为21块,乙酸和催化剂在第7块理论塔板进料,乙醇在第19块理论塔板进料,塔板持液量0.1L,回流比为4,塔顶乙酸乙酯的质量分数可以达到98.73%。     

催化精馏合成乙二醇乙醚的研究

催化精馏是将固体催化剂布于精馏塔内,它既加速了化学反应,又可作为分离过程的传质表面。本文研究了在内径为35mm的不锈钢塔中,用NKC—01催化剂从乙醇和环氧乙烷合成乙二醇乙醚(单醚)的过程,详细考察了进料比,操作压力,处理量等因素对过程的影响,找到的适宜条件为:进料比(乙醇/环氧乙烷)=6～8(摩尔);处理量为104.0Nm~3环氧乙烷/h(m~3催化剂);操作压力=2.35×10~5Pa。在此条件下乙二醇乙醚对环氧乙烷的收率为90％(mol);环氧乙烷的单程收率为93％;乙二醇乙醚的选择性为97％。为考察塔内的流体力学条件对催化反应的影响,在搅拌容器中测定了过程的反应动力学。为保证此搅拌容器中的液体流速接近塔内操作条件下的流速,以确定适宜的搅拌器转速,我们用DANTEC MODEL 2020激光测速仪测定了不同搅拌器转速下容器中液体的流速。通过研究可以看出:在塔内的操作条件下,与化学反应相比,扩散阻力可以被忽略。     

乙烯和苯催化精馏合成乙苯过程非平衡级模拟

对苯与乙烯合成乙苯的催化精馏过程建立了非平衡级模型 .在计算中对方程进行了一定程度的简化 ,并对变量的取值范围进行了一定的约束 ,使牛顿型法适用性增强 .得到了催化精馏塔内的温度及液相组成分布 .模拟结果与试验结果比较吻合     

Divided wall distillation column: rationalization of degree of freedom analysis

The present work attempts to rationalize the degrees of freedom analysis of a divided wall distillation column for steady-state simulation using detailed mathematical model, which contains the MESHD equations (conventional MESH equation plus the pressure drop equation). In a divided wall distillation column, pressure difference plays an important role in deciding vapour and liquid flow rates across trays in the divided section. It is observed that for a given divided wall distillation column or Petlyuk column operating under steady state conditions with known feed and condenser pressure, the degrees of freedom is four. This is one higher than that for a conventional distillation column with three product streams (distillate, bottoms and the intermediate product). If this extra degrees of freedom is used to specify liquid split, then no extra degrees of freedom is left to specify vapour split ratio.     

浆料催化精馏制备醋酸甲酯

在内径为76 mm的常压玻璃塔内,精馏段填充θ环,反应段为筛板,以甲醇与醋酸酯化反应合成醋酸甲酯为模型反应,采用平均粒径为4μm的强酸性大孔型离子交换树脂为催化剂,对浆料催化精馏工艺制备醋酸甲酯进行了试验研究。考察了催化剂浓度、进料比、进料总流量和回流比等因素对该过程的影响。在选定的试验条件下,醋酸甲酯收率可达86.4%,塔顶酯的纯度可达92.95%(质量分数)。     

离子液体催化反应精馏合成乙酸乙酯

利用1-己基吡啶四氟硼酸盐离子液体作溶剂和催化剂,在催化反应精馏塔内合成乙酸乙酯。结果表明该离子液体具有催化活性,反应的选择性为100%,分离后的1-已基吡啶四氟硼酸盐离子液体重复使用5次,其活性没有明显变化。考察了回流比、进料比、溶剂和催化剂用量对酯化反应结果的影响,优化了反应的工艺条件,适宜的反应条件为:物料比n(乙酸):n(乙醇)=1.1:1,离子液体用量n(乙酸):n(离子液体)=8:1,回流比为3。     

Optimal design of catalytic distillation columns: A case study on synthesis of TAEE

The design of catalytic distillation (CD) columns is a challenging task because of the superposition of chemical reaction and distillation in one apparatus. In this work, a method to design a cost-optimal CD column for chemical systems with large number of components and chemical reactions is presented. The method is based on the following steps: (1) estimation of the number of theoretical stages and catalyst volume by the decomposition of the CD column into a sequence of chemical reactors and non-reactive distillation columns, (2) estimation of the column diameter and operating conditions using an equilibrium stage model, and (3) design of the column applying an optimisation algorithm and using a rigorous non-equilibrium stage model to represent the CD process. The method is applied to determine the optimal column configuration and operating conditions for the synthesis of tert-amyl ethyl ether from ethanol and isoamylenes. Eight components and four chemical reactions were selected to represent the chemical system in the simulations.     

Design and control of butyl acrylate reactive distillation column system

In this study, the design and control of a reactive distillation column system for the production of butyl acrylate has been investigated. The proposed design is quite simple including only one reactive distillation column and an overhead decanter. The optimal design is selected based on the minimization of total annual cost (TAC) for the overall system. At this optimized flowsheet condition, output multiplicity was found with reboiler duty or feed ratio as the bifurcation parameter. The highest purity stable steady state was selected as the base case condition for the control study. The overall control of this system can be achieved with no on-line composition measurements. Simple single-point tray temperature control loop is designed to infer final product purity. From results of dynamic simulation, the proposed control strategy performs very well in rejecting various disturbances while maintaining butyl acrylate product at high purity. One of the important finding in this paper is that it is better to operate this reactive distillation column not at the exact feed stoichiometric balance point for better operability reason. The control performances of the proposed operating point and the operating condition right at the exact stoichiometric balance point will be compared.