Addition of an azeotropic ETBE/ethanol mixture in eurosuper-type gasolines

This study proposes an azeotropic ETBE/ethanol mixture as a possible oxygenated additive for the formulation of eurosuper-type gasolines. Two eurosuper gasolines with different chemical compositions and well defined characteristics of density, volatility and octane numbers are used. Gasoline formulations containing azeotropic mixtures display an intermediary behavior between that of ETBE (ethyl tert-butyl ether) and ethanol in gasoline blends. Formulations containing this additive offer advantages over ethanol (low volatility and low solubility in water) and ETBE (higher octane number and lower production cost). Gasolines with azeotropic additives show lower Reid vapor pressures (RVPs) than gasolines formulated with ethanol, and therefore low levels of volatile organic compounds, similarly to highly pure ETBE. The use of the azeotropic mixture containing ethanol (renewable, deriving from biomass) and ETBE (produced from ethanol and isobutene) in its formulation is environmentally attractive in industrialized countries due to the need to reduce carbon dioxide emissions.     

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.     

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。     

Separation of azeotropic mixtures using air microbubbles generated by fluidic oscillation

The feasibility of separating the azeotropic mixture of ethanol‐water using microbubble‐mediated batch distillation is presented. The effects of the depth of the liquid mixture in the bubble tank and of the inlet air microbubble temperature on the process efficiency were investigated. The enrichment of ethanol in the vapor phase was higher than that achieved at equilibrium conditions for all liquid ethanol mole fractions considered, including the azeotrope. On decreasing the depth of the liquid mixture and increasing the temperature of the air microbubbles, the separation efficiency of ethanol was improved. Ethanol with purity of about 98.2 vol % was obtained using the lowest liquid level (3 mm) in conjunction with the highest air microbubble temperature (90°C). Separation was achieved with a small rise in the temperature of the liquid mixture (4°C) at a depth of 3 mm and evaporation time of 90 min making this system suitable for treating thermally sensitive mixtures. © 2015 American Institute of Chemical Engineers AIChE J, 62: 1192–1199, 2016     

EQUILIBRIUM CONSTANTS FOR ETHYL tert-BUTYL ETHER LIQUID-PHASE SYNTHESIS

Thermodynamic equilibrium constants for the liquid-phase synthesis of ethyl terl-butyl ether (ETBE) were determined experimentally in the temperature range 40-80°C (313-353 K) at 1.6 MPa for an initial molar ratio of ethanol to isobutene ranging from 1 to 1.5. To reach etherification equilibrium a macroporous sulphonic acid resin (K-2631, Bayer) was used as a catalyst. The thermodynamic equilibrium constant and the enthalpy, free energy, and entropy changes are given as a temperature function. At 298 K, ΔH° = -34.8 kj mol^-1, ΔG° = -11.7kJmol^-1, and ΔS° = -77.3J mol^-1 K^-1. A comparison with the values obtained for MTBE is also included.     

Activated carbon supported silicotungstic acid catalysts for ethyl‐tert‐butyl ether synthesis

Vapor phase ethyl‐tert‐butyl ether (ETBE) production was conducted in the presence of Cesium salts of silicotungstic acid (Cs‐STA), activated carbon supported silicotungstic acid (AC‐STA), and activated carbon supported Cesium salts of silicotungstic acid (AC‐Cs‐STA) catalysts. Isobutene (IB) conversion to ETBE at 373 K were determined as 0.16 and 0.2 for STA and AC‐STA catalysts on constant space time basis. This increase of activity is one of the highlights of this study considering that STA loading in AC‐STA catalysts had been adjusted to 40%. IB conversion to ETBE obtained at 373 K in the presence of AC‐STA catalyst was found to be close to equilibrium. Stability of the synthesized catalysts were tested by applying a washing procedure with ethanol. Repeated ETBE synthesis with thoroughly washed samples indicated quite stable and active catalyts. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

氢氟酸改性USY分子筛催化合成乙基叔丁基醚的研究

以氢氟酸改性USY为催化剂,乙醇和叔丁醇为原料,合成乙基叔丁基醚(ETBE)。与未改性USY和国产强酸性阳离子树脂D005相比,氢氟酸改性USY的催化作用显著。分别考察了催化剂负载量、反应温度和反应时间等因素对醚化反应的影响。最佳操作条件为:n(乙醇)∶n(叔丁醇)=2∶1,原料质量为10 g,催化剂用量为1 g,USY分子筛上氢氟酸负载量6%,反应温度120 ℃,反应时间3 h。最佳操作条件下乙基叔丁基醚的产率为52.46%,叔丁醇转化率为55.83%,选择性为95%。     

Kinetic studies of liquid phase ethyl tert-butyl ether (ETBE) synthesis using macroporous and gelular ion exchange resin catalysts

Ethyl tert-butyl ether (ETBE) synthesis from ethanol (EtOH) and tert-butyl alcohol (TBA) was studied with different macroporous and gelular ion exchange resin catalysts. Purolite^® (CT-124, CT-145H, CT-151, CT-175 and CT-275) and Amberlyst^® (15 and 35) ion exchange resins were used for the present work. Effect of various parameters such as catalyst type, temperature, reactants feed molar ratio and catalyst loading were studied for the optimisation of reaction condition. Among the catalysts studied, Purolite CT-124 gave the best results for TBA conversion and selectivity towards ETBE. Kinetic modelling was performed with this catalyst and activation energy and water inhibition coefficient were determined. Heterogeneous kinetic models [e.g., Eley-Rideal (ER), Langmuir-Hinshelwood-Hougen-Watson (LHHW)] were unable to predict the behaviour of this etherification reaction, whilst the quasi-homogeneous (QH) model represented the system very well over wide range of reaction conditions.     

Separation of ethyl tert-butyl ether-ethanol by combined pervaporation and distillation

A cellulose derivative membrane (30 wt.% cellulose acetate butyrate (CAB) combined with 70 wt.% cellulose acetate propionate (CAP)) was prepared, and its properties were evaluated by the pervaporation separation of mixtures of ethyl tert-butyl ether (ETBE) and ethanol. The experimental results showed that the selectivity and permeability of the membrane were dependent on the blend composition, the processed feed and the experimental temperature. With respect to the temperature, the fluxes obeyed the Arrhenius equation. On the basis of these results, a separation process for the production of ETBE was developed by combining pervaporation and distillation. The distillation column was designed with the software ASPEN PLUS, and the liquid-vapour equilibria were predicted by the UNIFAC method. The area of the membrane was calculated according to the production capacity. It may be concluded that the combined process for the separation of mixtures of ETBE and ethanol is simple with high recovery of the ETBE product.     

An approximate model for binary azeotropic distillation design

A simple analytical model has been developed for representing vapor-liquid equilibrium data in binary azeotropic mixtures. The method treats the azeotrope as a new pure component and considers the mixture to be composed of two independent binary subsystems; component 1 + azeotrope and azeotrope + component 2. After suitable variable transformations, each subsystem can then be represented by a constant relative volatility type model. The resulting vapor-liquid equilibrium models have been used to derive design equations for binary azeotropic distillation columns.     

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.     

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.     

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.     

Recovery and Recycling of Isopropyl Alcohol Used in Biodiesel Production From Yellow Mustard Oil

The recovery of solvents used during biodiesel synthesis is an important factor in the economic feasibility and sustainability of the entire process. In this study, we looked at the use of isopropyl alcohol (IPA) for oil extraction and biodiesel production, as well as its potential for recovery and recycling. We found that multistage extraction improved oil recovery, with up to 86% oil yield using four stages of extraction at an IPA:mustard flour (volume:weight) ratio of 1.5:1 at room temperature. Using acid–base‐catalyzed transesterification, 99% of the mustard oil was converted to biodiesel. At the end of this process, IPA was recovered from the azeotrope by salting out using potassium carbonate or sodium carbonate. The solubility behavior of the components was evaluated by means of ternary‐phase diagrams of IPA/water/sodium carbonate and IPA/water/potassium carbonate, which determined their liquid–liquid–solid equilibrium constants at ambient pressure and at room temperature. Using 20% (w:w) potassium carbonate, 95% of the IPA was recovered at 99% purity from a starting mixture of IPA containing 13% water. Azeotropic distillation of the IPA–water azeotrope with 10% potassium carbonate resulted in the recovery of 99% of the IPA at 94% purity. These results suggest that IPA is not only a suitable solvent for mustard‐oil extraction but also for salt‐enhanced azeotropic distillation resulting in near‐complete recovery from aqueous solutions.     

乙基叔丁基醚合成催化剂的研究进展

综述了国内外合成乙基叔丁基醚(ETBE)的催化剂研究现状,介绍了ETBE在不同催化剂上合成的反应机理。比较了阳离子交换树脂、分子筛、固体超强酸和杂多酸等不同催化剂的催化活性、选择性、稳定性等特点;讨论了采用催化精馏法合成ETBE时催化剂的各种装填技术。指出今后的研究方向是采用引入拉电子基团的方法改善树脂催化剂的热稳定性和选择性,通过离子交换等调节酸性的方法进一步提高分子筛催化剂的催化活性;同时应加强对固体超强酸和杂多酸催化剂的基础研究。     

含水乙醇制备醇醚燃料的工艺研究

以A-15为催化剂,含水乙醇和异丁烯为原料合成乙基叔丁基醚（ETBE）。结果表明：在80℃下,n（乙醇）∶n（异丁烯）=3.0∶1,催化剂用量7 wt%～9 wt%,反应150 min,异丁烯的转化率为90.5%,乙基叔丁基醚（ETBE）的收率为77.2%,水的相对转化率为80.4%。反应产物脱丁烷后进行精馏分离,塔顶可得到高醚含量且易于萃取分离的含醚混合物,塔釜可得到含水量低于0.8%的一元醇产品。     

乙醇-叔丁醇合成ETBE催化剂研究进展

以液体酸催化剂、离子交换树脂催化剂、沸石分子筛催化剂、固体超强酸催化剂、杂多酸及其负载型催化剂等为线索,评述了各类乙醇-叔丁醇催化合成乙基叔丁基醚(ETBE)催化剂的特性和近年来的研究进展,展望了乙醇-叔丁醇催化合成乙基叔丁基醚催化剂的发展方向,提出以合成ETBE的催化机理和催化剂性质的关系为指导来研制高效、高稳定性催化剂是乙醇-叔丁醇合成ETBE的关键。     

New approach for the prediction of azeotropy in binary systems

A new approach for the prediction of azeotrope formation between components in a mixture, that does not require vapor–liquid equilibrium calculations, is presented. The method employs neural networks to correlate azeotropic data for binary mixtures with a series of macroscopic and microscopic properties of the pure components, without explicit consideration of non-ideality of mixture. The model fails to make a clear prediction regarding azeotropy in only a relatively small number of situations in which structurally homologous molecules are known to exhibit quite distinct azeotropic behavior.     

Comparison of extractive distillation and pressure-swing distillation for acetone/chloroform separation

The separation of acetone from chloroform is difficult because the highly nonideal vapor–liquid equilibrium produces a maximum-boiling azeotrope. An earlier paper (Luyben, W. L. (2008). Control of the maximum-boiling acetone/chloroform azeotropic distillation system. Industrial & Engineering Chemistry Research, 47, 6140–6149) discussed the use of extractive distillation for making this separation. This paper studies the use of pressure-swing distillation for making the same separation.Results show that the extractive distillation process is much more attractive from the standpoint of both capital investment and energy consumption. But pressure-swing distillation avoids the potential problem of product contamination by the extractive solvent that must be added to the binary system.     

Kinetics and mechanism of ethyl tert-butyl ether liquid-phase synthesis

This paper presents the results of an experimental investigation on ethyl tert-butyl ether (ETBE) liquid-phase synthesis from isobutene (IB) and ethanol (EtOH), catalyzed by an acidic macroreticular ion exchange resin, Amberlyst 15 (A15). The experiments were carried out batchwise in a Parr reactor in the range 323–363 K at 2 MPa for different initial EtOH/IB mole ratios and amounts of catalyst. Data collected at equilibrium gave thermodynamic information which was compared with theoretical calculations using the UNIFAC method. The kinetic results were used to develop a reaction mechanism and a kinetic model. The resin's affinity for polar substances and the strong nonideality of the liquid phase lead to a complex kinetic expression, which is valid both in the presence of high and low alcohol concentrations. Simulations performed with this kinetic model agree satisfactorily with the experimental results.