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Recent advances in separations

WS Winston Ho
William G. Lowrie Department of Chemical and Biomolecular Engineering, Department of Materials Science and Engineering, The Ohio State University, 2041 College Road, Columbus, OH 43210-1178, USA e-mail: [email protected] W.S. Winston Ho is University Scholar Professor at the Ohio State University. Recent research activities in Dr. Hos group have included molecularly based membrane separations, fuel-cell fuel processing and membranes, CO2-selective membranes, water purification, reverse osmosis, separations with chemical reaction, facilitated transport, supported liquid membranes with strip dispersion for antibiotic recovery, nanoporous membranes for controlled release, and transport phenomena in membranes.

Separation processes consume about 40% of the energy used in rening and petrochemical industries. For bulk separation processes such as ltration, the energy consumption is generally low due to its simplicity in separation. When separation applies to the molecular level, high energy consumption becomes inevitable. For example, distillation, the most employed technique for separation of liquids by evaporation and condensation, is an energy intensive process with a thermodynamic efciency as low as about 10%. Because of the high energy demand, in many industrial sectors, about 40 70% of the investment and operational costs are used for separation technology. Signicant advances in separations in recent years have been captured in the seven short articles which appear in the separation engineering section in this issue of Current Opinion in Chemical Engineering. These review articles cover research areas in mixed matrix membranes, inorganic membranes, mixed conducting membranes, dynamic membrane ltration, membrane crystallization, thermal degradation of amines for CO2 capture, and inorganic chemical adsorbents for wastewater treatment. Gas separation by membrane was rst commercialized by Monsanto in the late seventies as a result of the game-changing research contributions of Henis and Tripodi on overcoming membrane defects by covering them with a high-permeability caulking layer of polydimethylsiloxane (PDMS) [1,2]. Since then, membrane gas separation has been used for signicant applications including hydrogen recovery in rening and petrochemical plants, CO2 and H2S removal from natural gas, air separation for producing oxygenenriched air and nitrogen-enriched streams, and other uses including the dehydration of air [2]. Signicant understanding in the sorption and permeation of gases and in the improvement of membrane materials has been made in recent years. Grazia De Angelis and Sarti have reviewed the transport properties, solubility, diffusivity and permeability of gases in mixed matrix membranes (MMMs) based on glassy polymers and silica nanoparticles. MMMs are characterized generally by an increase of the gas solubility, diffusivity and permeability due to an increase of the polymer free volume induced by nano-ller insertion; however, the effects on selectivity may be different. The addition of specic llers in polymeric membranes has produced gas solubility, diffusivity and permeability improvements, as well as unexpected behaviors in the separation performance of polymeric membranes for gas separations, which are hard to rationalize and predict both quantitatively and qualitatively. For example, the addition of fumed silica nanoparticles in glassy polymeric membranes has exhibited unusual properties, for which only a specic experimental analysis could elucidate the information needed to determine the permeability and separation of the gases of interest. These
Current Opinion in Chemical Engineering 2012, 1:145147

Kang Li
Department of Chemical Engineering, Imperial College London, University of London, South Kensington Campus, London SW7 2AZ, UK e-mail: [email protected] Kang Li is Professor of Chemical Engineering at Imperial College London. His present research interests are in preparation and characterization of polymeric and inorganic hollow fibre membranes, membranes for fluid separation, membrane catalysis, multifunctional membranes and membrane reactors for energy application and CO2 capture.

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146 Separation Engineering

authors have reviewed the sorption and permeation in different glassy polymers containing fumed silica nanoparticles and revised the key modeling procedure, based on the polymer free volume, suitable for predicting the relevant transport properties in such MMMs. Inorganic membranes are characterized generally with high thermal stability for high-temperature applications, and dense inorganic membranes possess high selectivity for molecular separations, e.g., for O2 or H2 molecules. Micro-porous membranes (0.52 nm) can be highly selective for CO2, H2O, and hydrocarbons. Verweij has reviewed inorganic membranes for separations, including the state of the art, recent concepts and applications. He has reviewed and discussed membrane structures, which may be classied as (1) quasi-homogenous structures and (2) composite materials and structures. Quasi-homogenous structures may be subdivided into (1) dense structures, (2) micro-porous structures comprising small micro-pore structures, large micro-pore structures, and metal-organic framework (MOF) structures, (3) mesoporous membranes and layers, and (4) macro-porous membranes, layers and supports. In addition to the structures, he has reviewed and discussed the synthesis, processing, fabrication and characterization of the membranes. Although dense and micro-porous membranes can be highly selective as mentioned above, the potential of inorganic membranes can be realized only if their large-scale reproducible production issues are resolved and low cost modules can be fabricated [3]. In this regard, polymerinorganic hybrid composite membranes as well as mixed matrix membranes are important research avenues. Carbon capture and sequestration is a major research initiative in most industrialized countries. Considerable research has been directed toward separation processes which can be operated in harsh conditions such as oxyfuel combustion for CO2 capture. Dong and Jin have reviewed a variety of mixed-conducting materials and their chemical resistance in combustion environments. Structures and architectures of mixed conducting membranes, their possible application in oxyfuel combustion processes and their commercial prospects are also provided in the review. Conventional crossow ltration suffers from the buildup of a cake layer of rejected solutes on the membrane surface, which increases mass transfer resistances for the uids. In order to suppress the growth of the cake layer, very high uid velocity in the feed compartment is normally required, which results in a high energy penalty. Dynamic membrane ltration is, in this context, an attractive alternative as it consists of a moving part, which is capable of creating very high shear rates at the membrane surface to prevent cake layer build-up, especially when membrane fouling is important. Jaffrin has provided
Current Opinion in Chemical Engineering 2012, 1:145147

a review on dynamic ltration. The advantages and drawbacks of dynamic ltration have been discussed, and examples of currently available industrial dynamic ltration systems have been given. It is also suggested that dynamic ltration not only increases substantially the permeate ux, but also shows a favorable effect on membrane selectivity, and such benecial effects are more important in nanoltration and reverse osmosis. Drioli, Di Proo and Curcio have reviewed recent progress in membrane crystallization, an innovative concept related to the implementation of membrane technology in crystallization processes. They have pointed out several important advantages, which make this methodology of growing interest, including well-controlled nucleation and growth kinetics, fast crystallization rates and reduced induction time, membrane surfaces that promote heterogeneous nucleation, ne modulation of the level and rate of supersaturation, selection of polymorphic forms, applicability to anti-solvent, and production of co-crystals. As solute molecules are entrapped in the irregular topography of the membrane surface, they can establish nonspecic interactions with the chemical functionalities existing in the polymeric chains, giving rise to facilitated/preferential nucleation mechanisms. These authors have also reviewed and discussed an integrated membrane system consisting of membrane crystallizers operating on the brine of nanoltration and/or the reverse osmosis units to reduce the amount of brine and to recover valuable crystalline materials, with controlled characteristics, from seawater desalination installations. Amine scrubbing is the most developed technology for removal of CO2 and H2S used currently in reneries as well as petrochemical and natural gas plants and will undoubtedly play an important role in CO2 capture and storage [4]. However, the degradation of the amines used at 1001508C limits the maximum temperature and pressure and therefore the energy performance for solvent regeneration. Rochelle has reviewed the rate, products, and mechanisms for the thermal degradation of amines for CO2 capture from ue gas using aqueous amine scrubbing. As discussed in detail by him, primary and secondary ethanolamines and ethylenediamines degrade at 1001308C as they form cyclic ureas and oxazolidinones via carbamate formation and polymerization. Tertiary amines can be more stable and resistant to degradation if they do not comprise methyl and ethanol groups. On the other hand, the tertiary amines containing these groups degrade more easily due to transalkylation to form quaternary amine and elimination from the quaternary amine resulting in the net production of the secondary amine. Elimination may be faster with ethyl alcohol or ethyl amine attached to the tertiary nitrogen. Piperazine structures and long chain diamines, e.g., hexamethylenediamine, degrade by ring opening and closing, and they may be used at higher temperatures (1501608C). Blends
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Editorial overview Ho and Li 147

of alkanolamines with reactive amines such as piperazine are more easily degraded thermally as the reactive amine participates in carbamate polymerization. In addition, thermal degradation can produce products that are more volatile than the parent amines, leading to signicant loss due to volatility. In wastewater treatment industries, there is always particular interest in developing new adsorbents that exhibit high adsorption capacities for removing various pollutants from contaminated water. Jiang and Ashekuzzaman have provided a review on the development of various inorganic chemical adsorbents, providing an alternative to conventional activated carbon for the treatment of surface and ground water as well as industrial efuents. They have also covered the recent development of modied clays, zeolites and layered double

hydroxide based sorbents for the removal of aqueous contaminants such as heavy metals, natural and synthetic organic matter, and anion contaminants as well as a new type of sorbent, metalorganic frameworks (MOFs), for treating emerging organic micro-pollutants.

References
1. Henis JM, Tripodi MK: Composite hollow ber membranes for gas separation: the resistance model approach. J Membr Sci 1981, 8:233-246. Ho WSW, Sirkar KK (Eds): Membrane Handbook. Chapman & Hall; 1992; Ho WSW, Sirkar KK (Eds): Membrane Handbook. Kluwer Academic Publishers; 2001. Ramasubramanian K, Ho WSW: Recent developments on membranes for post-combustion carbon capture. Curr Opin Chem Eng 2011, 1:47-54. Rochelle GT: Amine scrubbing for CO2 capture. Science 2009, 325:1652-1654.

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Current Opinion in Chemical Engineering 2012, 1:145147