Residue curve maps for reactive distillation systems with liquid-phase splitting

A model has been developed to study the effects of chemical kinetics on the residue curve maps (RCM) for reactive distillation systems with liquid phase splitting. In the model, chemical reaction can occur in both or only one of the two liquid phases. The heating policy V/V₀=H/H₀ is applied so that the kinetic effect can be described by a single parameter, the Damköhler number Da. The effects of reaction kinetics on pseudohomogeneous and heterogeneous mixtures have been compared. The properties of their RCMs are the same outside, but are fully different inside the liquid-liquid (L-L) region if they have different chemical equilibrium curves. Inside the L-L region, the chemical equilibrium curve coincides to a unique reactive liquid-liquid tie line in case that the pseudohomogeneous chemical equilibrium curve intersects with the L-L envelope. When the reaction occurs in only one of the two liquid phases, the residue curves inside the L-L region are strongly affected by the L-L envelope, especially at high Da. In the present paper, first an illustrative arbitrary reaction system, and then the reaction of cyclohexene with water to cyclohexanol are analysed with respect to their RCMs.     

利用压力影响恒沸点由反应精馏精制THF

研究压力如何影响恒沸点,探索改变操作压力由反应精馏精制四氢呋喃（THF）可行性,模拟计算考察了压力对THF／水体系恒沸点的影响,结果表明体系压力增加,恒沸物中THF摩尔分率减少。通过两塔在不同压力下操作,利用反应精馏技术可从1,4－丁二醇制备高纯度的THF。     

原甲酸三甲酯-醋酸萃取精馏全局多目标优化

在生产杀菌剂嘧菌酯中间体过程中,反应物原甲酸三甲酯（TMOF）与生成物醋酸（HAc）发生共沸,导致反应物堆积和原料损耗。为解决共沸物分离问题,使用Hayden-O'Connell修正的UNIFAC基团贡献法研究其汽液平衡,设计常规萃取精馏（CED）、侧线萃取精馏（SED）、隔壁塔萃取精馏（EDWC）三种工艺,以分离组分摩尔纯度、再沸器热负荷（Q）、年度总费用（TAC）为目标,运用灵敏度耦合箱线图响应面法（S-BBD）对三种工艺参数分别优化。结果表明,优化方法预测值与实际值存在较优拟合关系, CED、SED、EDWC对TAC和Q的预测误差均不超过1%。分离纯度相同时,SED较CED节约10.37%TAC和6.88%热负荷,EDWC较CED节约10.65%TAC和10.53%热负荷,三种工艺方案均可为化工实际生产提供理论基础。     

四氢呋喃-乙醇变压精馏分离

共沸混合物分离是化工过程中常见的分离难题。变压精馏是根据物系压力改变而使液体混合物共沸点组成发生变化,进而使共沸物系得以分离的一种有效分离方法。在热力学分析基础上,提出了四氢呋喃-乙醇液体混合物变压精馏分离双塔工艺流程。以NRTL-RK为物性计算方法,利用Aspen Plus模拟软件对变压精馏分离工艺过程进行分析及模拟,并对工艺参数进行优化。研究结果表明:在常压塔和0.8 MPa高压塔组成的双塔流程中变压精馏可将四氢呋喃-乙醇最低共沸混合物进行较好的分离。     

填料毛细管精馏过程中气液两相流动特性及其影响因素的数值分析

通过构建数值模型,对填料毛细管精馏塔内气液两相的流场和速度场分布进行了计算分析,研究了在不同的填料孔隙率、气相和液相进口速率等系统结构和操作工艺条件下,填料毛细管精馏塔内气液两相的速度场分布特性.通过对气液两相分布状态的分析,明确了符合最优气液两相相际传质特性的结构和工艺参数,对后续填料毛细管精馏的实验具有良好的指导意...     

Synthesis and characterization of moisture‐cured polyurethane membranes and their applications in pervaporation separation of ethyl acetate/water azeotrope at 30°C

NCO‐terminated polyurethane membranes were prepared using diisocyanate, diol, and trimethylolpropane (TMP) using an NCO/OH ratio of 1.6 : 1. Prepolymer was chain‐extended using cellulose acetate butyrate (CAB) in the ratios of 2 : 1, 4 : 1, and 3 : 1 of NCO/OH. Polyurethane (PU) membranes were characterized by differential scanning calorimeter (DSC) and thermogravimetry (TGA) to investigate their thermal properties. Equilibrium sorption studies were carried out at 30°C in water and ethyl acetate media as well as in their binary mixtures. The influence of CAB on pervaporation (PV) separation of an ethyl acetate/water (92/8, w/w, i.e., azeotropic composition) mixture was investigated. Membranes in this study showed a selectivity of 42.42 with a flux value of 0.187 kg/m/h for 3 : 1% NCO/OH containing PU membrane. In order to gain a more detailed picture of the molecular transport phenomenon, we performed the sorption gravimetric experiments at 30°, 35°, 40°, and 50°C to compute diffusion, swelling, sorption, and permeability coefficients of PU membranes in the azeotropic mixture of ethyl acetate and water. Activation parameters for diffusion and permeation were computed from the Arrhenius equation to understand the polymer/solvent interactions. Sorption trends and diffusion anomalies were established through an empirical equation after estimating the diffusion parameters. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3405–3414, 2007     

Fuel grade ethanol by diffusion distillation: an experimental study

BACKGROUND: Fuel grade ethanol (anhydrous ethanol) is considered to be an excellent alternative clean burning fuel to gasoline. It is now used as an additive to gasoline to enhance its octane number and combustibility. Owing to its high energy values, ethanol is the most promising future biofuel. Because of azeotrope formation, anhydrous ethanol cannot be achieved by conventional distillation. Diffusion distillation is one of the several processes that can be used to separate azeotropes. Diffusion distillation takes advantage of differences in relative rates of diffusion using inert gas as selective filter. RESULTS: Effect of vaporization temperature and feed composition on diffusion distillation of an ethanol–water mixture using air as the inert gas has been studied. A new quantity S_az(N₂/N₁) has been suggested to find the optimum vaporization temperature. In the present study this was found to be about 46 °C. The pseudo‐azeotrope has been observed at 0.697 mole fraction of ethanol at a vaporization temperature of 50 °C. Separation is effected by diffusion distillation even at the azeotropic ethanol mole fraction of 0.894. The experimental results were compared with a Stefan–Maxwell equations based mathematical model and found to be in good agreement with theoretical results. CONCLUSIONS: Experimental results demonstrate that fuel grade ethanol can be produced by diffusion distillation. The new quantity S_az(N₂/N₁) is a key variable for vaporization temperature optimization. Copyright © 2011 Society of Chemical Industry     

2-甲氧基丙烯生产中有关体系的共沸点研究

利用基于精馏原理的加压共沸点测定装置，测定了2-甲氧基丙烯(MPP)与甲醇或丙酮二元体系在减压、常压及加压条件下的共沸点数据，并对数据进行了关联。从关联的结果可知，该体系共沸组成与共沸温度、压力的对数及共沸温度的倒数均呈良好的线性关系，计算结果与实验值符合良好。随着压力的降低，这两个二元体系中MPP的含量都增加，说明在减压条件下更利于MPP的分离和提纯。特别是MPP-丙酮体系，在49．7kPa下，其MPP的摩尔分数已达到0．997。这项研究为MPP工业化过程中共沸混合物的分离、提纯，以及共沸精馏、反应精馏等工艺与装置的研究与设计提供了重要的基础数据和参考依据。     

共沸物分离及深加工

介绍了甲基氯硅烷合成中的副产共沸物[SiCl4(CH3)3SiCl]的主要分离方法:恒沸精馏法和酯化分离法,并分述了共沸物分离后三甲基氯硅烷和四氯化硅的深加工方法。三甲基氯硅烷可用来制备六甲基二硅氧烷、六甲基二硅氮烷、六甲基二硅烷等;四氯化硅可用来制备四丁酮肟基硅烷、四乙酰氧基硅烷、正硅酸乙酯及其缩聚物、烧制气相法白炭黑等。     

加盐萃取精馏分离醋酸甲酯-甲醇二元恒沸物

用改进的O thm er汽液平衡釜测定了0.101 3M Pa下醋酸甲酯-甲醇体系在萃取剂和盐存在下的相对挥发度,测定了全浓度范围的汽液平衡数据,并进行了加盐萃取精馏工艺的实验。结果表明,水作为萃取剂,加入醋酸钾,可提高醋酸甲酯-甲醇体系的相对挥发度,加盐萃取精馏比普通的萃取精馏有优势,当溶剂体积比为1∶1时,萃取精馏塔塔顶采出的醋酸甲酯的质量分数可达到99%以上,萃取剂回收率达98%,盐可以全部回收。