Reducing the energy demand of corn‐based fuel ethanol through salt extractive distillation enabled by electrodialysis

The thermal energy demand for producing fuel ethanol from the fermentation broth of a contemporary corn‐to‐fuel ethanol plant in the U.S. is largely satisfied by combustion of fossil fuels, which impacts the possible economical and environmental advantages of bioethanol over fossil fuels. To reduce the thermal energy demand for producing fuel ethanol, a process integrating salt extractive distillation—enabled by a new scheme of electrodialysis and spray drying for salt recovery—in the water‐ethanol separation train of a contemporary corn‐to‐fuel ethanol plant is investigated. Process simulation using Aspen Plus® 2006.5, with the electrolyte nonrandom two liquid Redlich‐Kwong property method to model the vapor liquid equilibrium of the water‐ethanol‐salt system, was carried out. The integrated salt extractive distillation process may provide a thermal energy savings of about 30%, when compared with the contemporary process for separating fuel ethanol from the beer column distillate. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

加盐萃取精馏分离乙醇—水体系的研究进展

乙醇在化工、医药和电子等领域有广泛的应用,燃料乙醇作为可再生能源,已成为世界各国新型能源研发的重点。加盐萃取精馏是在溶盐精馏和萃取精馏的基础上发展起来,目前加盐萃取精馏是分离乙醇—水体系的重要方法。本文将分别介绍溶盐精馏和萃取精馏,以及加盐萃取精馏分离乙醇—水体系的研究现状及发展前景。     

Economic evaluation of energy saving alternatives in extractive distillation process

Until now, there has not been consensus about the superiority of thermally coupled sequence over the conventional sequence in the extractive distillation process. In this sense, the main goal of this paper is to analyze three approaches for saving energy in the extractive distillation process: optimization, thermal integration and thermal coupling. Three azeotropic mixtures were investigated: ethanol and water (M1); tetrahydrofuran and water (M2); and acetone and methanol (M3). The solvents were ethylene glycol for M1 and M2, and water for M3. The results are shown in terms of the total annual cost (TAC) and specific energy consumption (SEC), and revealed that a thermally coupled extractive distillation sequence with a side rectifier did not always present the best results. Taking the case studies from literature as a starting point (without thermal integration), the optimization procedure used in this work found that TACs are always lower. The inclusion of thermal integration in configurations led to reducing TAC for all mixtures under investigation when compared to the sequences without this integration. When comparing two modifications in the layout of extractive distillation, it can be seen that it is more advantageous to use the preheating of the azeotropic feed with the recycle stream from the recovery column of the conventional sequence than using a thermally coupled sequence.     

盐效应制取无水乙醇的研究现状及发展前景

无水乙醇广泛应用于制药、化工、能源等行业,需求量日益剧增。目前,利用盐效应制取无水乙醇的方法主要有溶盐精馏、加盐萃取精馏。文章对盐效应方法做了分析,对盐的选择和盐效应在分离工艺中的研究进展做了详细的阐述。     

Control analysis of an extractive dividing-wall column used for ethanol dehydration

This paper deals with design and control of an extractive dividing-wall distillation column (EDWC) for ethanol dehydration using ethylene glycol as entrainer. An initial design, based on a section analogy procedure for a conventional extractive distillation sequence, was obtained and then used in an optimization process to minimize the total annual cost. It was shown that the EDWC can result in significant savings over the conventional process. As these savings sometimes go along with a decrease in the control properties, an investigation of two control structures for the EDWC and one for the conventional column configuration was performed next.It was observed in closed-loop simulations that the EDWC with an appropriate structure exhibited good control properties and that its closed-loop responses were similar to those obtained for the operation of a conventional extractive distillation system.     

Energy-Efficient Process with a Decanter to Separate Toluene-Methanol-Water Ternary Azeotropic Mixtures

An extractive distillation process with two columns and a decanter was proposed to separate ternary toluene-methanol-water azeotropic mixtures in a previous study. Based on this process, six processes were established to explore further energy-efficient schemes to separate the ternary azeotropic system. The optimal parameters of the process were determined in terms of the minimum total annual cost (TAC). The processes with heat integration perform better than those with a side stream or thermal coupling in terms of energy savings and TAC reduction. A process in which both the feed stream of the extractive distillation column and the entrainer recovery column are preheated by the entrainer recycle stream can reduce energy consumption by up to 27.69 % and TAC by 21.36 %.     

Optimization of the Design and Operation of Extractive Distillation Processes

The achievement of the optimal operating point of extractive distillation systems involves determining the values of the process variables, such as the solvent flowrate, the reflux ratio of the extractive, and recovery columns. From the point of view of design, the optimum involves defining the number of stages of extractive and recovery columns, as well as the feed stage positions of these columns. The above-mentioned columns are coupled through a recycle stream, which makes obtaining the optimal operating and design points a more complex task. This study arose from a new procedure for the analysis of extractive distillation columns, in which the solvent mole fraction in the solvent feed stage is the primary variable to be analyzed. The procedure allows for determining the values of the process and design variables that provide the global minimum for the total annual cost and the specific energy consumption of the extractive distillation processes (extractive and recovery columns). Furthermore, it is possible to determine the minimum solvent flowrate and the minimum reflux ratio for separation. Obtaining anhydrous ethanol using ethylene glycol as solvent is the case study of this work.     

Optimal retrofit design of extractive distillation to energy efficient thermally coupled distillation scheme

Design and optimization procedures employing the response surface methodology (RSM) for retrofitting the conventional extractive distillation sequence to a thermally coupled extractive distillation scheme (TCEDS—SR) is presented. The optimum TCEDS—SR structure can be found in a practical manner with minimal simulation runs. Furthermore, the RSM allows the interactions between variables to be identified and quantified. The separation of close boiling point mixtures and azeotropic mixtures was examined to test the proposed method. The predictions agreed well with the results of a rigorous simulation. The results showed that a retrofit of the extractive distillation sequence to TCED—SR can achieve significant energy savings compared to the conventional extractive distillation sequence. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1175–1182, 2013     

Reducing energy consumption and CO2 emissions in extractive distillation: Part II. Dynamic behavior

The structure of thermally coupled distillation systems offers several control challenges arising from the transfer of vapor (or liquid) streams between columns. In particular, the presence of recycle streams for coupled schemes has led to the notion that control problems might be expected during the operation of these systems, in contrast to the rather well-known behavior of conventional distillation sequences. In this work, we analyze the control properties of thermally coupled extractive distillation schemes studied previously (Gutiérrez-Guerra, R., Segovia-Hernández, J.G. and Hernández, S., 2009, Reducing energy consumption and CO₂ emissions in extractive distillation. Chem Eng Res Des, 87: 145–152). Control properties are analyzed with the application of the singular value decomposition technique and a closed-loop analysis. The results showed that the energy savings predicted in the complex extractive distillation sequence can be achieved along with good dynamic behavior and reductions in greenhouse gas emissions.     

Mechanism analysis of solvent selectivity and energy-saving optimization in vapor recompression-assisted extractive distillation for separation of binary azeotrope

Octane and p-xylene are common components in crude gasoline, so their separation process is very important in petroleum industry. The azeotrope and near azeotrope are often separated by extractive distillation in industry, which can realize the recovery and utilization of resources. In this work, the vapor–liquid equilibrium experiment was used to obtain the vapor–liquid equilibrium properties of the difficult separation system, and on this basis, the solvent extraction mechanism was studied. The mechanism of solvent separation plays a guiding role in selecting suitable solvents for industrial separation. The interaction energy, bond length and charge density distribution of p-xylene with solvent are calculated by quantum chemistry method. The quantum chemistry calculation results and experiment results showed that N-formylmorpholine is the best solvent among the alternative solvents in the work. This work provides an effective and complete solvent screening process from phase equilibrium experiments to quantum chemical calculation. An extractive distillation simulation process with N-formylmorpholine as solvent is designed to separate octane and p-xylene. In addition, the feasibility and effectiveness of the intensified vapor recompression assisted extraction distillation are also discussed. In the extractive distillation process, the vapor recompression-assisted extraction distillation process is globally optimal. Compared with basic process, the total annual cost can be reduced by 43.2%. This study provides theoretical guidance for extractive distillation separation technology and solvent selection.     

A new process for fuel ethanol dehydration based on modeling the phase equilibria of the anhydrous MgCl2 + ethanol + water system

The use of ethanol as a fuel for motor engines has attracted significant attention because of its possible environmental and economic advantages over fossil fuel. However, the energy demand for the ethanol dehydration process significantly impacts its production cost. A new and energy efficient process is developed on the basis of salt extractive distillation, which uses recycled MgCl₂ granules as a separating agent. Vapor‐liquor‐equilibria (VLE) data for the ternary MgCl₂ + ethanol + water system, and the three constituent binary systems were measured at 30, 60, 90, and 101.3 kPa. A large enhancement of relative volatility of the ethanol + water system in the presence of MgCl₂ is observed throughout the entire ethanol concentration range, which completely broke the azeotrope. The salt effect of MgCl₂ is thought to be the result of energetic interactions and the hydration equilibrium reaction of the Mg²⁺ ion with water molecules. The calculation results by the mixed‐solvent electrolyte model embedded in the OLI platform equipped with new model interaction parameters and equilibrium constant (obtained via the regression of experimental VLE data), provided for a satisfactory means of simulating the MgCl₂ salt extractive distillation process. Finally, the process was proven feasible at the laboratory‐scale resulting in large granules of recovered MgCl₂ and a product of 99.5 wt % ethanol. © 2014 American Institute of Chemical Engineers AIChE J, 61: 664–676, 2015     

萃取精馏分离苯/环己烷共沸体系模拟与优化

以糠醛作为萃取剂分别使用常规萃取精馏、隔壁塔萃取精馏和差压热集成萃取精馏对苯和环己烷体系进行分离研究,使用流程模拟软件Aspen Plus V8.4进行模拟分析,对初步设计的三稳态流程,分别进行灵敏度分析,使用多目标遗传算法对过程进行整体优化以获得最优结构参数。结果表明,隔壁塔萃取精馏和差压热集成萃取精馏相对于常规萃取精馏所需再沸器热负荷可分别减小21.5%和15.7%。对三工艺流程进行经济性分析,发现与常规流程相比,隔壁塔萃取精馏的年总费用下降了6.0%,而差压热集成萃取精馏年总费用增加了50.8%,为萃取精馏分离苯/环己烷共沸体系工业化设计提供了理论依据和设计参考。     

Experimental validation of hybrid distillation‐vapor permeation process for energy efficient ethanol–water separation

BACKGROUND: The energy demand of distillation‐based systems for ethanol recovery and dehydration can be significant, particularly for dilute solutions. An alternative separation process integrating vapor stripping with a vapor compression step and a vapor permeation membrane separation step, termed membrane assisted vapor stripping (MAVS), has been proposed. The hydrophilic membrane separates the ethanol–water vapor into water‐rich permeate and ethanol‐enriched retentate vapor streams from which latent and sensible heat can be recovered. The objective of this work was to demonstrate experimentally the performance of a MAVS system and to compare the observed performance with chemical process simulation results using a 5 wt% ethanol aqueous feed stream as the benchmark. RESULTS: Performance of the steam stripping column alone was consistent with chemical process simulations of a stripping tower with six stages of vapor liquid equilibria (VLE). The overhead vapor from the stripper contained about 40 wt% ethanol and required 6.0 MJ of fuel‐equivalent energy per kg of ethanol recovered in the concentrate. Introduction of the vapor compressor and membrane separation unit and recovery of heat from both membrane permeate and retentate streams resulted in a retentate ethanol concentrate containing ca 80 wt% ethanol, but requiring only 2.2 MJ fuel kg^?1 ethanol, significantly less than steam stripping alone. CONCLUSION: Performance of the experimental unit with a 5 wt% ethanol feed liquid corroborated chemical process simulation predictions for the energy requirement of the MAVS system, demonstrating a 63% reduction in the fuel‐equivalent energy requirement for MAVS compared with conventional steam stripping or distillation. Published 2009 by John Wiley & Sons, Ltd.     

Novel applications of dividing‐wall column technology to biofuel production processes

Biofuels enjoy nowadays increased public and scientific attention, driven by key factors such as volatile oil price, the need for increased energy security, and concerns over greenhouse gas emissions from fossil fuels. However, in order to make biofuels a competitive alternative, the cost of production has to be significantly reduced by using enhanced process technologies. Distillation is heavily involved in the production processes of biofuels—taking the blame for the high energy requirements that have a negative impact on the operating costs. Dividing‐wall column (DWC) is one of the best examples of proven industrial process intensification technology in distillation, as it allows significantly lower investment and operating costs while also reducing the number of equipment units and the carbon footprint. This work presents an overview of novel applications using the DWC technology in the production of the most important biofuels, by employing multi‐component separations, azeotropic, extractive or reactive distillation in a DWC: enhanced methanol recovery and glycerol separation in biodiesel production, synthesis of fatty acid methyl esters and dimethyl ether (DME) by reactive distillation, integrated DME purification and methanol or CO₂ recovery in the dimethyl ether process, as well as bioethanol concentration and dehydration. The industrially relevant case studies presented here show that significant energy savings are possible (ranging from ∼20 to 60%) while simplifying the processes by using less equipment that requires a lower plant footprint. Remarkably, in most cases there is also the possibility of revamping existing plants producing biofuels, and thus reusing the already available equipment. © 2013 Society of Chemical Industry     

Analysis of Energy‐Efficient Complex Distillation Options to Purify Bioethanol

Three complex extractive distillation options were studied for the purification of a dilute mixture of ethanol and water. The first option uses an extractive distillation column and the other two options use thermally coupled extractive distillation sequences. The results indicate that the fully thermally coupled extractive option can reduce energy consumption by ca. 30 % compared to the scheme that uses an extractive distillation column. This fully thermally coupled extractive distillation sequence can produce ethanol as distillate with a mass fraction of 0.995, the entrainer as the bottoms product and a mixture of ethanol and water as the sidestream.     

A novel multistage vapor recompression reactive distillation system with intermediate reboilers

Most of the published studies have focused on the thermal integration of nonreactive distillation columns. The key limitation of reactive distillation (RD) technology is that the necessary conditions (such as pressure and temperature) for the reaction must match those of distillation. Owing to this constraint, the reaction conversion may be adversely affected at the elevated pressure in the reactive section of an internally heat integrated distillation column (HIDiC). This fact forces us to adopt an external heat integration approach for an industrial heterogeneously catalyzed ethyl tert‐butyl ether (ETBE) RD column. The direct vapor recompression column (VRC) is an external heat integration scheme that is successfully used as an energy efficient scheme for separating a close‐boiling mixture. Interestingly, there exists a large temperature difference between the two ends of the representative ETBE column, and it makes the external heat integration more challenging. Aiming to improve the thermal efficiency of the ETBE column under the VRC framework, various heat pump arrangements with intermediate reboiler(s) (IR(s)) are explored and analyzed with performing a comparative study in terms of energy consumption and economics. To improve further the thermal efficiency, in this contribution, a novel multistage vapor recompression RD column with IRs is introduced addressing a number of practical concerns. An algorithm for the proposed column is formulated showing the sequential steps involved in heat integration. It is inspected that the proposed multistage vapor recompression RD system appears overwhelmingly superior to the classical vapor recompression RD and its conventional stand alone column providing a significant savings in energy as well as cost. © 2012 American Institute of Chemical Engineers AIChE J, 59: 761–771, 2013     

纤维素燃料乙醇技术经济分析

考察了以玉米秸秆为原料生产燃料乙醇的工艺流程,对年产5万t燃料乙醇的生产工艺进行了技术经济和敏感性分析. 蒸馏能耗分析表明,当发酵醪中乙醇浓度高于4%(w)时蒸馏的能耗比较低. 年产5万t燃料乙醇的直接固定成本约1.37亿元,乙醇的最低成本为8425 ￥/t. 该工艺能副产3.75万t CO2和215 t杂醇油,可带来额外收益2386万元. 经济敏感性分析表明,纤维素酶价格对生产成本的影响较显著,副产物CO2的回收利用可明显增加收益.     

Salt effect in distillation: A literature review II

A salt dissolved in a mixed solvent is capable, through preferential association or other structure-related effects in the liquid phase, of altering the composition of the equilibrium vapor phase. Hence salt effect on vapor-liquid equilibrium relationships provides a potential technique of extractive distillation for difficult separations. The literature pertaining to salt effect in vapor-liquid equilibrium and in extractive distillation over the period 1966-present is reviewed, and also the remainder of work up to 1966 not covered in the Part I review.     

利用溶盐精馏法分离乙醇—水体系的研究

乙醇浓度达到95.57%时,乙醇—水形成共沸体系无法继续分离,必须通过其他途径实现无水乙醇的制备。目前工业上采用共沸精馏、萃取精馏、溶盐精馏等方法制备无水乙醇。本文采用溶盐精馏法,研究无水氯化钙及醋酸钾在乙醇—水体系中的分离作用。     

Analysis of control properties of intensified distillation sequences: Reactive and extractive cases

In this work, we obtain and compare the control properties of thermally coupled reactive distillation sequences and thermally coupled extractive distillation sequences with those of conventional reactive and extractive distillation configurations. All sequences have been designed using a multiobjective genetic algorithm with restrictions. The theoretical control properties of those schemes were obtained using the singular value decomposition technique in all frequency domain. In order to complete the control study, the distillation options were subjected to closed-loop dynamic simulations. The effects of total stages, reactive stages, and extractant/feed ratio on the energy consumption and control properties are obtained for the intensified distillation options. The results show that there are cases in which integrated reactive and extractive sequences do not only provide significant energy savings with respect to the conventional reactive and extractive arrangements, but also may offer dynamic advantages in high energy consumption conditions.