2-Methylpropylacetate synthesis via catalytic distillation

The paper deals with a 2-methylpropylacetate synthesis process development. The process is based on esterification of acetic acid with 2-methylpropanol by the reactive distillation method. A column in which separation of the reaction products takes place together with esterification in catalytic active separation packing is utilized in this process. Computer simulation of catalytic distillation has been performed to study the process and to evaluate the pilot plant experimental data. KATAPAK^® S structural packing was used in the reaction zone, while stripping and rectifying sections of the column were packed by CY^® packing. A good agreement between the simulation results and pilot plant data has been achieved.     

Reactive distillation with KATAPAK

KATAPAK-SP and -S are structured catalytic packings for reactive distillation or gas–liquid reactors available from laboratory to industrial scale. Applying the KATAPAK-SP concept, the ratio of catalyst volume fraction to separation efficiency can be varied over a wide range, therefore the design of a reactive distillation column can be further optimized to fit each reaction system best.

Pressure drop, separation efficiency, dynamic liquid hold-up and residence time distribution have been investigated for KATAPAK-SP in a diameter of 250 mm. Results for different gas and liquid loads are presented. The findings are compared with results for the structured laboratory scale packing KATAPAK-S and the industrial scale packing KATAPAK-S 170.Y.

The dehydration of tert-butyl alcohol was selected as a sample reaction to illustrate the influence of different catalytic structures on the performance of the reactive distillation column. The setups are compared with respect to dimensions and economics.     

催化精馏合成乙酸乙酯的工业试验

以固体酸为催化剂,在中试催化精馏塔中进行了乙酸与乙醇反应制备乙酸乙酯的工业试验,试验塔的精馏段塔径为600 mm,内装陶瓷规整填料,反应精馏段塔径为1 000mm,内装7层立体催化精馏塔板.采用连续操作,考察了不同的回流比、釜酸质量分数、进料流量对反应和分离过程的影响,同时测定了塔板上气液相质量分数的分布.通过试验得到...     

Quantitative comparison of dynamic controllability between a reactive distillation column and a conventional multi-unit process

A comparison of the steady-state economic optimum designs of two alternative chemical processes was presented in a previous paper [Kaymak, D. B., & Luyben, W. L. (2004). A quantitative comparison of reactive distillation with conventional multi-unit reactor/column/recycle systems for different chemical equilibrium constants. Industrial & Engineering Chemistry Research, 43, 2493–2507]. A generic exothermic reversible reaction A + B ↔ C + D occurs in both flowsheets, which consist of a conventional multi-unit reactor/separator/recycle structure and a reactive distillation column. Results showed that the reactive distillation process is significantly less expensive than the conventional process for a wide range of the chemical equilibrium constant when there is no mismatch between the temperature favorable for reaction and the temperature favorable for vapor–liquid separation.

A reactive distillation column has fewer control degrees of freedom than a conventional multi-unit system. Therefore a reactive distillation column may have worse dynamic response than a conventional process. The purpose of this paper is to compare the dynamic controllability of these two alternative processes.

Three different chemical equilibrium constants are considered. Several control structures are developed for each flowsheet, and their effectiveness is evaluated. Disturbances in production rate and fresh feed compositions are considered.

The conventional multi-unit process provides significantly better control. The operability region is much larger, there is less variability in product quality and the dynamic responses are faster than those of the reactive column. Thus, these results demonstrate that there is a significant trade-off in this system between optimum economic steady-state design and dynamic controllability.     

用新离子交换树脂催化剂优化连续催化精馏塔中乙基叔丁基醚的合成(英文)

Liquid phase synthesis of one of the important fuel oxygenate, ethyl tert-butyl ether （ETBE）, from etha-nol and tert-butyl alcohol （TBA） has been studied in catalytic distillation column （CDC） using ion exchange resin catalyst CT-145H. A packed CDC of 1.2 m height and 50 mm diameter with indigenously developed reactive sec-tion packing was used to generate experimental data. Effect of different key variables on product purity in distillate, was investigated to find the optimum operating conditions for ETBE synthesis. The optimum conditions for 0.2 kg·s-1 of ethanol feed were found：reboiler duty of 375 W, molar feed ratio of 1︰1.3 of reactants, and reflux ratio of 7. Concentration profiles for each component along each column section at optimum conditions were also drawn. Neither output nor input multiplicity was observed at experimental conditions.     

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%）。     

Performance Prediction of Structured Packing Column for Cryogenic Air Separation with Hybrid Model

A detailed investigation of a thermodynamic process in a structured packing distil ation column is of great impor-tance in prediction of process efficiency. In order to keep the simplicity of an equili...     

催化精馏在合成甲缩醛中的应用

开发了由离子交换树脂型固体酸催化剂和不锈钢丝网构成的催化填料。在内径25mm、高1000mm的玻璃反应精馏塔内进行的甲醇与甲醛合成甲缩醛的反应表明, 该催化填料具有优良的催化反应活性和高效的产物分离能力。2000h寿命考察未见活性衰退迹象。在内径150mm、高5400的不锈钢反应精馏塔内的反应同样达到了小试的水平, 显示了该催化填料良好的工业应用前景。     

Reactive distillation: Non-ideal flow behaviour of the liquid phase in structured catalytic packings

Reactive distillation, the combination of chemical reaction and multistage distillation, is one of the most important industrial applications of the multifunctional reactor concept. The most promising column internals for reactive distillation are the so-called structured catalytic packings that combine favourable characteristics of traditional structured packings and heterogeneous catalysts. The non-ideal flow behaviour of the gas and the liquid phase is a fundamental aspect in multiphase reactor design since it has a strong influence on the reactor performance. In this study, liquid phase residence time distributions for the catalytic structured packing MULTIPAK^® were measured by means of conductivity measurements under different liquid and gas flow rates and evaluated with differential models.     

新型催化蒸馏塔在合成甲基叔丁基醚中的应用

分析了已有的合成MTBE催化蒸馏塔结构,同时构思了新型填料式催化蒸馏塔.在模拟催化蒸馏试验装置上,利用YLQ-1型"异形”树脂催化剂进行了合成MTBE研究,获得了反应温度、液空速、回流比等有关工艺条件数据.     

Novel eco-efficient reactive distillation process for dimethyl carbonate production by indirect alcoholysis of urea

Dimethyl carbonate is an eco-friendly essential chemical that can be sustainably produced from CO₂,which is available from carbon capture activities or can even be captured from the air.The rapid increase in dimethyl carbonate demand is driven by the fast growth of polycarbonates,solvent,pharmaceutical,and lithium-ion battery industries.Dimethyl carbonate can be produced from CO₂through various chemical pathways,but the most convenient route reported is the indirect alcoholysis of urea.Previous research used techniques such as heat integration and reactive distillation to reduce the energy use and costs,but the use of an excess of methanol in the trans-esterification step led to an energy intensive extractive distillation required to break the dimethyl carbonate-methanol azeotrope.This work shows that the production of dimethyl carbonate by indirect alcoholysis of urea can be improved by using an excess of propylene carbonate(instead of an excess of methanol),a neat feat that we showed it requires only 2.64 kW·h·kg^-1 dimethyl carbonate in a reaction-separation-recycle process,and a reactive distillation column that effectively replaces two conventional distillation columns and the reactor for dimethyl carbonate synthesis.Therefore,less equipment is required,the methanol-dimethyl carbonate azeotrope does not need to be recycled,and the overall savings are higher.Moreover,we propose the use of a reactive distillation column in a heat integrated process to obtain high purity dimethyl carbonate(>99.8 wt-%).The energy requirement is reduced by heat integration to just 1.25 kW·h·kg^-1 dimethyl carbonate,which is about 52%lower than the reaction-separation-recycle process.To benefit from the energy savings,the dynamics and control of the process are provided for
10%changes in the nominal rate of 32 ktpy dimethyl carbonate,and for uncertainties in reaction kinetics.     

催化精馏合成醋酸甲酯的研究

以强酸型阳离子交换树脂为催化剂,在直径为40 mm的填料塔内对催化精馏合成醋酸甲酯进行了研究。实验塔的三段填料高度分别为810、270、450 mm,填料段之间放置直径为60 mm、高度为175 mm的2节催化剂床层,并在塔釜放置催化剂。采用连续操作,着重考察了醇酸进料摩尔比、醋酸进料位置、甲醇进料位置和回流比对催化精馏合成醋酸甲酯的影响。在选定实验条件下,塔顶醋酸甲酯的质量分数可达到98.43%,醋酸的转化率达到99.13%。     

环丁砜萃取精馏过程模拟分析及工艺参数优化

以环丁砜-烃类相平衡数据和NRTL-RK热力学方法为基础，对环丁砜萃取精馏过程进行了全流程模拟和工艺操作参数优化。综合考虑各个操作变量及其关联，提出了基于局部耦合参数迭代优化的整体协同优化的策略。通过文献数据回归和Aspen Plus物性估算系统相结合，补充修正了缺失的模型参数，并以此模拟分析了各关键操作参数对环丁砜萃取精馏过程能耗和分离效果的影响。结果表明：当萃取精馏塔操作压力为0.17 MPa，溶剂回收塔操作压力为0.05 MPa时，贫溶剂最佳温度为100℃，原料饱和气相进料的最佳进料位置为第50块塔板；溶剂回收塔最佳回流比为0.33；最佳进料位置为第6块塔板，汽提水量为2853 kg·h^-1。优化后，装置最小热公用工程由1.158 GJ·t^-1下降至0.802 GJ·t^-1，节能效果显著。     

Synthesis and oxygen transport characteristics of dense and porous cerium/gadolinium oxide materials: Interest in membrane reactors

Cerium/gadolinium oxide (CGO)-based ceramic ion conductive membranes (CICMs) have potential uses in catalytic membrane reactors (CMRs) and solid oxide fuel cells (SOFCs). A supercritical CO₂ aided sol–gel process allowed the synthesis of CGO materials with the composition Ce_0.9Gd_0.1O_1.95. The produced nanophase powders were non-agglomerated, with a controlled morphology, a high purity and a high specific surface area (>100 m²/g). The CGO cubic crystalline phase has been obtained at temperatures <300 °C, lower than those of conventional solid state chemistry routes. With respect to ionic oxygen transport, a high conductivity at intermediate temperature (2 × 10⁻² S cm⁻¹ at 600 °C), almost equivalent in dense and porous samples, has been obtained on sintered materials prepared from these powders. In relation to their porosity characteristics, a modelling approach successfully explained the high ionic oxygen transport of some specific porous samples. Future directions for preparing porous conductive ceramics well adapted to CMR or SOFC applications can be anticipated from this model.     

低浓度丙烯和苯催化精馏合成异丙苯过程非平衡级模拟

对苯与低浓度丙烯合成异丙苯的催化精馏过程建立非平衡级模型。针对模拟过程难以收敛的特点,在计算的开始阶段引入了模式搜索法（Hook-Jeeves method)求解。通过对变量的取值范围进行一定的约束,可比牛顿型法适用较宽的初值范围。计算中根据所用催化精馏塔的特点,对方程进行了一定程度的简化。得到了催化精馏塔内的温度及液相组成分布。模拟结果与试验数据吻合较好,可以为工艺设计提供参考。     

Synthesis of dimethyl ether (DME) by catalytic distillation

The intrinsic kinetics of liquid phase catalytic dehydration of methanol to dimethyl ether over a macroporous sulphonic acid ion exchange resin was determined in a fixed-bed micro-reactor in the temperature range of 391–423 K and pressures up to 2.0 MPa. The kinetic model based on Eley–Rideal mechanism, as well as the power-rate law model, was adopted for fitting the experimental data. However, the Langmuir–Hinshelwood mechanism is not feasible for describing the dehydration reaction of methanol, as deduced from the macroscopic kinetic data and/or no dependence of methanol conversion on initial methanol concentration in the absence of water at the inlet using acetone as inert solvent. Moreover, an improved process consisting of the combination of a fixed-bed reactor and a catalytic distillation column for the synthesis of DME (Process A) was proposed, and a mathematical model was established, into which the intrinsic kinetics obtained in this work was incorporated. The comparison of operating performance among the improved process, Process B consisting of a fixed-bed reactor and two ordinary distillation columns, and Process C consisting of a catalytic distillation column and an ordinary distillation column was also made. It was found that the improved process is more promising than others in energy consumption, production capacity and column number under the same product purity, and is easy to be implemented based on Process B that is currently used in the actual industrial plants with a long catalyst lifetime.     

浆料催化精馏合成碳酸二甲酯的模拟研究

以浆料催化精馏酯交换合成碳酸二甲酯实验为基础,应用Aspen Plus软件建立了浆料催化精馏合成过程的稳态模型并进行研究。研究结果表明,模型的计算值与实验值吻合良好。通过计算机模拟还得到了实验难以测定的塔内温度分布、塔内气液相流率及组成和碳酸二甲酯在各板的生成速率的变化规律。     

合成异丙苯的烷基化与烷基转移催化精馏

分别对苯与丙烯烷基化合成异丙苯的固定床和悬浮床精馏塔进行了模拟计算.结果表明,采用这两种催化精馏塔,均能在一个塔内同时实现烷基化与烷基转移反应.指出悬浮床催化精馏由于其独特的优点因而具有更强的竞争力.     

甲缩醛合成流化催化精馏过程的非平衡级模拟

以酸性离子交换树脂为催化剂、在筛板塔内进行甲缩醛合成流化催化精馏过程，建立了非平衡级模型，采用ＮｅｗｔｏｎＲａｐｈｓｏｎ方法进行了模拟计算，得到了催化精馏塔内温度、浓度和流率等的分布规律，筛选了适宜的工艺条件     

甲醇和三甲氧基硅烷共沸物分离过程模拟和优化

三甲氧基硅烷（trimethoxysilane）是合成功能性有机硅化合物的重要中间体。在以甲醇和硅为原料合成三甲氧基硅烷的工业化生产过程中,过量的甲醇和产物三甲氧基硅烷会形成最高共沸物。本文探究了变压精馏、萃取精馏和隔壁塔萃取精馏三种分离提纯甲醇和三甲氧基硅烷的工艺,以最小年度总费用（TAC）为目标函数,运用混合整数非线性规划（MINLP）对三种流程进行了优化,比较了三种流程的效率和二氧化碳排放量。结果表明,与变压精馏相比,通过隔壁塔萃取精馏分离甲醇与三甲氧基硅烷共沸物具有明显的优势。分离100kmol/h甲醇（摩尔分数50.00%）和三甲氧基硅烷的TAC从198.84万美元/年降低到98.93万美元/年,降幅高达50.25%,效率从8.17%提高到13.82%,二氧化碳排放量从1217.53kg/h减少到684.22kg/h,减少了43.80%。