Ces travaux sont centrés sur l’étude des potentialités d’utilisation de la pervaporation, procédé de séparation par membrane, en couplage avec des procédés de séparation ou de réaction. L’objectif principal est d’évaluer la faisabilité technico-économique, le gain potentiel mais aussi les limites de son application compatible avec une exploitation industrielle. La détermination de ce gain passe par la simulation des procédés qui nécessite une modélisation correcte des processus élémentaires. Une modélisation à plusieurs niveaux est proposée. Elle permet de prendre en compte les différents systèmes d’études : matériaux membranaires et cas d’application et de donner le choix du nombre de paramètres ajustables en fonction des données expérimentales disponibles. Cette démarche a été appliquée à deux applications différentes. Le premier cas correspond à la récupération de butanol à partir de milieu de fermentation. Cette étude a montré des gains sur la productivité de la fermentation par couplage direct du fermenteur avec la pervaporation équipée de membrane hydrophobe. Le second cas correspond à la séparation eau/acide acétique, avec pour objectif la minimisation de la consommation énergétique pour un cahier des charges fixé. Le couplage retenu met en œuvre une étape de distillation suivie d’une étape de pervaporation équipée d’une membrane hydrophile. Les performances de quatre membranes ont été déterminées expérimentalement pour cette application. Enfin, une méthodologie est proposée permettant de déterminer les performances minimales de membrane permettant d’atteindre, en fonction des spécifications du cahier des charges, un gain énergétique par rapport au procédé conventionnel / The potential economical interest of using pervaporation, a membrane separation process, in hybrid processes (with separation or reaction unit) has been investigated. The main objective is to determine benefits and limitations of its use for an industrial application. The determination of the interest is predicted by simulation which requires a good understanding and a good representation of the elementary phenomenon of mass transfer and thermodynamic. A multilevel pervaporation modelling is developed, which takes into account the system variability (membranes and compounds) and allows choosing the number of fitted parameters according to the available experimental data. Two different industrial applications are studied. First, the recuperation of butanol from a fermentation medium is exposed. This case study has shown the gain on fermentation productivity when pervaporation, equipped with hydrophobic membrane, is used in direct coupling with fermenter. Next, the dehydration of acetic acid is studied with the aim of reduction the energy consumption of the conventional process. The configuration which has been selected involves a distillation column followed by a pervaporation module, equipped with a hydrophilic membrane. Performances of four membranes have been experimentally determined by for this application. Finally, a simulation methodology is developed, which can be applied to determine the membrane performances that need to be achieved to replace conventional processes with a hybrid process while respecting industrial specifications

Commercial pure terephthalic acid (PTA) manufacturing generates process streams mainly containing acetic acid (HAc) and water. A large financial incentive exists to replace the costly and energy intensive distillation column used to recycle HAc-water mixtures. This work focuses on the development of pervaporation technology to separate HAc-water mixtures using a hollow fiber-based membrane unit. Currently a 250 m outer diameter Matrimid® hollow fiber is used in industry for gas separation. Due to the difference between gas and liquid separations, the fiber performance associated with high flux in pervaporation is limited by a pressure change inside the bore along the axial direction of the fiber. A mathematical model was developed to describe the bore pressure change in pervaporation in this work, which demonstrated that spinning a large bore size fiber was a good solution to minimize the bore pressure change. Spinning technology has been adapted to obtain a large bore size defect-free Matrimid® hollow fiber. In addition to a large bore size, the asymmetric fiber exhibits an intrinsically defect-free selective layer supported on an open porous substrate. This eliminates the post-treatment with a caulking layer and has a special advantage for aggressive liquid separation. A proof of concept was provided by testing both small and large bore size defect-free fibers with a model 20% wt HAc feed in a pervaporation system at 101.5oC. The membrane selectivity (~ 25) and water flux (~ 4.5 kg/m2hr) were increased by about 150% with a diameter (O.D. ~ 500 m) twice as large as the regular fiber. Further, a decrease in the HAc flux was observed with the increased bore size due to the reduction in HAc-induced plasticization. Sub-Tg thermal annealing was used to stabilize the fiber by suppressing HAc-induced plasticization. This improves the polymer discrimination of shape and size for penetrants although no chemical reaction occurs with thermal annealing. The resulting membrane selectivity was increased from 10 to about 95 using a large bore size defect-free annealed fiber with acceptable water flux (~ 1.5 kg/m2hr) for 20% wt HAc concentration feed streams. These improvements make Matrimid® hollow fiber membranes very attractive for future scale-up and commercial development.

Organic/inorganic materials have a high potential to enable major advances in membrane performance. It has previously been impossible to develop polymeric systems with adequate transport properties for xylene purification. Zeolite membranes have been created with the appropriate selectivities; however low productivity, low mechanical durability, and high capital costs have kept these materials from being utilized. So-called mixed matrix hybrid organic/inorganic membranes combine the mechanical durability and cost effectiveness of polymeric membranes with the enhanced performance of zeolitic structures. This project will focus on investigating polymeric and molecular sieve materials for mixed matrix membrane use in xylene isomer separation as a model system. Torlon polyamide-imide has unique properties that should be potentially useful in a mixed matrix composite. Silicalite will be investigated as the dispersed phased given its proven applicability with xylene isomers. The overarching goal is to establish an approach for creation of mixed matrix materials that can be broadly applied to challenging organic separations. This project has three specific goals: (1) characterization of Torlons inherent properties, processing ability, and important transport potential, (2) characterization of zeolite matching properties and the effect of interfacial engineering on these properties, and (3) development of appropriate approaches to combine the sieve and polymer to obtain a hybrid material with properties that match theoretically predicted separation property enhancements relative to the neat polymer. High temperature pervaporation will be used to evaluate material transport properties, as this experimental setup closely mimics the high activity vapor streams found in many industrial xylene processes. The results of this research will be used to develop a protocol for development of future mixed matrix membranes that may be applied to a variety of organic liquid systems.

Les composés organiques volatils (COV) sont source de nuisances pour l'Homme et le milieu naturel. Des réglementations de plus en plus strictes imposent d'équiper les unités industrielles d'un procédé de traitement des effluents gazeux chargés en COV lorsque cela est nécessaire. Ce travail étudie la faisabilité technique d'un procédé hybride innovant parmi les techniques actuellement disponibles : le couplage d'un procédé d'absorption et un procédé membranaire, la pervaporation. Les différents aspects de ce procédé sont examinés : choix de l'absorbant, étude de l'hydrodynamique et du transfert de matière en colonne garnie, séparation des polluants contenus dans l'absorbant par pervaporation, couplage des deux procédés. Au final, une analyse du procédé met en lumière les grandeurs influentes et leur impact sur l'efficacité du couplage. Il est montré que le procédé hybride s'avère faisable techniquement.

Zugl.: Magdeburg, Univ., Diss., 2007

Zugl.: Dortmund, Techn. Univ., Diss., 2008

In this thesis, a theoretical description of mass transport through membranes used in pervaporation separation processes has been investigated for both dense polymeric membranes and mixed matrix membranes (MMMs). Regarding the dense polymeric membranes, the Maxwell-Stefan model was extended to consider the effect of the operating temperature and membrane swelling on the mass transport of species within the membrane. The model was applied semi-empirically to predict the membrane properties and separation performance of a commercial Polydimethylsiloxane (PDMS) membrane used in the pervaporation separation of butanol from binary aqueous solutions. It was observed that the extended Maxwell-Stefan model has an average error of 10.5 % for the prediction of partial permeate fluxes of species compared to roughly 22% for the average prediction error of the Maxwell-Stefan model. Moreover, the parameters of the model were used to estimate the sorption properties and diffusion coefficients of components through the PDMS membrane at different butanol feed concentrations and operating temperatures. The estimated values of the sorption properties were observed to be in agreement with the literature experimental data for transport properties of butanol and water in silicone membranes while an exact comparison for the diffusion coefficient was not possible due to large fluctuations in literature values. With respect to the MMMs, a new model was developed by combining a one-directional transport Resistance-Based (RB) model with the Finite Difference (FD) method to derive an analytical model for the prediction of three-directional (3D) effective permeability of species within ideal mixed matrix membranes. The main novelty of the proposed model is to avoid the long convergence time of the FD method while the three-directional (3D) mass transport is still considered for the simulation. The model was validated using experimental pervaporation data for the separation of butanol from aqueous solutions using Polydimethylsiloxane (PDMS)/activated carbon nanoparticles membranes and using data from the literature for gas separation application with MMMs. Accurate predictions were obtained with high coefficient of regression (R2) between the calculated and experimental values for both applications.

No description available.

No description available.

The separation of aqueous and organic mixtures with thermal separation processes is an important and challenging task in the chemical industry. Rising prices for energy, stricter environmental regulations and the increasing demand for high purity chemicals are the main driving forces to find alternative solutions to common separation technologies such as distillation and absorption. These are mostly too energy consumptive and can show limited separation performance, especially when applied to close boiling or azeotropic mixtures. Pervaporation can overcome these thermodynamic limitations and requires less energy because only the separated components need to be evaporated. This separation technology is already well established for the production of anhydrous solvents, but not yet widely distributed in the chemical and petrochemical industry due to some crucial challenges, which are still to overcome. Besides the need of high selective membranes, the development of membrane modules adapted to the specific requirements of organoselective pervaporation needs more research effort. Furthermore, only few modelling and simulation tools are available, which hinders the distribution of this process in industrial scale. In this work, these issues are addressed in a combined approach. In close collaboration with our cooperation partners, a novel membrane module for organophilic pervaporation is developed. A novel technology to manufacture high selective polymeric pervaporation membranes is applied to produce a membrane for an industrially relevant organic-organic separation task. A three step modelling approach ranging from a shortcut and a discrete to a rigorous model is developed and implemented in a user interface. A hydrophilic and an organophilic membrane are characterised for the separation of a 2-butanol/water mixture in a wide range of feed temperature and feed concentration in order to establish a generally valid description of the membrane performances. This approach is implemented in the three developed models to simulate the novel membrane module in industrial scale. The simulations are compared to the results of pilot scale experiments conducted with the novel membrane module. Good agreement between simulated and experimental values is reached.