Optimization of the ETBE (ethyl tert-butyl ether) production process

The synthesis of ETBE (ethyl tert-butyl ether) from the reaction of ethanol with isobutene is an exothermic reaction of equilibrium. To increase the conversion of isobutene requires operating the reaction system at low temperatures and with excess ethanol in order to displace the equilibrium towards the products. ETBE and ethanol form an azeotropic mixture which hinders the recycling of nonreacted ethanol in the process. The purpose of this work is to optimize the synthesis of ETBE eliminating the introduction of water into the system to break the ETBE/Ethanol azeotrope. The production process model proposed here eliminates the recycling of ethanol and suggests the use of the azeotropic mixture (ETBE/Ethanol) in the formulation of gasolines. The direct use of the azeotrope in the formulation of automotive gasolines reduces the implementation and production costs of ETBE.     

Volatility and phase stability of petrol blends with ethanol

Blending ethanol in to petrol can be associated with problems related to volatility and phase stability of the blends. Ethanol up to 20 vol% in petrol forms an azeotropic mixture with hydrocarbons. Ethanol has affinity to water and air humidity and it increases the water solubility in ethanol-petrol blends. In this work, the influence of ethanol up to 10 vol%, ETBE up to 10 vol% and hydrocarbon composition over volatility, distillation characteristics and miscibility of ethanol-petrol blends with water was studied. It was found that higher content of saturated hydrocarbons in petrol increased the vapour pressure of azeotropic ethanol blend. Aromatics and alkenes influenced the azeotrope vapour pressure, phase separation temperature and ethanol extraction in a positive way. The results showed that the ETBE can soften effects of the ethanol blending to petrol. ETBE decreased the vapour pressure and the phase separation temperature of the ethanol-petrol blends.     

Effect of ethers and ether/ethanol additives on the physicochemical properties of diesel fuel and on engine tests

This study evaluates the effect of ether additives (ETBE and TAEE) in diesel and of ether/ethanol/diesel blends on the properties of density, volatility, viscosity, characteristics at cold temperatures, cetane number and performance in engine tests. The formulations were carried out with 5, 10 and 20% v/v of ethyl ter-butyl ether (ETBE) and ter-amyl ethyl ether (TAEE) and with 5, 10 and 20% v/v of ether/ethanol blends (50/50% v/v) starting from a base diesel. The formulations containing up to 5% v/v of TAEE displayed satisfactory results in the evaluation of physicochemical properties and greater efficiency in the engine tests. The results indicate that the ETBE and TAEE ethers act as cosolvents of ethanol in diesel. The presence of ethanol and ETBE significantly alter the characteristics of volatility (flashpoint and distillation curve) and reduce the cetane number, impairing the fuel's performance in engine tests.     

Effect of additives on the antiknock properties and Reid vapor pressure of gasoline

An evaluation was made of the effect produced by the addition of oxygenates such as ethanol, ETBE and MTBE and nonoxygenates such as isooctane and toluene on the Reid vapor pressure (RVP) and octane number of two types of gasoline with different chemical compositions. Locally produced gasoline was blended with five different percentages (v/v) of the additives, i.e. 5, 10, 15, 20 and 25%. Ethanol and MTBE increased significantly the RVP of the mixtures, but ETBE, and particularly toluene and isooctane, decreased the RVP of the original fractions when mixed with gasoline. The octane rating of gasoline was found to increase continuously and linearly with the addition of the oxygenated compounds toluene and isooctane. Moreover, the mixture octane number of the oxygenated compounds was superior to the octane number of the same compounds of high purity grade.     

Recovery of Near-Anhydrous Ethanol as Gasoline Additive from Fermentation Products

Abstract

The use of near-anhydrous ethanol, obtained from fermentation products through low pressure distillation, as a gasoline additive is examined. To this purpose, a reliable model for predicting the azeotropic composition of an ethanol-water mixture as a function of the pressure is presented. It is developed by considering the available thermodynamic consistent experimental data and using the Wilson and the Virial equations for the liquid- and vapor-phase nonideality, respectively. It is concluded that, for an area with no extremely cold winters—minimum ambient temperature ?20°C—alcohol with 96.5% (wt) purity can be used in a 90/10 (vol) gasohol mixture. Such an alcohol can be produced with a single distillation column operating at 140 mmHg pressure with an energy consumption of 5150 kJ/kg of product; or with a system of two columns with lower energy consumption but higher capital cost. These energy consumptions are very sensitive to the accuracy of the predicted azeotropic composition at the operating pressures.     

萃取精馏分离呋喃酚中邻苯二酚

In this study,extractive distillation has been applied to separate catechol(CAT) from carbofuran phenol(CFP) with high purity and yield.The relative volatility of CFP to CAT was measured,and the choice of separating agents was investigated.The experimental results indicated that CFP/CAT is an azeotropic system with an azeotropic point at 93.40℃/0.400 kPa and an azeotropic mixture containing 49.96% of CFP and 50.04% of CAT.Data from the determination of the relative volatility have shown that separating agents such as diglycol and 4-butylcatechol(4-TBC) are able to increase the relative volatility up to 1.90.In one shot process batch extractive distillation of CFP mixture with 3%(by mass) diglycol as separating agent,the purity and yield of the obtained CFP was 99.0% and 95.0%,respectively,while the distillation without separating agent provided a purity and yield of only 98.0% and 90.0%,respectively.There was no residual separating agent found in the product.     

Separating Some Crude Oil Products (azeotropic mixture) by Gas Extraction with Carbon Dioxide at Elevated Pressure

Abstract

The ethanol/octane system has an azeotrope at normal pressure. This renders separation by simple distillation impossible. The system was studied at elevated pressure to see whether it was possible to separate the azeotropic mixture by gas extraction with carbon dioxide. It was found that the ternary had isologous phases with a ratio not very different from that in the azeotrope.     

反应精馏与渗透蒸发膜分离耦合法合成乙基叔丁基醚

以乙醇和叔丁醇为原料 ,通过催化反应、精馏与渗透蒸发膜分离三单元耦合过程合成了乙基叔丁基醚(ETBE) ,建立了相关五元高度非理想体系的耦合过程数学模型 ,以改进的超松弛法对模型求解 ,并进行了模型校验和工艺操作参数的模拟寻优     

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     

Vapor-liquid equilibrium of ethanol/ethyl acetate mixture in ultrasonic intensified environment

A vapor-liquid equilibrium (VLE) study was conducted on ethanol/ethylacetate mixture as a preliminary step towards developing an ultrasonic-assisted distillation process for separating azeotropic mixtures. The influence of ultrasonic intensity and frequency on the vapor-liquid equilibrium (VLE) of the mixture was examined using a combination of four ultrasonic intensities in range of 100–400W/cm² and three frequencies ranging from 25–68 kHz. The sonication was found to have significant impacts on the VLE of the system as it alters both the relative volatility and azeotrope point, with preference to lower frequency operation. A maximum relative volatility of 2.32 was obtained at an intensity of 300 W/cm2 and a frequency of 25 kHz coupled with complete elimination of ethanol-ethyl acetate azeotrope. Results from this work were also congruent with some experimental and theoretical works presented in the literature. These findings set a good beginning towards the development of an ultrasonic assisted distillation that is currently in progress.     

乙基叔丁基醚合成研究进展

乙基叔丁基醚具有较高的辛烷值,是一种环境友好的汽油添加剂。介绍乙基叔丁基醚在不同催化剂上合成的反应机理,综述国内外合成乙基叔丁基醚的催化剂研究现状及国外几种典型的乙基叔丁基醚生产工艺流程。比较不同催化剂的催化活性、稳定性和选择性。指出通过改性提高树脂催化剂的热稳定性是该领域重要的研究方向。国外已拥有成熟的乙基叔丁基醚合成技术,国内大部分还处于研究阶段,应尽快加强技术开发,早日实现产业化。     

Pervaporation of nonaqueous ethanol azeotropes through interpenetrating polymer network membranes prepared from poly(4-vinylpyridine) and poly(vinyl alcohol)

Highly hydrophilic interpenetrating polymer network (IPN) membranes were prepared from a mixture system of poly(4-vinylpyridine) (P4VP) and poly(vinyl alcohol) (PVA) by quaternizing crosslinking of P4VP with 1,4-dibromobutane (DBB) and simultaneous crosslinking of PVA with hexamethylene diisocyanate (HMDI). The membrane performance in pervaporation (PV) for the azeotropic mixture of ethanol with a less polar organic liquid (chloroform, benzene, carbon tetrachloride, and cyclohexane) was investigated. The strength of these IPN membranes was higher than that of the cellulose acetate membrane and depended on the membrane composition. All the membranes were ethanol permselective for the azeotropic feeds and equimolar mixture feeds as well. Only the swelling degree Q of the membrane, among several physicochemical factors, showed a relationship with the separation performance for the four feeds; a lower value of Q generally corresponded to a higher separation factor and smaller permeability. The membrane composition, which exhibited an optimum membrane performance, was examined in detail for some membranes. Both the separation factor for sorption and that for diffusion far exceeded unity, but the latter was greater in most cases than was the former and dominated the overall separation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2729–2738, 2001     

共沸蒸馏在化工生产中的应用与研究进展

共沸蒸馏为共沸物或相对挥发度接近于1的非理想物系的分离过程提供了选择。介绍了蒸馏残余曲线图的热力学原理,并以反应蒸馏生产乙酸乙酯工艺为例说明了蒸馏残余曲线图在流程设计等方面的应用。分别从夹带剂选择、过程设计、过程集成强化、过程控制等角度阐述了共沸蒸馏过程相关理论研究进展;在应用方面,主要综述了乙醇、异丙醇稀溶液、稀乙酸等脱水及回收利用情况,共沸蒸馏过程强化反应蒸馏、变压共沸蒸馏、共沸蒸馏耦合膜分离研究进展情况以及反应蒸馏工艺的局限性,并对其未来的发展前景作了展望。     

离子液体对乙腈-水共沸物系汽液平衡的影响

选择离子液体1-丁基-3-甲基咪唑氯盐（Bmin[Cl]）作为分离乙腈-水共沸物系的溶剂。在0.101MPa下测定了在离子液体Bmin[Cl]含量为10%、20%和30%时乙腈-水物系的汽液平衡数据。实验结果表明,离子液体Bmin[Cl] 可以提高乙腈对水的相对挥发度,离子液体Bmin[Cl]含量在20%以上时可以消除乙腈-水物系的共沸点。离子液体Bmin[Cl]可以用作分离乙腈-水物系的萃取剂。用改进的Furter方程对数据进行了关联,得到了离子液体Bmin[Cl]对乙腈-水物系的盐效应参数。     

常压下乙醇-水-醋酸钾系统汽液平衡数据的测定与关联

采用Ellis汽液两相双循环平衡蒸馏仪测定了常压下乙醇(1)-水(2)和乙醇(1)-水(2)-醋酸钾(3)物系的汽液平衡数据,结果表明：醋酸钾对乙醇(1)-水(2)系统具有盐析效应,乙醇对水的相对挥发度α₁₂上升。系统中10%(质量)的醋酸钾已经消除了乙醇-水间的共沸点,可作为加盐萃取精馏的分离剂。采用已授权的Aspen Plus软件自带的eNRTL、Wilson和UNIQUAC模型,以及eNRTL模型分别对乙醇(1)-水(2)、乙醇(1)-水(2)-10%(质量)醋酸钾(3)系统实验数据进行了关联,计算结果表明：乙醇(1)-水(2)系统中,平衡温度的平均绝对偏差（AAD）为0.72℃(eNRTL)、0.78℃(Wilson)和0.71℃(UNIQUAC),气相组成计算值的平均绝对偏差为0.0083(eNRTL)、0.0077(Wilson)和0.0101(UNIQUAC)。而在乙醇(1)-水(2)-10%(质量)醋酸钾(3)系统中平衡温度和气相组成平均绝对偏差分别为0.25℃和0.0168(eNRTL)。     

车用乙醇汽油挥发性研究

分析了车用乙醇汽油中影响挥发性的组分,介绍了变性燃料乙醇对汽油挥发性及车用乙醇汽油挥发性对汽车运行和环境的影响。通过对车用乙醇汽油族组成、蒸汽压和蒸馏特性的解析,明确了催化裂化汽油、催化重整汽油、烷基化汽油、异构化汽油、直馏汽油及含氧化合物等的调合作用。车用乙醇汽油挥发性的增大使汽车的启动性能增强、驱动性能变差、发生光化学污染的可能性变大。针对环保方面提出了车用乙醇汽油调合组分偏重一些,少加或不加其他含氧化合物,增加高辛烷值调合组分调合量的建议。     

Energy saving in acetic acid process using an azeotropic distillation column with a side stripper

Dilute acetic acid is obtained primarily from fermentation and synthesis processes and cannot be produced by simple distillation due to relatively low volatility of acetic acid compared to water. Instead, an azeotropic distillation is applied to increase the concentration of dilute acetic acid. When acetic acid is extracted from a dilute aqueous solution using a solvent mixture of ester and alcohol, its recovery requires an energy-intensive azeotropic distillation. In the water stripping process that follows azeotropic distillation, two distillation columns handle the acetic acid and water mixture in similar composition. Therefore, the two columns can be combined as a side stripper connected to the azeotropic distillation column. The energy-saving effect is examined with the HYSYS (Aspentech Corporation) evaluation of the process. Compared to the conventional process, the modified process suggests 39% reduction in heating duty and 24% coolant savings. The economic analysis shows 32% decrease in investment and 36% utility savings. Based on heat utilization analysis, the thermodynamic efficiency is enhanced by 11%.     

Pervaporation with Reactive Distillation for the Production of Ethyl tert-Butyl Ether

Abstract

The combined process of pervaporation with reactive distillation was studied for the production of ethyl tert-butyl ether (ETBE) from ethanol (EtOH) and tert-butyl alcohol (TBA). on an ion-exchange catalyst. An apparatus consisting of a stirred batch reactor, a distillation column, and a pervaporation membrane was used to test this technique. The permeation flux and selectivity of water in the membrane were investigated in water-alcohols system. The etherification was performed in the liquid phase by using a batch reactor. The reactive distillation was examined with and without pervaporation at the boiling point of the reactant mixture under atmospheric pressure. When pervaporation was not conducted, two layers formed in the top products because of a higher concentration of water. However, these phenomena were not observed when pervaporation was added. It was revealed that pervapovation might be effective for removing water from the bottom and that a higher fraction of ETBE could be obtained as a top product.     

Mass transfer effects on kinetics of nonideal liquid phase ethyl tert-butyl ether formation

Ethyl tert-butyl ether (ETBE) is an alternative fuel oxygenate that can be produced in the liquid phase by addition of ethanol to isobutene catalyzed by sulfonic acid ion exchange resins. A generalized Langmuir-Hinshelwood rate expression is formulated in terms of the liquid phase activities of the reactants that is quasi-autocatalytic due to ethanol. This microkinetic model is combined with the generalized Maxwell-Stefan equations for a detailed investigation of the influence of multicomponent mass transfer limitations inside the macropores of the heterogeneous catalyst. The model is used for revision of experimental rate data for ETBE synthesis in the literature. The analysis reveals that reverse diffusion of isobutene can occur by strong interaction with ethanol and the catalyst effectiveness factor can exceed unity.     

Polylactide. II. Discontinuous dry spinning–hot drawing preparation of fibers

The mechanical properties and morphology of poly(L-lactide) fibers, prepared by the dry spinning–hot drawing process using different nonsolvent/chloroform spinning solutions, were studied in relation to fiber in vitro degradability. Acetone, methanol, ethanol, and cyclohexane were used as nonsolvents in the spinning mixture with as-polymerized PLLA, i.e., PLLA containing 10% of residual L-lactide. The tensile strength, structure, and degradability of obtained fibers were mainly governed by the nonsolvent volatility. Generally, the higher the volatility, the higher the strength, and the faster the degradation. The acetone/chloroform spinning system produced fiber with an increased degradation rate in comparison to the pure chloroform spinning system. © 1994 John Wiley & Sons, Inc.