Process Analysis of Asymmetric Hollow Fiber Permeators, Unsteady State Permeation and Membrane-Amine Hybrid Systems for Gas Separations

The global market for membrane separation technologies is forecast to reach $16 billion by the year 2017 due to wide adoption of the membrane technology across various end-use markets. With the growth in demand for high quality products, stringent regulations, environmental concerns, and exhausting natural resources, membrane separation technologies are forecast to witness significant growth over the long term (Global Industry Analysts Inc., 2011). The future of membrane technology promises to be equally exciting as new membrane materials, processes and innovations make their way to the marketplace. The current trend in membrane gas separation industry is, however, to develop robust membranes, which exhibit superior separation performance, and are reliable and durable for particular applications. Process simulation allows the investigation of operating and design variables in the process, and in new process configurations. An optimal operating condition and/or process configuration could possibly yield a better separation performance as well as cost savings. Moreover, with the development of new process concepts, new membrane applications will emerge. The thesis addresses developing models that can be used to help in the design and operation of CO2 capture processes. A mathematical model for the dynamic performance of gas separation with high flux, asymmetric hollow fiber membranes was developed considering the permeate pressure build-up inside the fiber bore and cross flow pattern with respect to the membrane skin. The solution technique is advantageous since it requires minimal computational effort and provides improved solution stability. The model predictions and the robustness of the numerical technique were validated with experimental data for several membrane systems with different flow configurations. The model and solution technique were applied to investigate the performance of several membrane module configurations for air separation and methane recovery from biogas (landfill gas or digester gas). Recycle ratio plays a crucial role, and optimum recycle ratios vital for the retentate recycle to permeate and permeate recycle to feed operation were found. From the concept of two recycle operations, complexities involved in the design and operation of continuous membrane column were simplified. Membrane permselectivity required for a targeted separation to produce pipeline quality natural gas by methane-selective or nitrogen-selective membranes was calculated. The study demonstrates that the new solution technique can conveniently handle the high-flux hollow fiber membrane problems with different module configurations. A section of the study was aimed at rectifying some commonly believed perceptions about pressure build-up in hollow fiber membranes. It is a general intuition that operating at higher pressures permeates more gases, and therefore sometimes the membrane module is tested or characterized at lower pressures to save gas consumption. It is also perceived that higher pressure build-up occurs at higher feed pressures, and membrane performance deteriorates at higher feed pressures. The apparent and intrinsic permeances of H2 and N2 for asymmetric cellulose acetate-based hollow fiber membranes were evaluated from pure gas permeation experiments and numerical analysis, respectively. It was shown that though the pressure build-up increases as feed pressure increases, the effect of pressure build-up on membrane performance is actually minimized at higher feed pressures. Membrane performs close to its actual separation properties if it is operated at high feed pressures, under which conditions the effect of pressure build-up on the membrane performance is minimized. The pressure build-up effect was further investigated by calculating the average loss and percentage loss in the driving force due to pressure build-up, and it was found that percentage loss in driving force is less at high feed pressures than that at low feed pressures. It is true that unsteady state cyclic permeation process can potentially compete with the most selective polymers available to date, both in terms selectivity and productivity. A novel process mode of gas separation by means of cyclic pressure-vacuum swings for feed pressurization and permeate evacuation using a single pump was evaluated for CO2 separation from flue gas. Unlike transient permeation processes reported in the literature which were based on the differences in sorption uptake rates or desorption falloff rates, this process was based on the selective permeability of the membrane for separations. The process was analyzed to elucidate the working principle, and a parametric study was carried out to evaluate the effects of design and operating parameters on the separation performance. It was shown that improved separation efficiency (i.e., product purity and throughput) better than that of conventional steady-state permeation could be obtained by means of pressure-vacuum swing permeation. The effectiveness of membrane processes and feasibility of hybrid processes combining membrane permeation and conventional amine absorption process were investigated for post-combustion CO2 capture. Traditional MEA process uses a substantial amount of energy at the stripper reboiler when CO2 concentration increases. Several single stage and multi-stage membrane process configurations were simulated for a target design specification aiming at possible application in enhanced oil recovery. It was shown that membrane processes offer the lowest energy penalty for post-combustion CO2 capture and likely to expand as more and more CO2 selective membranes are developed. Membrane processes can save up to 20~45% energy compared to the stand-alone MEA capture processes. A comparison of energy perspective for the CO2 capture processes studied was drawn, and it was shown that the energy requirements of the hybrid processes are less than conventional MEA processes. The total energy penalty of the hybrid processes decreases as more and more CO2 is removed by the membranes

Assessment of the Industrial Potentials for an Innovative High-tech Separation Method

Currently, we are facing a general technological gap for the separation of mixtures containing colloidal particles (metallic nano-particles, macro-molecules, etc.). This project aims to extend the principle of Hollow Fiber Flow Field-Flow Fractionation (HF5) toward continuous size-based separation of colloidal suspensions. HF5 is an analytical technique used for particle fractionation (according to their size) in view of their characterization. The principle of particle separation is based on consecutive focusing of particles of different sizes on different ow streamlines with the aid of a permeate ow applied across the hollow-ber wall and their differential elution by the main ow streamlines at the ber outlet. In this Ph.D., we developed an automated sequential prototype based on the HF5 principles. The accumulation and elution conditions were explored, leading to the prescription of a separation methodology, which applies for stable negatively charged Brownian particles (in order to limit particle aggregation and adsorption on the membrane). A CFD model was developed to guide the initial prototype design and the choice of the operating conditions. The numerical model was extended to include an original description of colloidal dynamics near phase transition and its impact on near-membrane particle accumulation and relaxation processes. We evidenced the existence of a permeate ow-rate (during elution) at which the Brownian diffusion prevails over the drag force, and that allows controlling particle differential elution: this reveals to be a crucial condition for successful separation. The developed prototype allows the processing of higher sample amount than classical HF5, by using the total membrane surface during particle focusing. We performed the separation of latex polystyrene nanoparticles with a size ratio of 5, using 4.74 μg of particles per cm 2 of membrane without compromising the peak resolution (similar to AF4 conguration and superior to HF5). Moreover, the prototype allows running several consecutive separation cycles (up to ve cycles were tested), without increasing membrane fouling. To allow prototype scale-up, further optimization of particle accumulation along the membrane and permeate-ow control during elution are needed. Finally, a system for continuous operation was developed. It is not included in this manuscript for confidentiality reasons

Analysis and theory of gas transport in microporous sol-gel derived ceramic membranes

Sol-gel modification of mesoporous alumina membranes is a very successful technique to improve gas separation performance. Due to the formed microporous top layer, the membranes show activated transport and molecular sieve-like separation factors. This paper concentrates on the mechanism of activated transport (also often referred to as micropore diffusion or molecular sieving). Based on a theoretical analysis, results from permeation and separation experiments with H2, CO2, O2, N2, CH4 and iso-C4H10 on microporous sol-gel modified supported ceramic membranes are integrated with sorption data.\ud \ud Gas permeation through these membranes is activated, and for defect-free membranes the activation energies are in the order of 13¿15 kJ.mol¿1 and 5¿6 kJ.mol¿1 for H2 and CO2 respectively. Representative permeation values are in the order of 6×10¿7 mol.m¿2.s¿1.Pa¿1 and 20×10¿7 mol.m¿2.s¿1.Pa¿1 for H2 at 25°C and 200°C, respectively. Separation factors for H2/CH4 and H2/iso-butane are in the order of 30 and 200 at 200°C, respectively, for high quality membranes.\ud \ud Processes which strongly determine gas transport through microporous materials are sorption and micropore diffusion. Consequently, the activation energy for permeation is an apparent one, consisting of a contribution from the isosteric heat of adsorption and the activation energy for micropore diffusion. An extensive model is given to analyse these contributions.\ud \ud For the experimental conditions studied, the analysis of the gas transport mechanism shows that interface processes are not rate determining. The calculated activation energies for micropore diffusion are 21 kJ.mol¿1 and 32 kJ.mol¿1 for H2 and CO2, respectively. Comparison with zeolite diffusion data shows that these activation energies are higher than for zeolite 4A (dpore=4Å), indicating that the average pore size of the sol-gel derived membranes is probably smaller

Mechanisms of pattern formation during T cell adhesion

T cells form intriguing patterns during adhesion to antigen-presenting cells. The patterns at the cell-cell contact zone are composed of two types of domains, which either contain short TCR/MHCp receptor-ligand complexes or the longer LFA-1/ICAM-1 complexes. The final pattern consists of a central TCR/MHCp domain surrounded by a ring-shaped LFA-1/ICAM-1 domain, while the characteristic pattern formed at intermediate times is inverted with TCR/MHCp complexes at the periphery of the contact zone and LFA-1/ICAM-1 complexes in the center. In this article, we present a statistical-mechanical model of cell adhesion and propose a novel mechanism for the T cell pattern formation. Our mechanism for the formation of the intermediate inverted pattern is based (i) on the initial nucleation of numerous TCR/MHCp microdomains, and (ii) on the diffusion of free receptors and ligands into the contact zone. Due to this inward diffusion, TCR/MHCp microdomains at the rim of the contact zone grow faster and form an intermediate peripheral ring for sufficiently large TCR/MHCp concentrations. In agreement with experiments, we find that the formation of the final pattern with a central TCR/MHCp domain requires active cytoskeletal transport processes. Without active transport, the intermediate inverted pattern seems to be metastable in our model, which might explain patterns observed during natural killer (NK) cell adhesion. At smaller TCR/MHCp complex concentrations, we observe a different regime of pattern formation with intermediate multifocal TCR/MHCp patterns which resemble experimental patterns found during thymozyte adhesion.Comment: 12 pages, 8 figure

Phase separation processes in polymer solutions in relation to membrane formation

This review covers new experimental and theoretical physical research related to the formation of polymeric membranes by phase separation of a polymer solution, and to the morphology of these membranes. Two main phase separation processes for polymeric membrane formation are discussed: thermally induced phase separation and immersion precipitation. Special attention is paid to phase transitions like liquid-liquid demixing, crystallization, gelation, and vitrification, and their relation to membrane morphology. In addition, the mass transfer processes involved in immersion precipitation, and their influence on membrane morphology are discussed

Diffusional phenomena in membrane separation processes

Nowadays membrane filtration processes are used industrially as an alternative to conventional separation methods. Membrane separation methods can be divided into classes according to their separation characteristics: (i) separation by sieving action; (ii) separation due to a difference in affinity and diffusivity; (iii) separation due to a difference in charge of molecules; (iv) carrier-facilitated transport, and (v) the process of (time-) controlled released by diffusion. In all these cases diffusion processes play an important role in the transport mechanism of the solutes. Various mechanisms have been distinguished to describe the transport in membranes: transport through bulk material (dense membranes), Knudsen diffusion in narrow pores, viscous flow in wide pores or surface diffusion along pore walls. In practice, the transport can be a result of more than only one of these mechanisms. For all of these mechanisms models have been derived. The characteristics of a membrane, e.g. its crystallinity or its charge, can also have major consequences for the rate of diffusion in the membrane, and hence for the flux obtained. Apart from the diffusion transport processes in membranes mentioned above, other important diffusion processes are related to membrane processes, viz. diffusion in the boundary layer near the membrane (concentration polarization phenomena) and diffusion during membrane formation. The degree of concentration polarization is related to the magnitude of the mass transfer coefficient which, in turn, is influenced by the diffusion coefficient. The effect of concentration polarization can be rather different for the various membrane processes. The phase inversion membrane formation mechanism is determined to a large extent by the kinetic aspects during membrane formation, which are diffusion of solvent and of non-solvent and the kinetics of the phase separation itself

Polyaniline membranes for use in organic solvent nanofiltration

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Selective emulsion liquid membrane extraction of silver from photographic waste industries

The field of liquid membrane technology is currently undergoing a rapid expansion in research as well as its application as an industrial separation process. Liquid membrane can be manipulated to selectively separate a specific solute from a mixture and even to extract a solute against its concentration gradient. A liquid membrane system comprises of three liquid phases; feed phase, liquid membrane organic phase and receiving phase. Liquid membrane can be prepared using support or as emulsion (unsupported) liquid membrane. Emulsion liquid membrane is a liquid membrane in which the membrane phase of an emulsion is dispersed into the feed phase to be treated. This method was investigated as an alternative process for the recovery of silver from photographic waste, which contains various metals ions such as silver, iron, sodium and potassium. The important parameters governing the extraction process of silver such as agitation speed, homogenizer speed, surfactant and carrier concentrations, type of diluents, treat ratio and types of stripping solution were investigated. This process has been conducted in a batch system using a mixer-settler. The results show that the mobile carrier Cyanex 302 is selective towards silver and almost completely extract silver over the other metals that existed in the photographic waste. The optimum silver extraction was obtained by using 0.03 M Cyanex 302, 3 % (w/v) Span 80, 250 rpm stirring speed, 1.0 M thiourea in 1.0 M H2SO4 stripping agent, 1:5 of treat ratio, and kerosene as a diluents. The experimental result also shows that the emulsion liquid membrane system could be recycled twice having 80% of silver was extracted. In addition, theoretical studies show that the developed model could predict the extraction performance of the system understudied as obtained from experimental data

Universal features of cell polarization processes

Cell polarization plays a central role in the development of complex organisms. It has been recently shown that cell polarization may follow from the proximity to a phase separation instability in a bistable network of chemical reactions. An example which has been thoroughly studied is the formation of signaling domains during eukaryotic chemotaxis. In this case, the process of domain growth may be described by the use of a constrained time-dependent Landau-Ginzburg equation, admitting scale-invariant solutions {\textit{\`a la}} Lifshitz and Slyozov. The constraint results here from a mechanism of fast cycling of molecules between a cytosolic, inactive state and a membrane-bound, active state, which dynamically tunes the chemical potential for membrane binding to a value corresponding to the coexistence of different phases on the cell membrane. We provide here a universal description of this process both in the presence and absence of a gradient in the external activation field. Universal power laws are derived for the time needed for the cell to polarize in a chemotactic gradient, and for the value of the smallest detectable gradient. We also describe a concrete realization of our scheme based on the analysis of available biochemical and biophysical data.Comment: Submitted to Journal of Statistical Mechanics -Theory and Experiment

Near-critical fluctuations and cytoskeleton-assisted phase separation lead to subdiffusion in cell membranes

We address the relationship between membrane microheterogeneity and anomalous subdiffusion in cell membranes by carrying out Monte Carlo simulations of two-component lipid membranes. We find that near-critical fluctuations in the membrane lead to transient subdiffusion, while membrane-cytoskeleton interaction strongly affects phase separation, enhances subdiffusion, and eventually leads to hop diffusion of lipids. Thus, we present a minimum realistic model for membrane rafts showing the features of both microscopic phase separation and subdiffusion.Comment: 21 pages, 5 figures; Supporting Material 5 pages, 1 figure, 1 tabl