Heterogeneous Extractive Batch Distillation of Chloroform - Methanol – Water : Feasibility and Experiments

A novel heterogeneous extractive distillation process is considered for separating the azeotropic mixture chloroform – methanol in a batch rectifying column, including for the first time an experimental validation of the process. Heterogeneous heavy entrainer water is selected inducing an unstable ternary heteroazeotrope and a saddle binary heteroazeotrope with chloroform (ternary diagram class 2.1-2b). Unlike to well-known heterogeneous azeotropic distillation process and thanks to continuous water feeding at the column top, the saddle binary heteroazeotrope chloroform – water is obtained at the column top, condensed and further split into the liquid – liquid decanter where the chloroform-rich phase is drawn as distillate. First, feasibility analysis is carried out by using a simplified differential model in the extractive section for determining the proper range of the entrainer flowrate and the reflux ratio. The operating conditions and reflux policy are validated by rigorous simulation with ProSim Batch Column® where technical features of a bench scale distillation column have been described. Six reproducible experiments are run in the bench scale column matching the simulated operating conditions with two sequentially increasing reflux ratio values. Simulation and experiments agree well. With an average molar purity higher than 99%, more than 85% of recovery yield was obtained for chloroform and methanol

Heterogeneous batch distillation processes for waste solvent recovery in pharmaceutical industry

A summary about our experiences in the introduction of heterogeneous entrainers in azeotropic and extractive batch distillation is presented in this work. Essential advantages of the application of heterogeneous entrainers are showed by rigorous simulation and experimental verification in a bench batch distillation column for separating several azeotropic mixtures such as acetonitrile – water, n hexane – ethyl acetate and chloroform – methanol, commonly found in pharmaceutical industry

Generalised model for heteroazeotropic batch distillation with variable decanter hold-up

A general model of batch heteroazeotropic distillation is proposed. Both liquid phases present in the decanter can be refluxed or withdrawn as distillate, their hold-up can be increased, decreased or kept constant, as well. By assuming maximal separation, that is, that the composition of the condensate always equals to that of the heteroazeotrope, the still path equation was derived. The still path directions are determined for all the 16 possible operational policies. It is possible to steer the still path in a desired direction by changing the operational parameters, which allows the recovery of a pure component in the still. The still path directions are validated by rigorous simulations for three policies not published yet using the mixture water – formaldehyde – propyl formate. From the 16 operational policies, 11 can be considered as useful in practice. To demonstrate the advantage of using a non-traditional policy, the separation of the mixture aniline – ethylene glycol – water was investigated, as well. By using a non-traditional operational policy with hold-up reduction in the decanter a higher purity of ethylene glycol was obtained in the still

Feasibility of extractive distillation process variants in batch rectifier column

A systematic comparison is presented about the separation tasks of azeotropic and close-boiling mixtures applying batch extractive distillation (BED) in rectifier. All the eight possible mixture types with at most a single azeotrope (minimum and maximum boiling azeotropes with heavy, light, and intermediate boiling entrainers; and close boiling mixtures with heavy and light entrainers) are compared. The main results of the feasibility studies on the hitherto unpublished cases are presented. All the cases are feasible in batch rectifier, applying BED. The operation steps are determined by the relative position of the azeotropic composition and entrainer in bubble point ranking. The main limiting parameters (F/V, N, Epremix) are also determined by the mentioned relative position; only the existence of maximum number of stages in the rectifying section is determined by the type of the azeotrope. Use of residue curves maps (RCMs) for predicting feasibility is not generally satisfactory, but profiles maps can be used instead. Studying only the total reflux case can be misleading, and should be treated with great care. The theoretical results of separation variants applying intermediate boiling entrainer were proved experimentally

Extractive distillation: recent advances in operation strategies

Extractive distillation is one of the efficient techniques for separating azeotropic and low-relativevolatility mixtures in various chemical industries. This paper first provides an overview of thermodynamic insight covering residue curve map analysis, the application of univolatility and unidistribution curves, and thermodynamic feasibility study. The pinch-point analysis method combining bifurcation shortcut presents another branch of study, and several achievements have been realized by the identification of possible product cut under the following key parameters: reflux ratio, reboil ratio, and entrainer-feed flow rate ratio. Process operation policies and strategy concerning batch extractive distillation processes are summarized in four operation steps. Several configurations and technological alternatives can be used when extractive distillation processes take place in a continuous or batch column, depending on the strategy selected for the recycle streams and for the main azeotropic feeds

Nouveaux systèmes de double colonne pour distillation hétéroazéotropique discontinue

J'ai étudié deux nouvelles configurations de double-colonne pour distillation hétéroazéotropique. Ces configurations sont appropriées à la récupération simultanée des composants des mélanges binaires hétéroazéotropiques et homoazéotropiques (en utilisant un tiers corps (entraîneur)). Elle sont opérées en système fermé, c'est-à-dire, il n'y a pas de soutirage de produit continu. D'abord, en appliquant un modèle simplifié, j'ai étudié la faisabilité de la séparation d'un mélange hétéroazéotropique (1-butanol eau), puis celle d'un mélange homoazéotropique (2-propanol eau) aidé par entraîneur benzène ou cyclohexane, en utilisant le SDC. Puis, j'ai étudié cette configuration par modélisation rigoureuse, en appliquant le simulateur dynamique du logiciel professionnel ChemCAD (CC-DColumn). J'ai comparé la nouvelle configuration avec le RD, sur la base des résultats obtenus par toutes les deux méthodes d'étude. Le SDC s'est avéré faisable et compétitif avec le RD : pendant la même durée ou plus courte, les rendements des composants ont été plus élevés. Puis, on a étendu le SDC à un système plus flexible (système de double-colonne généralisé, SDCG) qui est approprié à la séparation des mélanges binaires homoazéotropiques aidé par entraîneur (en le cas présent : cyclohexane ou n-hexane). J'ai étendu la méthode de faisabilité aussi à l'étude de cette configuration. Le SDCG s'est avéré aussi faisable. En appliquant modélisation rigoureuse, j'ai étudié les effets des nouveaux paramètres opératoires sur la durée, et j'ai comparé le DCG avec le SDC. Le SDCG s'est avéré encore plus avantageux que le SDC : la durée a été plus courte, et les besoins spécifiques d'énergie des produits ont été plus bas. J'ai étudié le SDC et le SDCG aussi par des manipulations exécutées sur installations de taille laboratoire et pilote. D'abord, j'ai fait des manipulations laboratoires pour la séparation du mélange binaire hétéroazéotropique, en utilisant une installation en verre qui a été opérée aussi comme RD et SDC. Le SDC s'est avéré faisable et compétitif avec le RD aussi sur la base des résultats de ces manipulations : pendant la même durée, les rendements des tous les deux composants ont été plus élevés. Puis, en utilisant l'installation pilote comme SDC, j'ai étudié la séparation ci-dessus. Après cette manipulation, j'ai étudié la séparation du mélange binaire homoazéotropique en appliquant n-hexane comme entraîneur, en opérant le système comme RD et SDCG. La manipulation faite avec le SDCG a montré que la production simultanée de deux composants est faisable avec cette configuration.Distillation is the method the most frequently applied for the separation of liquid mixtures, e.g. for the recovery of the components of the waste solvent mixtures. Because of the high energy demand of these processes the optimal design and operation of the distillation equipments are important from economic and also environmental points of view. The separation of the azeotropic mixtures needs special distillation methods like heteroazeotropic distillation. In the pharmaceutical and fine chemical industries it is often applied in batch mode. The aims of the thesis are to study the feasibility of a new Double-Column System (DCS) for batch heteroazeotropic distillation and to compare it with the traditional Batch Rectifier (BR) equipped with a decanterto study the above configurations by rigorous simulationto extend the DCS (Generalised Double-Column System, GDCS) and to study this new configuration by the above methodsto do laboratory experiments for both configurations in order to prove the feasibility of the separation and validate the calculations, respectively. Two new double-column configurations for batch heteroazeotropic distillation were studied. These configurations are designed to produce simultaneously the components of binary heteroazeotropic and homoazeotropic mixtures (by using an entrainer). They are operated in closed system (without continuous product withdrawal). First the feasibility of the separation of a heteroazeotropic mixture (1-butanol water) and that of a homoazeotropic one by using an entrainer (isopropanol water + benzene or cyclohexane) in the DCS were investigated by a simplified model. Then the operation of this configuration was modelled by rigorous simulation by using the dynamic simulator of the professional flowsheet simulator ChemCAD (CC-DColumn). On the basis of the results obtained by both methods the new configuration was compared with the BR. The DCS proved to be feasible and competitive with the BR: during the same or shorter time the recoveries of the components were higher. Then the DCS was extended to a more flexible version (Generalised Double-Column System, GDCS), which is suitable for the separation of binary homoazeotropic mixtures (by using an entrainer, in this work: cyclohexane or n- exane). The feasibility method was extended for the study of this configuration, as well. The GDCS proved to be feasible. Then the effects of its additional operational parameters on the duration were studied by rigorous simulation. The GDCS was compared with the DCS by rigorous simulation, as well. The GDCS proved to be more advantageous than the DCS: the duration was shorter and the specific energy demands of the products were lower. The DCS and GDCS were also investigated by laboratory and pilot plant experiments. First laboratory experiments were done for the separation of the binary heteroazeotropic mixture in a simple small size glass equipment operated as BR and DCS. The DCS proved to be feasible and competitive with the BR also on the basis of the results of these experiments: during the same time the recovery of both components were higher. Then a pilot plant was used for the same separation as a DCS. After this experiment the separation of the binary homoazeotropic mixture by using n-hexane as entrainer was studied in the equipment operated as BR and GDCS. The experiment showed that the simultaneous production of two components is feasible also in the GDCS.TOULOUSE-INP (315552154) / SudocSudocFranceF

New Double-Column Systems for Batch Heteroazeotropic Distillation

J'ai étudié deux nouvelles configurations de double-colonne pour distillation hétéroazéotropique. Ces configurations sont appropriées à la récupération simultanée des composants des mélanges binaires hétéroazéotropiques et homoazéotropiques (en utilisant un tiers corps (entraîneur)). Elle sont opérées en système fermé, c'est-à-dire, il n'y a pas de soutirage de produit continu. D'abord, en appliquant un modèle simplifié, j'ai étudié la faisabilité de la séparation d'un mélange hétéroazéotropique (1-butanol – eau), puis celle d'un mélange homoazéotropique (2-propanol – eau) aidé par entraîneur benzène ou cyclohexane, en utilisant le SDC. Puis, j'ai étudié cette configuration par modélisation rigoureuse, en appliquant le simulateur dynamique du logiciel professionnel ChemCAD (CC-DColumn). J'ai comparé la nouvelle configuration avec le RD, sur la base des résultats obtenus par toutes les deux méthodes d'étude. Le SDC s'est avéré faisable et compétitif avec le RD : pendant la même durée ou plus courte, les rendements des composants ont été plus élevés. Puis, on a étendu le SDC à un système plus flexible (système de double-colonne généralisé, SDCG) qui est approprié à la séparation des mélanges binaires homoazéotropiques aidé par entraîneur (en le cas présent : cyclohexane ou n-hexane). J'ai étendu la méthode de faisabilité aussi à l'étude de cette configuration. Le SDCG s'est avéré aussi faisable. En appliquant modélisation rigoureuse, j'ai étudié les effets des nouveaux paramètres opératoires sur la durée, et j'ai comparé le DCG avec le SDC. Le SDCG s'est avéré encore plus avantageux que le SDC : la durée a été plus courte, et les besoins spécifiques d'énergie des produits ont été plus bas. J'ai étudié le SDC et le SDCG aussi par des manipulations exécutées sur installations de taille laboratoire et pilote. D'abord, j'ai fait des manipulations laboratoires pour la séparation du mélange binaire hétéroazéotropique, en utilisant une installation en verre qui a été opérée aussi comme RD et SDC. Le SDC s'est avéré faisable et compétitif avec le RD aussi sur la base des résultats de ces manipulations : pendant la même durée, les rendements des tous les deux composants ont été plus élevés. Puis, en utilisant l'installation pilote comme SDC, j'ai étudié la séparation ci-dessus. Après cette manipulation, j'ai étudié la séparation du mélange binaire homoazéotropique en appliquant n-hexane comme entraîneur, en opérant le système comme RD et SDCG. La manipulation faite avec le SDCG a montré que la production simultanée de deux composants est faisable avec cette configuration. ABSTRACT : Distillation is the method the most frequently applied for the separation of liquid mixtures, e.g. for the recovery of the components of the waste solvent mixtures. Because of the high energy demand of these processes the optimal design and operation of the distillation equipments are important from economic and also environmental points of view. The separation of the azeotropic mixtures needs special distillation methods like heteroazeotropic distillation. In the pharmaceutical and fine chemical industries it is often applied in batch mode. The aims of the thesis are to study the feasibility of a new Double-Column System (DCS) for batch heteroazeotropic distillation and to compare it with the traditional Batch Rectifier (BR) equipped with a decanter to study the above configurations by rigorous simulation to extend the DCS (Generalised Double-Column System, GDCS) and to study this new configuration by the above methods to do laboratory experiments for both configurations in order to prove the feasibility of the separation and validate the calculations, respectively. Two new double-column configurations for batch heteroazeotropic distillation were studied. These configurations are designed to produce simultaneously the components of binary heteroazeotropic and homoazeotropic mixtures (by using an entrainer). They are operated in closed system (without continuous product withdrawal). First the feasibility of the separation of a heteroazeotropic mixture (1-butanol – water) and that of a homoazeotropic one by using an entrainer (isopropanol – water + benzene or cyclohexane) in the DCS were investigated by a simplified model. Then the operation of this configuration was modelled by rigorous simulation by using the dynamic simulator of the professional flowsheet simulator ChemCAD (CC-DColumn). On the basis of the results obtained by both methods the new configuration was compared with the BR. The DCS proved to be feasible and competitive with the BR: during the same or shorter time the recoveries of the components were higher. Then the DCS was extended to a more flexible version (Generalised Double-Column System, GDCS), which is suitable for the separation of binary homoazeotropic mixtures (by using an entrainer, in this work: cyclohexane or n- exane). The feasibility method was extended for the study of this configuration, as well. The GDCS proved to be feasible. Then the effects of its additional operational parameters on the duration were studied by rigorous simulation. The GDCS was compared with the DCS by rigorous simulation, as well. The GDCS proved to be more advantageous than the DCS: the duration was shorter and the specific energy demands of the products were lower. The DCS and GDCS were also investigated by laboratory and pilot plant experiments. First laboratory experiments were done for the separation of the binary heteroazeotropic mixture in a simple small size glass equipment operated as BR and DCS. The DCS proved to be feasible and competitive with the BR also on the basis of the results of these experiments: during the same time the recovery of both components were higher. Then a pilot plant was used for the same separation as a DCS. After this experiment the separation of the binary homoazeotropic mixture by using n-hexane as entrainer was studied in the equipment operated as BR and GDCS. The experiment showed that the simultaneous production of two components is feasible also in the GDCS

Thermodynamic Insights on the Feasibility of Homogeneous Batch Extractive Distillation. 3. Azeotropic Mixtures with Light Boiling Entrainer

This article shows how knowledge of the location of univolatility lines and residue curve analysis helps in assessing the feasibility of extractive distillation of minimum-boiling (minT) or maximum-boiling (maxT) azeotropic mixtures or low-relative volatility (low-α) mixtures (A-B) by using a light-boiling entrainer (E), in accordance with the general feasibility criterion of Rodriguez-Donis et al. [Ind. Eng. Chem. Res. 2009, 48 (7), 3544-3559]. Considering all possible locations of the univolatility line αAB, three minT azeotropic mixtures with a light entrainer (1.0-2 class), namely, ethanol-water with methanol, ethanol-toluene with acetone, and methyl ethyl ketone-benzene with acetone; three maxT azeotropic mixtures with a light entrainer (1.0-1a class), namely, water-ethylenediamine with methanol, acetone-chloroform with dichlomethane, and propanoic acid-dimethyl formamide withmethyl isobutyl ketone; and one low-α mixture with a light entrainer (0.0-1 class), namely, ethyl acetate-benzene with acetone, were studied in a stripping extractive column. For the 1.0-2 class, both A and B can be recovered as the bottom product, depending on the location of αAB = 1, which sets limiting values for the entrainer feed flow rate FE/LT for one of the product. In addition, the feasible region of the extractive distillation process is larger than for the azeotropic distillation process. For the 1.0-1a class, the product is either A or B, depending on the location of αAB = 1, which sets a minimum value of (FE/LT)min for one of the product. For the 0.0-1 class, feasibility depends on the existence αAB = 1. When it does not exist, B is the unique possible product. When it does, both A and B are products, with B below a maximum value of (FE/LT)max,B and A above a minimum value (FE/LT)min,

Improvement of Batch Distillation Separation of Azeotropic Mixtures

La distillation est le procédé de séparation le plus répandu dans l'industrie chimique. Pour la séparation des mélanges azéotropiques, une méthode spéciale de distillation doit être appliquée. Le but de mon travail était d'améliorer la séparation des mélanges azéotropiques par distillation discontinue (DD). Un nouvel algorithme a été présenté pour la détermination de la séquence des produits de DD pour des mélanges multicomposants azéotropiques. Contrairement aux méthodes publiées précédemment, cet algorithme n'a pas besoin des paramètres d'équilibre. Configurations non-conventionnelles de DD ont été étudiées par simulation rigoureuse avec un accent sur l'opération fermée. Nombreux modes d'opération fermés étaient proposés, lesquelles diffèrent en l'opération de réservoir supérieur. Les effets du recyclage des fractions sur un procédé de séparation existant de 6 lots d'un mélange déchet azéotropique ont été étudiés. Les études ont été étendues pour un procédé de distillation extractive discontinue (DED). Un volume minimal de pré-fraction doit être incinéré. Le cas optimal de DED a donné un profit plus grand que celui de DD. DED a été étudié pour la séparation des deux mélanges azéotropiques. La séparation a été infaisable ou le rendement a été bas par DD, mais DED et le procédé hybride ont donné des rendements élevés. Une nouvelle politique de DED a été aussi proposée. Un modèle généralisé de la distillation hétéroazéotropique discontinue avec une rétention variable de décanteur a été développé. Dans une analyse de faisabilité, toutes les politiques opérationnelles possibles ont été identifiées. Ce modèle a été étendu pour la distillation extractive hétérogène discontinue. ABSTRACT : Distillation is the most widespread method for separating liquid mixtures. The separation of azeotropic mixtures requires a special distillation method. My aim was to improve the batch distillation separation of azeotropic mixtures. A new algorithm was presented for the determination of product sequences of batch distillation of multicomponent azeotropic mixtures. Non-conventional configurations were studied by simulation with emphasis on closed operation. The effects of off-cut recycle on a six-batch separation process of a waste solvent mixture were also investigated. Batch extractive distillation was studied for the separation of two azeotropic mixtures. A new extractive policy was also proposed. A generalised model of batch heteroazeotropic distillation with variable decanter hold-up was developed. This model was extended for batch heterogeneous extractive distillation

Tray efficiency effects in batch distillation

Computer simulation has long been recognised as a useful tool in improved process operation and design studies. Commercial simulation packages now available for batch distillation studies typically assume constant tray efficiency. Here, on the basis of both practical work and computer simulation, the effects of tray efficiency variation with tray liquid composition on model accuracy and column performance are investigated. Detailed modelling studies were carried out on a pilot batch distillation unit and tray efficiency was found to be an important factor affecting the model fidelity. Distillation of different methanol/water mixtures revealed that tray efficiency varies with the mixture composition on the tray, the form of the variation being for the efficiency to pass through a minimum at intermediate compositions. This variation of tray efficiency with tray composition is a known phenomenon, which has not been included in batch distillation simulations even though tray compositions change significantly during a batch run. The model developed in this work (Variable Efficiency Model) includes the tray efficiency variation with mixture composition and results in an evident improvement in model accuracy for methanol/water distillation. The potential effects of strong tray efficiency dependence on mixture composition, at a more general level, are investigated using two case studies, based on hypothetical extensions of the tray efficiency concentration dependence observed for methanol/water mixtures. In extreme cases, the efficiency-composition dependence could introduce a significant additional non-linearity to the process behaviour, resulting in unexpected composition and temperature movements. To quantify the potential significance of these effects, the economic performance of a column based on simulation using the Variable Efficiency Model was compared with its performance, using an overall column efficiency (which is the common practice). Using fixed column efficiency was found to under-predict column performance for low purity products and over-predict performance for high purity products