I&EC 1

How should we define Green Nanotechnology and this symposium?

Barbara Karn(1), karn.barbara@epa.gov, 1200 Pennsylvania Ave. NW, Washington DC 20460, United States . (1) Office of Research and Development, US EPA, Washington DC 20460, United States

This paper will set the stage for the symposium on Nanotechnology and the Environment: Focus on Green Nanotechnology. I will discuss the various aspects of green nano and the progress in the field. Several of these aspects are seemingly incompatible, for example, producing nanomaterials in a green manner and learning that they are ultimately toxic to humans or other organisms; using nanomaterials in consumer products without planning for their ultimate disposal or recycle; developing environmentally friendly nanomaterials for dispersive use may have unintended consequences. I will also discuss this symposium itself, including its evolution and the current papers. The motivation behind the symposium will be expanded through a discussion of how Green Nanotechnology fits in with sustainability.

I&EC 2

Nanotechnology and sustainability: Overview of the Nano2 Report – nanotechnology long-term impacts and research directions, 2000-2020

Mamadou S. Diallo(1)(2), diallo@wag.caltech.edu, M/C 139-74, Pasadena CA 91125, United States . (1) Graduate School of Energy, Environment, Water and Sustainability, Korea Advanced Institute of Science and Technology (KAIST), Daejon 305-701, Republic of Korea (2) Division of Engineering and Applied Sciences, California Institute of Technology, Daejon 305-701, Republic of Korea

On March 2010, I became a member of a team of scientists and engineers charged to conduct an ”International Study of the Long-term Impacts and Future Opportunities for Nanoscale Science and Engineering" by the US National Science Foundation. Our team has held workshops in four different countries: USA (Evantson), Germany (Hamburg), Japan (Tokyo) and Singapore. Our Nano2 report was presented to NSF on September 10, 2010 (http://www.tvworldwide.com/events/NSFnano2/100930/). In this seminar, I will give an overview of Chapter 5 of the Nano2 report,which focuses on nanotechnology solutions for water, food, habitat, transportation, mineral resources, green manufacturing, clean environment, climate change and biodiversity. In each of these areas, I will discuss key advances that have occurred during the last 10 years. I will also outline the vision and major goals for the next 10-20 years.

I&EC 3

U.S. Environmental Protection Agency: Nanotechnology research directions and initiatives

Michael McKittrick(1), mckittrick.michael@epa.gov, 1200 Pennsylvania Ave. NW, Mailcode: 8722F, Washington D.C. 20004, United States . (1) Office of Research and Development, U.S. Environmental Protection Agency, Washington D.C. 20004, United States

Engineered nanomaterials are expected to provide major environmental benefits in the many areas. These materials can also have severe implications for the environment. The U.S. Environmental Protection Agency (EPA) has a key role to help protect public health and the environment as the field of nanotechnology continues to emerge. This talk will discuss the EPA's role and efforts in supporting research in this area while evaluating its regulatory responsibility to protect the environment and human health. Specifically, key research themes for EPA's Nanotechnology program include: identifying sources, fate, transport, and exposure; understanding human health and ecological effects to inform risk assessments and test methods; developing risk assessment approaches; and preventing and mitigating risks. Key research results from previously funded initiatives, as well as potential future directions, will be addressed.

I&EC 4

Crisis in risk communication

David M. Berube(1), dmberube@unity.ncsu.edu, 201 Winston Hall, Campus Box 8104,, Raleigh NC 27695-8104, United States . (1) Department of Communication, North Carolina State University, Raleigh NC 27695-8104, United States

Risk is a socially constructed sometimes non-rational phenomenon when integrated into assessment and management as well as a more objective and data driven exercise when incorporated into analysis and assessment. There are many different equations to estimate risk. Set theory complicates these equations as phenomena become more difficult to quantify since each phenomenon belong to many different sets in different concentrations. Emerging sciences and technologies, e.g., nanoscience and synthetic biology are fraught with levels of uncertainty heretofore not experienced. The release of scientific findings, pace of technological development, escalation of variance among phenomena, and number of methods to test loss have proliferated. Using data on emerging sciences and technologies plagued as they are with uncertainty and designing messages for public audiences who use non-rational heuristics when decoding messages have become more problematic. If the public matters in risk decision-

making then new approaches to frame emerging sciences and technologies must occur.

I&EC 5

Nanostructured membranes for green synthesis of nanoparticles and enzyme catalysis

Dibakar Bhattacharyya(1), db@engr.uky.edu, 177 FPAT Bldg, Lexington KY, United States ; Vasile Smuleac(2); Scott Lewis(3); Li Xiao(4); R. Varma(5). (1) Chemical and Materials Engineering, University of Kentucky, Lexington KY 40506, United States (2) Chemical and Materials Engineering, University of Kentucky, United States (3) Chemical and Materials Engineering, University of Kentucky, United States (4) University of Kentucky, United States (5) US EPA, Cincinnati OH, United States

Macroporous membranes functionalized with ionizable macromolecules provide promising applications in toxic metal capture at high capacity, nanoparticle synthesis, and catalysis. Our low-pressure membrane approach is marked by reaction and separation selectivity and their tunability by operating pH, ionic strength or pressure. The sustainable, green chemistry, approach using ambient conditions and the evaluation of reactive membranes comprising poly acrylic acid (PAA)-modified poly vinylidene fluoride (PVDF) membrane is described. Two distinct membrane types were obtained: 1) stacked-membrane with layer-by-layer assembly approach for incorporation of enzymes (catalase, glucose oxidase) for tunable product yields, and 2) in-situ, green synthesis of 20 – 50 nm iron-based nanoparticles. Here,we report for the synthesis of supported Fe and Fe/Pd nanoparticles in membrane pores using vitamin C and tea polyphenols as reducing agents and demonstrated the reactivity of these NPs toward dechlorination of toxic organics.The formation of bioreactor with nano-domain interactions and mixed matrix nano-composite membranes display remarkable versatility compared to conventional membranes. This research is funded by NIEHS-SRP and by DOE-KRCEE.

I&EC 6

Production of nanoparticles under benign conditions using vitamins, sugars, glutathione and polyphenols from tea and winery waste

Rajender S Varma(1), Varma.Rajender@epa.gov, 26 West M.L.K. Dr., MS 443, Cincinnati Ohio 45268, United States . (1) Sustainable Technology Division, National Risk Management Research Laboratory, U. S. Environmental Protection Agency, Cincinnati Ohio 45268, United States

In continuation of our developmental program for sustainable pathways to nanomaterials, an account of greener preparation of nanoparticles utilizing

naturally occurring reagents such as vitamins, sugars, tea extracts, and biodegradable polymers will be presented which reduces or eliminates the use and generation of hazardous substances. Using completely benign conditions and an innocuous source for reduction and capping the ensuing nanomaterials, we describe several greener alternatives for the production of nanoparticles utilizing vitamins, poly(ethylene) glycol (PEG), glutathione, and polyphenols from tea, wine and winery waste, red grape pomace. The use of microwave heating in some cases has reduced the processing time to merely few minutes. The application of ensuing particles in catalysis and environment will be highlighted.

I&EC 7

Nanoengineered catalysts: From greener processing method to green energy application

Chuan-Jian Zhong(1), cjzhong@binghamton.edu, Vestal pkwy east, Binghamton NY 13902, United States . (1) Department of Chemistry, State University of New York at Binghamton, Binghamton NY 13902, United States

Nanoengineered catalysts have been increasingly utilized for green energy applications (e.g., fuel cells, lithium-air batteries, solar cells, etc.). The control of size, shape, composition, phase and surface properties of such catalysts is very important. Most existing methods used for such a control involved use of large amounts of organic solvents in the synthesis and processing. This report discusses recent findings of our investigation of thermally activated processing methods with minimum or no organic solvents for the control of these nanostructural parameters. A key focus of the investigation is the understanding of the thermal evolution of size, shape, and composition for bimetallic/trimetallic nanoparticles. Examples illustrating the applications of the nanoengineered catalysts in PEM fuel cells and lithium-oxygen batteries will also be discussed.

I&EC 8

Award Address (E. V. Murphree Award in Industrial and Engineering Chemistry sponsored by The ExxonMobil Research and Engineering Co.). Membrane technology for a thirsty world

Norman N. Li(1), nlchem@aol.com, 479 Business Center Drive, Mount Prospect IL 60056, United States . (1) NL Chemical Technology, Inc., Mount Prospect Illinois 60056, United States

The speaker will first review the membrane technology for water treatment and seawater desalination. He will then discuss the current emphases in industrial applied research as well as the needs of conducting fundamental research to improve our understanding and insights about membrane morphology and the effects of various process parameters on membrane characteristics and

performance in a separation process. He will also discuss his own research of developing advanced membranes and, finally, the future directions of the development of membrane science and technology.

I&EC 9

Engineering separation processes

C. Judson King(1), cjking@berkeley.edu, MC #4650, Berkeley CA 9472--4650, United States . (1) Center for Studies in Higher Education, MC #4650, University of California, Berkeley CA 94720-4650, United States

Separation processes became a field via two main historical threads -- recognition of the commonalities of a number of chemical engineering unit operations that accomplish separation and a nearly independent line of development within analytical chemistry and chromatography. These developments are traced, and the essential and useful common features of different types of separation processes are identified. Building on this background, key innovations that have advanced and enabled the field are identified. From an examination of these key innovations, conclusions are drawn as to the most effective and productive sources of innovations in separations. These sources are then examined with regard to their status and vigor in the world today.

I&EC 10

Effect of pyrolysis atmosphere on asymmetric hollow fiber carbon molecular sieve membranes

William J. Koros(1), William.Koros@chbe.gatech.edu, 778 Atlantic Drive, Atlanta GA 30332-0100, United States ; Mayumi Kiyono(1); Paul J. Williams(2). (1) School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta GA 30332-0100, United States (2) Westhollow Technology Center, Shell Global Solutions (US) Inc., Houston TX 77210, United States

Carbon molecular sieve (CMS) membranes have attractive separation performance properties, greatly exceeding an “upper bound” trade-off curve of polymeric membrane performance for many challenging gas separations. An asymmetric hollow fiber membrane morphology is preferred for such applications due to the ability to form high surface area to volume ratio modules. Fortunately, CMS fibers appear to have an additional advantage over dense films, since they offer better mechanical strength and flexibility and ability to be handled. CMS fibers are prepared by pyrolyzing polymer fibers, well above their glass transition temperatures. In this study, asymmetric hollow fiber precursor membranes were pyrolyzed to

create CMS fibers by adapting an oxygen “doping” method previously developed using CMS dense films. Defect-free asymmetric hollow fibers are spun and used to evaluate efficacy of the CMS membrane production method which involves careful tuning of oxygen concentration during the pyrolysis process. Mixed gas feed of CO2 and CH4 with high feed pressure are used to characterize these CMS fibers. The experimental mixed gas separation properties are compared with theoretical values predicted using the single gas permeation and sorption experimental results. The effect of permeate pressure is also discussed to evaluate high performing CMS fibers under realistic conditions.

I&EC 11

Polymer-based gas and liquid separation membranes

Benny D. Freeman(1), freeman@che.utexas.edu, 10100 Burnet Road, Bldg. 133 (CEER), Austin Texas 78758, United States . (1) Department of Chemical Engineering, The University of Texas at Austin, Austin Texas 78758, United States Polymermembranes will be critically important in addressing urgent global needs in the 21st century for reliable, sustainable, efficient access to clean energy and clean water. This presentation will focus on recent advances and applications of polymer membranes for gas separations and water purification.

I&EC 12

Several approaches to reduce membrane fouling

Hideto Matsuyama(1), matuyama@kobe-u.ac.jp, 1-1, Rokkodai, Nada Kobe 657-8501, Japan . (1) Center for Membrane and Film Technology, Department of Chemical Science and Engineering, Kobe University, Kobe 657-8501, Japan

Membrane technology is widely applied for water treatment and receiving more attention since it is an outstanding process for the removal of particles, turbidity and microorganisms of natural and wastewaters. Especially, microfiltration (MF) and ultrafiltration (UF) membranes have been getting more and more application in the field of drinking water treatment associated with their advantages including superior water quality, easier control of operation, lower cost and maintenance. Nevertheless, one of the serious problems arising during membrane filtration is membrane fouling by natural organic matter (NOM). Membrane fouling can cause an increase of hydraulic resistance and a flux decline, increase operation and maintenance costs, and shorten the membrane life. For the membrane side, it is considered that morphology, charge and hydrophilicity of membrane surface affected membrane fouling. In this study, the effect of membrane surface morphology on fouling behaviour was studied.

Membranes with different structures and the same material (cellulose acetate butylate (CAB)) were prepared by different fabrication conditions. Since these membranes were made from the same material, the material hydrophilicity and membrane surface charge were the same. The membrane (TIPS2-C) with the roughest outer surface showed the highest antifouling property and the highest efficiency of backwashing on the recovery of water permeability among the membranes. Four types of membranes were prepared to study the effect of membrane surface microstructure on fouling. Membranes with smaller pore on the outer surfaces had higher antifouling property and higher efficiency of backwashing. Since NIPS2 membrane had larger pore structure on the outer surface and a dense layer on the inner surface, sodium alginate molecule was easily captured inside the membrane and resulted in most severe membrane fouling. In my presentation, effects of grafting of several materials on the membrane surface and impregnation of Ag nanoparticle on fouling property will be also mentioned.

I&EC 13

Functionalized nanostructures for biological and biomedical applications

Stanislaus S Wong(1)(2), sswong@notes.cc.sunysb.edu, Joint appointment with Brookhaven National Laboratory, Stony Brook New York, United States . (1) SUNY Stony Brook, Stony Brook NY 11794-3400, United States (2) Brookhaven National Laboratory, Stony Brook NY 11794-3400, United States

We describe a multifunctional one-dimensional (1-D) nanostructure incorporating both CdSe quantum dots (QDs) and Fe3O4 nanoparticles (NPs) within a SiO2 nanotube matrix, which has been successfully synthesized, based on a self-assembly of pre-formed functional nanoparticles allowing for control over the size and amount of nanoparticles contained within the composite nanostructures. In addition, a simple and effective template-mediated protocol has also been developed for the large-scale, room-temperature preparation of high-aspect-ratio, single-crystalline Tb-doped CePO4 nanowires, measuring ~12 nm in diameter and over 10 microns in length. Lastly, we evaluated the cytotoxicity of various morphological classes of TiO2 nanostructures (including 0-D nanoparticles, 1-D nanorods, and 3-D assemblies) to cells. Specifically, we noted that both TiO2 1-D nanorods and 0-D nanoparticles could internalize into cells after 24 h of incubation time.

I&EC 14

Interrogating the biotic/abiotic interface to control the activity of bio-inspired nanocatalysts

Marc R. Knecht(1), mrknec2@email.uky.edu, 101 Chemistry-Physics Building, Lexington KY 40506-0055, United States . (1) Department of Chemistry, University of Kentucky, Lexington KY 40506-0055, United States

Bio-inspired approaches represent new avenues towards multifunctional materials that employ biomimetic conditions to minimize energy and environmental impacts. While biocombinatorial pathways have isolated peptides with the ability to fabricate specific nanomaterials compositions, the interactions at the bio/nano interface remain poorly understood. This region mediates the activity and could be used to enhance functionality, thus it is important to elucidate these biomolecular surface interactions. In this talk, a description of these interactions will be discussed for biomimetic Pd nanocatalysts. Using peptides, Pd nanoparticles are fabricated that drive C-coupling reactions under energy efficient and eco-friendly conditions employing low catalyst concentrations. The effect of the peptide surface was assessed by using modified peptide sequences that demonstrate a >two-fold enhancement in activity for a single residue substitution. These results indicate that bio-inspired materials may possess desired activity for future catalyst materials where the peptide surface can be tuned to enhance stability and reactivity.

I&EC 15

Green nanotechnology: Soft nanomaterials from crops

George John(1), john@sci.ccny.cuny.edu, 1237 Marshak Hall, New York NY 10031, United States . (1) Chemistry, the City College of the City University of New York, New York New York 10031, United States

The self-assembly of low molecular weight building blocks into nanoscale molecular objects has recently attracted considerable interest in terms of the bottom-up fabrication of soft materials. The building blocks currently used in supramolecular chemistry are synthesized mainly from petroleum-based starting materials. However, biobased organic synthesis presents distinct advantages for the generation of new building blocks since they are obtainable from renewable resources. Our research efforts are deeply devoted toward developing chemicals and intermediates from renewable resources to generate soft materials such as surfactants, emulsifiers, liquid crystals, lipid nanotubes, molecular gels and antibacterial coatings. Present talk illustrates few successful examples of generating soft materials from agri-sources, through simple organic transformations and by enzyme catalysis in a biorefinery concept. To take these materials to the next level, we have successfully showed the utility of these hydrogels as delivery vehicles. Intriguingly, by combining biocatalysis, with principles of green and supramolecular chemistry, we developed building blocks-to-assembled materials from crops.

I&EC 16

Ultra-fast and greener synthesis of gold nanoparticles

Sang-Kee Eah(1), eahs@rpi.edu, 110 8th St, Troy NY 12180, United States . (1) Department of Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Institute, Troy NY 12180, United States

Recently we have developed a new chemical synthesis method for colloidal gold nanoparticles. The diameter can be precisely and reproducibly tuned from 3.2 to 5.2 nm and the size distribution is nearly monodisperse. In addition, this ultra-fast synthesis takes only 10 minutes by using two immiscible solvents. This is a much greener method, since minimal amounts of solvents are used and more importantly no post-synthesis cleaning is needed. These gold nanoparticles have a special property for ultra-simple 2D self-assembly with a toluene droplet on any substrate of any size. I will present two more easy-to-follow, ultra-fast and greener synthesis methods for gold nanoclusters (d<2 nm, 2-min) and monodisperse gold nanoparticles (d<= 8 nm, 60-min). In this diameter range of 1-8 nm, almost all the properties of nanoparticles are strongly size-dependent due to the transition from molecule to bulk. Green applications of precisely size-controlled gold nanoclusters/nanoparticles will be also briefly discussed.

I&EC 17

Ultrafast laser based "green" synthesis of inorganic nanoparticles and nanoalloys in biocompatible aqueous solution

Michel Meunier(1), michel.meunier@polymtl.ca, P.O. Box 6079 Station Downtown, Montreal Quebec H3C 3A7, Canada ; Sebastien Besner(1); David Rioux(1); Paul Boyer(1). (1) Department of Engineering Physics, Ecole Polytechnique de Montreal, Montreal Quebec H3C 3A7, Canada

Inorganic nanoparticles offer novel promising properties for biological sensing and imaging, as well as in therapeutics. However, these applications are often complicated by the possible toxicity of conventional nanomaterials, arising as a result of inadequate purification procedures of nanoparticles obtained via synthetic pathways using toxic or non-biocompatible substances. We review novel femtosecond laser-assisted methods, which enable the preparation of metal nanomaterials and metastable nanoalloys in clean, biologically friendly aqueous environment (“green” synthesis) and thus completely solve the toxicity problem. The proposed methods, including laser ablation as well as fragmentation based on the self-transformation of the femtosecond pulse into a supercontinuum to initiate a controlled laser-induced growth (LIG) or fragmentation (LIF) of micro/nanoparticles in solution. Stable metal colloids of extremely small size (~2 nm) with a low coefficient of variation (15–25%) can be produced. The techniques can also be used to fabricate metastable nanoalloys based on various elements, including Au, Ag, Cu, Co and Fe which some are currently difficult to synthesize using standard chemical synthesis due to the

strongly dissimilar reduction kinetic of the individual metal salts. Unique properties of the laser-synthesized AgAu and CoAu nanoalloys will be discussed.

I&EC 18

Engineering metal nanoparticles for environmental monitoring

Luis M. Liz-Marzán(1), lmarzan@uvigo.es, Campus Universitario s/n, Vigo Pontevedra 36310, Spain ; Ramón A. Alvarez-Puebla(1). (1) Departamento de Química Física, Universidade de Vigo, Vigo 36310, Spain

Metal nanoparticles display interesting optical properties related to localized surface plasmon resonances (LSPR), which give rise to well-defined absorption and scattering peaks in the visible and near-IR spectral range. Such resonances can be tuned through the size and shape of the nanoparticles, but are also extremely sensitive towards dielectric changes in the near proximity of the particles surface. Therefore, metal nanoparticles have been proposed as ideal candidates for biosensing applications. Additionally, surface plasmon resonances are characterized by largely enhanced electric fields at the nanoparticle surface, which are responsible for the so-called surface enhanced Raman scattering (SERS) effect. SERS has rendered Raman spectroscopy a powerful analytical technique that allows ultrasensitive chemical or biochemical analysis, since the Raman scattering cross sections can be enhanced up to 10 orders of magnitude, so that very small amounts of analyte can be detected. In this communication, several examples are presented of novel strategies to employ colloidal nanostructures comprising gold and/or silver in various morphologies, as substrates for ultrasensitive detection of a wide variety of analytes, including drug metabolites and environmental contaminants such as dioxins or DDT, which require the design of novel techniques for trapping them close to the metal nanostructures.

I&EC 19

Building better cathode catalysis for fuel cells

Jingbo L Liu(1), kfjll00@tamuk.edu, MSC 161, 700 University Blvd, Kingsville TX 78363, United States ; Sajid Bashir(2); Di-Jia Liu(3). (1) Chemistry, Texas A&M University-Kingsville, Kingsville TX 78363, United States (2) Chemistry, Texas A&M University-Kingsville, Kingsville TX 78363, United States (3) Division of Chemical Sciences and Engineering, The Argonne National Laboratory, Argonne IL 60439, United States

A significant obstacle in the field of portable energy generation using fuel cells is to approach the power characteristics of conventional generators without the drawbacks through development of new materials, which yield high power density with zero or near zero emission. One type of fuel cells in development is

classified as proton exchange membrane fuel cells (PEMFCs). These devices in theory can yield high efficiencies in power density with low emission profiles and have been examined as a viable alternative to conventional power generators in hybrid automobiles. In this study, we demonstrate an improvement of PEMFCs performance using the well-aligned carbon nanotubes decorated with platinum nanoparticles (Pt-NPs). The electrochemical performance of PEMFC with structured cathode containing various loadings of Pt was investigated (data shown < 0.2 mg/cm2 Pt loading). Our investigation indicates that nanotubes structured Pt-catalysts with minimal noble metal loading result in superior electrocatalytic activity when compared to traditional Pt/carbon designs for the electrochemical behavior of PEMFCs. The observed enhancements could be attributed to greater surface area of the structured nanotubes-support and greater accessibility to the active metal catalyst, leading to a more efficient electrocatalyst usage in the nanocomposite for the oxygen reduction reaction at the cathode. The latter due to formation of ultrafine Pt NPs providing large triple phase boundaries, thereby promoting PEMFC electrochemical behavior between the ion conducting phase (membrane) and current collector. Collectively, these enhancements led to a further improvement in PEMFC device performance with increased likelihood of widespread adaptation.

I&EC 20

What is optimization for downstream processing?

Edwin N. Lightfoot(1), lightfoot@engr.wisc.edu, 1415 Engineering Drive, Madison WI 53706-1691, United States . (1) Department of Chemical and Biological Engineering, University of Wisconsin, Madison WI 53706-1691, United States

Useful goals of optimization, like foraging, appear in lumps, and discovery must be heuristic. All of process chromatography, the backbone of downstream processing, is but one fundamental example, all variants comprising one basically unattractive family or “lump”. Moreover, the parameter space within which superior processes must be sought is not only extremely large; it is also heterogeneous, consisting of unconnected regions of an individually extremely large parameter spaces. One cannot therefore simply use a more effective search strategy, such as the optimized Levy flight used in the animal world as opposed to a Brownian search. Rather we must fall back on the emergence combining of well known sub-processes into a more complex “unit-process" with previously unsuspected properties – and which can then be combined with other unit processes into the next higher-order of downstream processing. Chromatography sacrifices the desirability of low capital and operating costs for flexibility and multi-component separations. It is well suited to laboratory scale investigation, but it is inherently very expensive. The small adsorbent beads needed to promote equilibration result in very high pressure drops, low space velocities and very high capital costs. There many ways to mitigate these

problems, but we shall introduce only two. The first is an ideal counter flow cascade using true dia-filtration with small adsorbent beads introduced with the retentate stream. The membrane pores of the diafilter must be large relative to the solutes being separated but small relative to the adsorbent beads. These conditions can be met with existing technology. The second is a solids handling centrifuge permitting counter flow of adsorbents and feed solution. Here too apparatus and adsorbents are available with no truly difficult modification. However, neither has yet been tested in the laboratory.

I&EC 21

Sedimentation of nanoparticle dispersions: Role of collective interparticle forces

Darsh Wasan(1), wasan@iit.edu, 10 West 33rd Street, Chicago IL 60616, United States ; Alex Nikolov(1); Jason S. Vesaratchanon(1). (1) Department of Chemical and Biological Engineering, Illinois Institute of Technology, Chicago IL 60616, United States

The sedimentation of colloidal particles is an important separation process used in many practical applications like gravity settling and purification processes involving fine particulate slurries and sludge. This presentation will highlight the role of collective particle-particle interaction forces such as the attractive depletion force caused by the excluded volume effect, and the repulsive structural force arising from the energy barrier caused by particle microstructuring in the sedimentation process. We used a nondestructive Kossel diffraction technique to monitor particle concentration profiles and changes in sedimentation rates to investigate the effect of depletion attraction and structural barrier experimentally. The data were then compared with our theoretical results based on stochastical particle dynamics simulations. The many-body (collective) effect resulting in particle crystallization is highlighted.

I&EC 22

Characteristics of hydrogen spillover across dissociation sources and adsorbents

Nicholas R Stuckert(1), nickstuckert@gmail.com, 3074 Dow, Ann Arbor MI 48105, United States ; Ralph T Yang(1). (1) Department of Chemical Engineering, University of Michigan, Ann Arbor MI 48105, United States

The effects of dissociation sources and differing adsorbents are examined for their application in hydrogen storage via hydrogen spillover.

I&EC 23

Using a nonselective hollow-fiber membrane to facilitate selective crystallization of chiral compounds

Ronald W. Rousseau(1), ronald.rousseau@chbe.gatech.edu, 311 Ferst Drive NW, Atlanta GA 30332, United States ; Apichit Svang-Ariyaskul(1); William J. Koros(1). (1) School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta GA 30332, United States

There is substantial interest in separation of chirally pure stereoisomers from one another, especially those having pharmaceutical relevance. However, since stereoisomers of a specific chemical species differ only in their spatial configuration, their separation presents an especially difficult challenge. Preferential crystallization has been studied by several research groups but most proposed processes require complex flow geometries, which has the potential of making them less robust. If low yield from batch crystallization is satisfactory, such complexity is greatly reduced and a simple operation involving only one crystallization chamber can suffice. However, high yields in preferential crystallization can only be achieved if the system is manipulated so that each enantiomer is crystallized in a separate chamber. Even so, such an operation requires careful control of seeding and cooling while simultaneously facilitating solute exchange between the chambers. Resolution of DL-glutamic acid was used as a model system in demonstrating how solute exchange between two crystallizers results in an operation giving both high purity and high yield. A hollow-fiber membrane was used to allow transport of enantiomers between the two crystallizers, thereby keeping concentrations below that stimulating primary nucleation, while restraining crystals growing in each chamber from moving to the other. The hollow-fiber membrane area was selected so as to provide a rate of mass transport across the membrane that allowed rapid cooling rate without the occurrence of primary nucleation. Experimental results show that yield was a factor of 11.4 times that which could be achieved with simple crystallization, and the product purity was over 99.9%.

I&EC 24

Standing wave design of simulated moving beds for high-purity and high-yield multicomponent separations

Nien-Hwa Linda Wang(1), wangn@ecn.purdue.edu, 480 Stadium Mall Drive, West Lafayette IN 47907-2100, United States . (1) School of Chemical Engineering, Purdue University, West Lafayette IN 47907-2100, United States

Simulated Moving Bed (SMB) is more economical than batch adsorption for large scale purification. They have been used to produce para-xylene since 1970's, high-fructose corn syrup since 1980's, and chiral pharmaceuticals since 1990's. However, SMB has not been widely used for multicomponent separation. A major barrier is the difficulty in designing zone flow rates and port velocity to ensure

high purity and high yield in systems with significant diffusion effects. SMB has three or more zones, which have different zone flow rates. Design the flow rates and port velocity by trial and error using either experiments or process simulations will require a large number of trials. A second barrier is the lack of design method to control the split of a mixture of three or more components. To overcome these barriers, a design method based on the concept of standing concentration waves in SMB was developed. A difference between port velocity and wave velocity is designed to focus a key wave in each zone to control product purity, yield, and the split. When intrinsic adsorption and diffusion parameters are known, the necessary flow rates and step times can be found quickly using minimal calculations in EXCEL. This method also reduces optimization search space by four dimensions or more. This method was used to develop the first tandem SMB for insulin purification, in which insulin was recovered from a ternary mixture with high purity (>99.8%) and high yield (>99%). It was also used to develop a nine-zone SMB for ternary separation, and the first five-zone SMB, where six sugars from biomass hydrolysates (a complex mixture with 10 components) were recovered with high purity (>95%) and high yield (>99%).

I&EC 25

Solving protein structures in-house with SHELX: Experiences with SAD phasing

Matthew M Benning(1), matt.benning@bruker-axs.com, 5465 East Cheryl Parkway, Madison WI 53711, United States . (1) Sales and Marketing, Bruker AXS, Madison WI 53711, United States

Recent advances in software tools have made it easier to obtain de novo structural information in the home lab. Single-wavelength anomalous diffraction (SAD) techniques with Cu radiation are now widely used for structure solution even in cases involving weak scatterers. The anomalous signal can also provide assistance when using other techniques such as molecular replacement and model refinement. Over the last 10 years, SHELXD has been a great resource for solving protein substructures. Recently, a feature has been incorporated in SHELXE which combines a main-chain trace together with density modification to help improve noisy electron density maps. Phases calculated from the traced resides are combined with the initial estimates to help in cases where the starting phases are poor. Examples of SAD experiments conducted on Bruker X8 PROTEUM and PROSPECTOR systems and phased using the SHELX suite will be discussed.

I&EC 26

Complexation chemistry, separation science, and X-Ray crystallography in the early 90's: A great time to be a chemist

Cary Bauer(1), cary.bauer@bruker-axs.com, 5465 E. Cheryl Parkway, Madison WI, United States . (1) X-Ray Diffraction, Bruker AXS, Inc, Madison WI 53593, United States

Although we did not realize it at the time, the early 1990's was a wonderful time to be a chemist. Technology was emerging in ways we could not comprehend at the time and the resulting impact was profound. This presentation will focus on some of the research done in Professor Roger's laboratory at that time in coordination/complexation chemistry, X-Ray crystallography and new methods in separation science and how the results have changed the way we do research in those areas today.

I&EC 27

Exploring the effects of structure conformation on the thermal properties of ionic liquids: Dialkylpyrrolidinium and dialkylpiperidinium iodide salts

W Matthew Reichert(1), reichert@jaguar1.usouthal.edu, 6040 USA Dr. South, Room 229, Mobile AL 36688, United States ; Luke Haverhals(2); Wesley A. Henderson(3); Paul C Trulove(2); Joseph J. Urban(2); Hugh C De Long(4). (1) Chemistry, University of South Alabama, Mobile AL 36608, United States (2) Chemistry, United States Naval Academy, Annapolis MD 21402, United States (3) Chemistry and Biomolecular Engineering, NC State University, Raleigh NC 27695, United States (4) Air Force Office of Scientific Research, Arlington VA 22203, United States

This research explores the link between the conformational changes and the complex thermal properties of ionic liquids (ILs) through DSC, XRD, Raman spectroscopy, and a computational approach. The focus of this study was a series of pyrrolidinium, PYRxx, and piperidinium, PIPxx, iodide salts. We can observe the influence of alkyl chain length on the cation-anion interactions by varying the alkyl chain length while maintaining the anion as iodide. DSC provides insight in the various thermal transitions that the ionic liquid can go through. Single crystal XRD provided a baseline for the conformation of the cation. While variable temperature Raman spectroscopy is able to identify the ring and alkyl chain conformations through various temperature shifts. A comparison of vibrational spectra from DFT calculations and Raman experimental data will provide insight in the conformations present at various temperatures during the thermal scan.

I&EC 28

Temperature controlled release of nicotine from its metal complexes

C.V.Krishnamohan Sharma(1), ksharma@simbolmining.com, 6920 Koll Center Parkway, Pleasanton CA 94566, United States ; C. Corey Hines(2); Robin D

Rogers(2). (1) Research & Development, Simbol Materials Inc., Pleasanton CA 94566, United States (2) Department of Chemistry and Center for Green Manufacturing, The University of Alabama, Tuscaloosa AL 35487, United States

Generation of pure nicotine aerosols for inhalation drug delivery provides a novel means for delivering nicotine for smoking cessation purposes. However, the delivery of nicotine aerosols without any additives is a challenging task given its high vapor pressures, the need for dosing accuracy, safety, and cost related issues. In this presentation, we demonstrate that the concepts of crystal engineering and separation science could be applied to drug delivery applications – where the thermally reversible coordination complexes of nicotine-metal halides release therapeutically relevant doses of pure nicotine aerosols upon rapid heating

I&EC 29

Actinide chemistry in ionic liquids

Steven P. Kelley(1), spkelley@crimson.ua.edu, Box 870336, Tuscaloosa Alabama 35487-0036, United States ; T. Gannon Parker(1); Robin D. Rogers(1). (1) Center for Green Manufacturing and Department of Chemistry, The University of Alabama, Tuscaloosa Alabama 35487-0036, United States

Ionic liquids are a class of organic salts with melting points below 100 °C. They have been heavily investigated as non-volatile replacements for organic solvents in many processes. One such area of interest is the extraction of actinides in nuclear waste. Fundamental questions about the speciation of actinides in ILs must be answered in order to design better solvents for separation and understand the speciation of pollutants that may be leaked into the environment. We are investigating the chemistry of actinides in ILs. We will present our research into this area and unique possibilities for separations, new materials, low melting f-element salt phases, and a better fundamental understanding of the reactivity of actinides and lanthanides. Our results include phase change behavior of f-element salts in the presence of ILs, and crystal structures of f-element salts synthesized from pure ILs.

I&EC 30

Synthesis and characterization of silica polyamine composites via the sol-gel route

Edward Rosenberg(1), edward.rosenberg@mso.umt.edu, 32 Campus Dr, Missoula MT 59812, United States ; Jesse James Allen(2); Erik Johnston(3). (1) Chemistry, University of Montana, Missoula MT 59812, United States (2) Chemistry, University of Montana, Missoula MT 59812, United States (3) Chemistry, University of Montana, Missoula MT 59812, United States

We have been studying the synthesis, characterization and applications of silica-polyamine composites (SPC) starting with amorphous silica gels and available polyamines. The polyamines have been further modified with metal selective ligands and these composites have been commercialized and are currently in use in the mining and mine-waste remediation industries.1-3 Amorphous silica gels have significant drawbacks for these types of application, such as uneven distribution of the silane-binding surface hydroxyl groups and wide pore size distributions. The sol-gel approach to synthesizing functionalized silica matrices offers a possible solution to the shortcomings of commercially available silica gels. We have made a detailed investigation of the synthesis of the SPC using established sol-gel methods, as well as a comparison with the commercialized technology, and arrived at some firm conclusions as to the suitability and commercial viability of this approach 1. Kailasam, V.; Rosenberg, E.; Nielsen, D Ind.& Eng. Chem. Res. 2009 48, 3991.

I&EC 31

Water separation from gas streams using inorganic membranes

Melanie Moses-DeBusk(1), mosesmj@ornl.gov, PO Box 2008-6133, Oak Ridge TN 37831, United States ; Brian Bischoff(1); James Klett(1); James Hunter(1); K. Dale Adcock(1). (1) Materials Science and Technology Division, Oak Ridge National Laboratory, United States

The separation of water from gaseous streams is important for use in areas affected by natural disasters with disrupted water supply, in arid areas, and for military campaigns in areas with limited or no natural water supplies. For such usage, capture of water from engine exhaust and air can significantly reduce the need to transport water. In view of this, we are developing inorganic membranes that can effectively separate and capture water from gaseous streams. Through control of pore parameters and test conditions, our membrane system can achieve greater water separation than attainable by standard condensation methods. Recent tests have achieved 68% efficiency which is expected to increase with membrane modifications. In this presentation, we will describe the effect of membrane pore size, temperature and flow rate on separation efficiency. We will also present results that show the system's ability to significantly reduce dissolution of vapor contaminates, such as NOx and SOx, in the separated water. Research sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory (ORNL), managed by UT-Battelle, LLC for the U. S. Department of Energy.

I&EC 32

Overcoming Pt resistant tumors using engineered nanoparticles

Luis Nunez(1), luisteo@aol.com, 4701 Innovation Dr, Lincoln NE 68521, United States ; Sandra Noriega(1); Ruben Spretz(1); Gustavo Larsen(1); Bakhtiar Yamini(2); Ezra Cohen(2); Michael LaRiviere(2). (1) 4701 Innovation Dr., LNK Chemsolutions, Lincoln Nebraska 68521, United States (2) Neurosurgery and Oncology, The University of Chicago, Chicago Illinois 60637, United States

Various types of cancers are regularly treated with the chemotherapy drug cis-diammine dichloroplatinum (II) (CDDP) and its derivatives, the platinum compounds are effective until detrimental side effects dominate the patient's health and the treatment is discontinued. Engineered nano particle systems are promising due to their protective nature toward normal cells and receptor mediated uptake mechanism in the treatment of CDDP-resistant tumors. Some reasons for CDDP-resistant are due to limited cellular uptake, efflux of the drug, and drug detoxification by O(6)-methylguanine-DNA methyltransferase (MGMT), a DNA repair protein that protects tissues against toxic and carcinogenic effects of alkylating agents. We have engineered nanoparticles with effective diameter of 250nm, CDDP loaded in a core shell structure targeting overexpression of the epidermal growth factor receptor (EGFR). We report the physical characteristics of the nanoparticles and in vitro and in vivo results to demonstrate their efficacy and distribution in animal models.

I&EC 33

Green nanotechnology and pesticides: Scientific and regulatory implications and applications

Najm Shamim(1), Shamim.Najm@epa.gov, 2777 Potomac Yard, Arlington, VA 22202, United States . (1) Department of: Office of Pesticides Programs, Antimicrobials Division, Risk Assessment & Science Support Branch, US Environmental Protection Agency, 2777 Potomac Yard, Arlington, VA 22202, United States

Pesticides, whether classified as agricultural, antimicrobials or biopesticides inherently carry risks.Nanotechnology applications show promise for pesticides: Smaller use amounts, and lower application rates, more efficient methods of delivery systems etc. These scenarios will reduce exposure and hazards, resulting in reduced risks and smoother risk management process and fewer societal concerns. To this paradigm, if Green Nanotechnology is added as a key concept to the applications of nanotechnology to manufacture, uses, and diposal of pesticides could result in lesser economic burden, greater reduction in risks at every stage of the life of a pesticide. though idealistic at this time but one step at a time will evolve a new paradigm of risk assessments /management. This presentation will briefly discuss the present scientific and regulatory approach for risk assessment and risk management and how green nanotechnology applications for pescitides will change the paradigm. Copper nanoaprticles will be used as an example

I&EC 34

Green synthesized silver nanoparticles exhibit reduced toxicity to mammalian cells and retain antimicrobial activity

Jayne B Robinson(1), jayne.robinson@notes.udayton.edu, 300 College Park Ave, Dayton OH 45177, United States ; Brittany Demmitt(1); Tracy Collins(1); Tim Gorey(1); Ryan Posgai(1); Rajender Varma(2); Saber Hussain(3); John Rowe(1). (1) Biology, University of Dayton, Dayton OH 45177, United States (2) National Risk Management Laboratory, Environmental Protection Agency, Cincinnatti OH 45268, United States (3) Applied Biotechnology Branch, Air Force Research Laboratory, Wright Patterson Air Force Base, Dayton OH 45433, United States

The interest in silver nanoparticles (AgNPs) and silver nanomaterial stems from their antimicrobial properties. AgNPs are being added to clothing, paint, refrigerators, washing machines and a variety of other commercially available items. Recent in vitro and in vivo studies, however, have shown their toxicity is not limited to bacteria and may involve acute and long term, chronic effects to humans and other organisms. Recently it has been reported that green tea and epicatechin synthesized AgNPs have a significantly lower in vitro toxicity to human mammalian kerotinocytes. We report here the antimicrobial activity of traditionally synthesized uncoated, and polysaccharide coated AgNPs and compare the results to epicatechin synthesized AgNPs. Our results indicate that traditionally synthesized coated and uncoated AgNPs are toxic to both bacteria and human kerotinocytes. In contrast, the epicatechin-synthesized particles were significantly less toxic to kerotinocytes but still retained antimicrobial activity. These initial results suggest that green synthesis of AgNPs might be applied to create particles that can be used as an effective antimicrobial without significant side effects to higher organisms.

I&EC 35

Controlled release of biologically active silver from nanosilver surfaces

Jingyu Liu(1), jingyu_liu@brown.edu, 324 Brook Street, Box H, Providence RI 02912, United States ; David A. Sonshine(2); Saira Shervani(2); Robert H. Hurt(2). (1) Department of Chemistry, Brown University, Providence RI 02912, United States (2) Division of Engineering, Brown University, Providence RI 02912, United States

Major pathways in the antibacterial activity and eukaryotic toxicity of nano-silver involve the silver cation, which is an established thiol toxicant. In this pathway, nano-silver particles serve as delivery vehicles that transport and release bioactive silver ions to biological target sites. This work applies elements of the drug delivery paradigm to develop “controlled release” formulations of nAg. After presenting thermodynamic calculations of silver species partitioning in biological

media, a variety of approaches are evaluated for controlling ion release rate over four orders of magnitude, including particle size selection, ligand binding, polymeric coatings, sulfidic films, and pre-oxidation treatment. The ability to tune biological activity is demonstrated through bacterial inhibition zone assays. The environmental advantage of controlled release nanosilver lies in the optimal dosing of silver ion, which avoids unintended or excess ion release to waste water streams over and above that required for antibacterial product performance.

I&EC 36

Green nanotechnology for water treatment

Allen Apblett(1), allen.apblett@okstate.edu, 107 Physical Sciences, Stillwater OK 74078, United States ; Satish Kuriyavar(1). (1) Department of Chemistry, Oklahoma State University, Stillwater OK 74078, United States

Nanoparticles have been demonstrated to have useful absorption and catalytic properties but it is difficult to take advantage of these properties in the real world due to their small size. For example, in a water treatment column, they would simply suspend and flow away with the water or clog any filter that might be used to keep them in place. In fluidized catalytic beds they would tend to escape from a reactor with the fluidizing gases. We addressed this challenge by finding a way to make spherical aggregates of nanoparticles that have a similar size and shape as the resin beads already used for water purification - indeed they are made from ion exchange resins. When a cationic ion exchange resin is loaded with a metal ion and then fired at 500-600˚C, ceramic replicas are produced that are spherical aggregates of nanocrystalline (ca. 12 nm) metal oxides. In this manner, iron oxide and zinc oxide have been produced as porous aggregates with surface areas approximately 30 m2/g. The resulting materials have proven very successful for removal of arsenic from water and for photocatalytic decomposition of organic contaminants in water.

I&EC 37

Adsorption of environmental contaminants on nanoscale zeolites

Sarah C Larsen(1), sarah-larsen@uiowa.edu, Chemistry Building, Iowa City IA 52242, United States ; Yulia Tataurova(1); Melissa Torres(1). (1) Chemistry, University of Iowa, Iowa City IA 52242, United States

Adsorption is an effective method for removal of environmental contaminants from polluted water. Zeolites are porous aluminosilicates or silicates. Nanoscale zeolites (crystal sizes less than 100 nm) have large internal and external surface areas, which make surface modification an effective method for tailoring these materials for adsorption. Varying the surface properties of the nanoscale zeolite

improves the adsorption properties by creating favorable interactions with the environmental contaminant. For example, protonated amine groups may lead to an electrostatic interaction with anionic contaminant species, such as arsenate and chromate. Nanoscale zeolites, such as Y and silicalite, were synthesized and functionalized with organosilanes. Solution NMR methods for studying the interface between the nanoscale zeolite and the environmental contaminant are being developed and preliminary results will be presented. Functionalized nanocrystalline zeolites were evaluated for removal of anions, such as chromate and arsenate, and metals, such as copper, from aqueous solution.

I&EC 38

Boron-selective chelating resins from dendritic macromolecules

Himanshu Mishra(1), hmishra@caltech.edu, Keck laboratories M/C 13878, 1200 E California Blvd, Pasadena CA 91125, United States ; C. J. Yu(1)(2); W. A. Goddard(1)(3); M. S. Diallo(1)(4); N. F. Dalleska(5). (1) Division of Engineering and Applied Sciences, California Institute of Technology, Pasadena CA 91125, United States (2) AquaNanoTechnologies, Pasadena CA 91125, United States (3) Division of Chemistry, California Institute of Technology, Pasadena, Pasadena CA 91125, United States (4) Graduate School of Energy, Environment, Water and Sustainability, Korea Advanced Institute of Science and Technology, Pasadena CA 91125, United States (5) Environmental Analysis Center, California Institute of Technology, Pasadena CA 91125, United States

Desalination of seawater is a promising approach to supply coastal areas with clean water for human consumption and agriculture. Boron concentrations in seawater range from 0.5 to 5 mg/L. While boron is an essential nutrient for plants, its overdose can adversely impact their growth. For example, boron concentrations above 0.3 mg/L can cause serious damage to citrus crops. Although conventional seawater reverse osmosis (SWRO) desalination systems have very rejection for salts (>95%), their rejection of small and neutral compounds such boric acid is poor (~30%). Because of this, 1-2 additional RO passes with high pH (~9) are often used in SWRO desalination plants to produce water with acceptable boron concentration (<0.3 mg/L). Thus, there is a great need for more efficient and cost effective post-treatment systems to remove boron from the permeates of SWRO desalination plants. This paper describes the synthesis and characterization of a new generation of boron-selective chelating resins. We show that dendritic macromolecules such as hyperbranched polymers provide ideal building blocks for preparing boron-selective resins that have much larger binding capacity that commercial boron-selective resins that are synthesized by functionalization of styrene divinyl-benzene microparticles with n-methly glucamine.

I&EC 39

Bromide-selective resins from dendritic macromolecules

Dae Jung Kwon(1)(2), diallo@wag.caltech.edu, 1300E California Blvd, MC139-74, Pasadena CA 91125, United States ; Mamadou S Diallo(1)(3), diallo@wag.caltech.edu, 1300E California Blvd, MC139-74, Pasadena CA 91125, United States ; Chang Jun Yu(1)(4); Denis P Chen(3); Michael R Hoffmann(1). (1) Division of Engineering and Applied Sciences, California Institute of Technology, Pasadena CA 91125, United States (2) K-water Co., Pasadena CA 91125, United States (3) Graduate School of Energy, Environment, Water and Sustainability, Korea Advanced Institute of Science and Technology, Pasadena CA 91125, United States (4) AquaNanoTechnologies, Pasadena CA 91125, United States

Bromide (Br-) is commonly found in surface water and groundwater near costal areas. It can become a contaminant in drinking water when it is oxidized with ozone to bromate (BrO3

-) during primary disinfection. The United States Environmental Agency (USEPA) has identified bromate as a potential carcinogen and has established a maximum contaminant limit (MCL) of 0.01 mg/L in potable water. Because ozone does not generate a residual taste, color and odor in water, the bottled water industry often uses ozonation to disinfect water prior to bottling and shipping. Removal of bromide from drinking water sources prior to ozonation is an effective means of controlling the formation and concentration of bromate. Reverse osmosis (RO) is currently being used as the primary treatment process to remove bromide from water sources at most bottled water treatment plants. However, 2-3 RO passes are often required to reduce bromide to acceptable levels prior to ozonation because of the limited bromide rejection capability of current RO membranes. This paper describes the synthesis and characterization of a new generation of bromide-selective resins. We show that dendritic macromolecules such as hyperbranched polymers provide ideal building blocks for preparing bromide-selective resins that have large binding capacity. These new bromide-selective resins can be regenerated without using salts such as sodium chloride that contain up to 0.3 wt% of Br-.

I&EC 40

Enhanced environmental remediation and dealination using carbon nanotubes immobilized porous polymeric membranes

Somenath Mitra(1), mitra@njit.edu, 151 Warren St., Newark NJ 07102, United States ; Ornthida Sae-Khow(1); Kenneth Gethard(1). (1) Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark NJ 07102, United States

We demonstrate that carbon nanotubes (CNTs) can be readily immobilized into the pore structure of a polymeric membrane which can dramatically improve its performance. This is accomplished by developing a nanocomposite on hollow

fiber under pressure. The nanotubes are trapped and held within the pores and serve as sorbents facilitating solute exchange from the donor to the acceptor phase. SEM and Raman measurement showed the presence and interaction of the nanocomposite with the membrane surface. The effectiveness of this carbon nanocomposite mediated process is studied by several membrane extraction processes including pervaporation for water treatment, membrane distillation for desalination and solvent extraction (1,2). The enhancement in performance led to the development of more energy efficient processes, leading to lower temperature operation and higher throughput. References: 1. Ornthida Sae-Khow and Somenath Mitra. Anal. Chem. 2010, 82, 5561-5567. 2. Ornthida Sae-Khow and Somenath Mitra. J. Phys. Chem. C, 2010, 114, 16351-16356.

I&EC 41

Novel NF-TiO2-P25 composite photocatalyst for the removal of microcystins and cylindrospermopsin under visible and solar light

Dionysios D. Dionysiou(1), dionysios.d.dionysiou@uc.edu, 765 Baldwin Hall, Cincinnati OH 45220, United States ; Miguel Pelaez(1); Polycarpos Falaras(2); Vlassis Likodimos(2); Athanassios G. Kontos(2); Armah A. de la Cruz(3). (1) School of Energy, Environment, Biological, and Medical Engineering (SEEBME), University of Cincinnati, Cincinnati OH 45220, United States (2) Institute of Physical Chemistry, NCSR Demokritos, Greece (3) Office of Research and Development, US EPA, Cincinnati OH 45220, United States

Visible light-activated titanium dioxide (TiO2), an environmental friendly material with very promising photocatalytic properties, has already being recognized as a potential and sustainable alternative for drinking water treatment. Recently, nanostructured NF-TiO2 films synthesized by a novel modified sol-gel method had been proven effective to treat aqueous solutions of hepatotoxin microcystin-LR (MC-LR) under visible light. In this work, we investigate the effect of the addition of different loadings of TiO2-Degussa P25 during synthesis of these films. The modified films were characterized with XRD, ESEM, HR-TEM, AFM and evaluated for the photocatalytic degradation of different microcystins isoforms (i.e., MC-LR, MC-RR, MC-LA and MC-YR) and cylindrospermopsin under visible and solar light, in both DI and natural water samples. Preliminary results suggest that the incorporation of Degussa P25 nanoparticles plays a significant role improving the adsorption capacity and the photocatalytic efficiency of NF-TiO2, with an optimum of 5g/L of TiO2-Degussa P25 loading in the sol under acidic conditions. The obtained results are discussed in terms of kinetics competition between microcystins and corresponding adsorption mechanisms on the novel nanomaterials.

I&EC 42

Numerical simulation study of biomass pyrolysis

Cristian Campos(1), ledesme@stthom.edu, 3800 Montrose Blvd., Houston TX 77006, United States ; Elmer B. Ledesma(1). (1) Department of Chemistry and Physics, University of St. Thomas, Houston TX 77006, United States

The rapid pyrolysis of biomass has the potential to be a renewable source of hydrocarbons. To design and optimize reactors for the industrial–scale production of hydrocarbons from biomass, mathematical models coupling transport phenomena to pyrolysis kinetics are of great benefit. The objective of this research is to develop single particle models for biomass pyrolysis. The literature reports several studies on such models. However, due to the wide variety in the data used for the pyrolysis kinetics and a focus on intra–particle phenomena, the majority of the published models are difficult to apply in reactor design. What are needed are models capable of predicting both reaction rate data and product distributions as functions of operating reactor parameters. In this work, numerical simulation results of species concentrations (tar, light hydrocarbons, CO) as functions of operating parameters (particle size, temperature) from a 1D and 2D model will be presented and discussed.

I&EC 43

Determination of nicotine and polyaromatic hydrocarbons in mainstream cigarette smoke using gas chromatography - mass spectrometry (GC-MS)

Nelsy Carcamo(1), nmc2583@g.rit.edu, 52 Lomb Memorial Drive, Rochester NY 14623, United States ; Risa Robinson(1); Todd Pagano(1). (1) Dept. of Science & Mathematics, Rochester Institute of Technology, Rochester NY 14623, United States

Cigarette smoke was generated using a custom-engineered smoking machine and different kinds of cigarettes were used as samples. Mainstream cigarette smoke was collected on silicate filter pads and run through a complex extraction procedure before being analyzed by gas chromatography-mass spectrometry (GC-MS). The analytes of interest are four suspected carcinogens that are polyaromatic hydrocarbons (Benzo[a]anthracene, Benzo[b]fluoranthene, Benzo[k]fluoranthene and Benzo[a]pyrene) and nicotine. The major developments in this research were the optimization of the GC-MS instrumentation and extraction procedure involving solid phase extraction (SPE)-based techniques. Deuterated molecules of four polyaromatic hydrocarbons were used as surrogate standards and multiple calibration curves were established in order to quantify concentrations in the collected smoke samples. Additional studies were performed for the simultaneous analysis of Nicotine. This work will help researchers understand the deposition of carcinogens in the lungs that are resultant of the smoking process.

I&EC 44

Feasibility study of the installation of a new hydrogenation reactor in AMPCO

Asenat Ngomo Onquene(1), john.galiotos@hccs.edu, 555 Community College Drive, Houston Texas 77013, United States ; Homer Stewart(1); John Galiotos(1). (1) Houston Community College-NE Energy Institute, United States

This project directly addresses the feasibility study of the installation of a new hydrogenation reactor in an existing methanol plant. The hydrodesulphurization unit consists of a catalytic reactor charged with three different catalysts: hydrogenation catalyst (NiMo), absorbent (ZnO), and ultrapure (CuO+ZnO). In order to come up with a good conclusion, two cases were considered: Case 1 was to leave the process as it is and Case 2 was to install the new reactor. Both cases were compared to evaluate which one was more economical. From the study and the results obtained, it was determined that Case 2 was economically feasible. Therefore, it is recommended to install the new reactor for hydrogenation and replace the volume of NiMo in the current reactors with ZnO.

I&EC 45

Improvements in qualitative and quantitative fluorescence spectroscopy

Kyle Edenzon(1), kde5097@rit.edu, 52 Lomb Memorial Drive, Rochester NY 14623, United States ; Todd Pagano(1). (1) Department of Science and Mathematics, Rochester Institute of Technology, Rochester NY 14623, United States

Understanding both quenching mechanisms and inner filtering is crucial to the quantitative and qualitative utilization of fluorescence spectroscopy. In the presence of both oxygen quenching and the inner filter effect, the analysis of fluorescence data can be difficult without a proper understanding of the discussed quenching mechanisms. The inner filter effect involves the radiative transfer of photons between chromophores/fluorophores in a sample. In accordance with the Stern-Volmer equation, dynamic quenching of fluorescence spectra involves the non-radiative deexcitation of a fluorophore through collisions with a quencher (often dissolved oxygen) during the fluorophore's lifetime. Also presented will be a novel fiber-optic based instrumental set-up that collects simultaneously the steady state fluorescence, absorbance, and fluorescence lifetime. This custom fabricated instrument provides valuable real-time relationships between steady-state fluorescence and fluorescence lifetime data, while the absorbance measurements monitor potential solution concentration changes during the process of deoxygenation while in a nitrogen filled environment. The results will allow researchers to better understand the impact of inner filtering and dynamic oxygen quenching on fluorescence spectra.

I&EC 46

Promotion of undergraduate research at teaching institutions

Steven Lingenfelter(1), lingens@ferris.edu, 820 Campus Drive ASC 3021, Big Rapids MI 49307, United States . (1) Department of Chemistry, Ferris State University, Big Rapids MI 49307, United States

Undergraduate research is an important part of the curriculum for a science major. It provides students with experience in scientific inquiry as well as exposing them to a specific area of science. The focus here will be on the science of chemistry. Students attending research institutions are able to perform research at the undergraduate level. Teaching institutions such as Ferris State University usually do not have the faculties to conduct novel research. Therefore it is vital to persuade students at such institutions to pursue research opportunities at universities which are research-oriented. There can, however, be a barrier to obtaining such an opportunity. It can be difficult to convince a professor to let students from another university into his or her research group. The best way around this problem is to develop a relationship with the professor in question and to show that you are a capable chemist. The advantages of such an experience for the student are immeasurable. The experience helps to reinforce their knowledge of chemistry as well as obtaining hands-on experience in chemistry.

I&EC 47

Preparation of sol-gel substrates for surface enhanced Raman scattering analysis of melamine with computational confirmation of spectral vibrational frequencies

Tara N Greer(1), tng2n@mtmail.mtsu.edu, 1540 Lascasses Highway, Murfreesboro Tennessee 37128, United States ; Ngee S Chong(1); William H Ilsley(1); Judith M Iriarte-Gross(1). (1) Department of Chemistry, Middle Tennessee State University, Murfreesboro Tennessee 37132, United States

Silica-based sol-gel materials impregnated with colloidal silver nanoparticles were synthesized for use as substrates for Surface Enhanced Raman Spectroscopy (SERS). The sol-gel matrix was modified with sorbents suitable for pre-concentrating trace analytes. The goal is to use new sol-gel based substrates for challenging applications in the analysis of environmental pollutants. Sol-gel substrates were characterized and evaluated according to the catalyst used and silicon starting materials. Target compounds encountered in environmental analysis such as polycyclic aromatic hydrocarbons and aromatic amines were used to assess the performance of the substrates. Raman spectral background and signal-to-noise ratio of the SERS spectra of selected target compounds adsorbed onto sol-gels with sorbent and silver nanoparticles were compared to those adsorbed onto silver colloids alone, and also modeled using Hartree- Fock

calculations. Reproducibility and long-term stability of the of SERS signals will also be evaluated.

I&EC 48

Experimental design of undergraduate research projects from the perspective of associate degree level deaf and hard-of-hearing students: Analysis of dissolved organic matter in natural waters

Noel Mertes(1), nmm1278@rit.edu, 52 Lomb Memorial Drive, Rochester NY 14623, United States ; Annemarie D Ross(1); Todd Pagano(1). (1) Department of Science and Mathematics, Rochester Institute of Technology, Rochester NY 14623, United States

Designing a research project is a multi-step process that involves conducting literature reviews, designing experiments, troubleshooting, and analyzing results. Such projects can be prohibitive to the Associate Degree level student, whose time in a program, and therefore time to devote to research, is limited. The National Technical Institute for the Deaf (NTID), a college of Rochester Institute of Technology (RIT), is devoted to involving Associate degree level students in undergraduate research projects. The scientific merit of the project related to the analysis of dissolved organic matter in natural waters, steps involved in the design of the experiment, and preliminary results will be presented. In particular, this presentation will provide an Associate degree level deaf/hard-of-hearing student's perspective on the process and experiences in conducting undergraduate research.

I&EC 49

Innovations in chemical lab and chemical engineering technology education and training: Soil engineering and mechanics technology

Sabri George(1), john.galiotos@hccs.edu, 555 Community College Drive, Houston Texas 77013, United States ; John Galiotos(1). (1) Houston Community College-NE Energy Institute, United States

There is tremendus need for the enhancement of skills and competencies associated with soil engineering and mechnaics for chemistry based technical programs at community colleges. Topics address recently identified applied soil technology, knowledge needs, current events, aptitude, expertise, and/or attitudes and behaviors pertinent to the practical applications and measuremsnt best pratcices of soil samples. This course concentrates in hands-on applications that include (but not limited to) determination of water content, specific gravity, sieve analysis of soil and sand, physical measurements, use of a hydrometer in soil analysis, liquid limit and plastic limit testing, shrinkage limit testing,

engineering classifications and applications, mechanical aspects of soil, dynamic applications of soil in transportation and construction, and asphalt analysis.

I&EC 50

Sulfonated polymer membranes for water applications

Donald R. Paul(1), drp@che.utexas.edu, 1 University Station C0400, Austin TX 78712, United States ; Geoffrey M. Geise(1); Benny D. Freeman(1). (1) Department of Chemical Engineering, University of Texas at Austin, Austin TX 78712, United States

@font-face { font-family: "Cambria"; }p.MsoNormal, li.MsoNormal, div.MsoNormal { margin: 0in 0in 0.0001pt; font-size: 12pt; font-family: "Times New Roman"; }div.Section1 { page: Section1; } There are a growing number of applications for polymeric membranes that regulate the transport of water and other species, e.g., salts, including desalination, osmotic power generation, fuel cells, batteries, protective clothing, humidity control, etc. where better membrane materials are needed. The improvements needed include better control of the transport processes and greater resistance to chemical and biological attack. Sulfonation of polymers is an attractive approach for tailoring membranes for such applications; it allows a convenient way to tune the water sorption in the membrane without limiting the chemical robustness of the polymer backbone. This presentation will consider how the introduction of charged sulfonate groups affects water and salt uptake and transport in sulfonated polysulfones and sulfonated styrenic block copolymers.

I&EC 51

Membrane pore functionalization approaches for water and bio applications

Dibakar Bhattacharyya(1), db@engr.uky.edu, 177 FPAT Bldg, Lexington KY 40506, United States ; Scott Lewis(2); Vasile Smuleac(3); Li Xiao(4). (1) Dept. of Chemical and Materials Engineering, University of Kentucky, Lexington KY 40506, United States (2) Dept. of Chemical and Materials Engineering, University of Kentucky, United States (3) University of Kentucky, United States (4) University of Kentucky, United States

The development of nanocomposite membranes with tunable and responsive properties provides opportunities in flux modulations, and separation/reaction selectivity control for various applications. Depending on the types of functionalized groups (such as, chain length, charge of groups, biomolecule, etc.) these membranes could be used in applications ranging from metal (or oxyanions) separation to protein purification, and enzymatic catalysis to water detoxification by iron nanoparticles. The functionalization of microfiltration (MF)

membrane pores with polypeptides provides nano-scale interactions in a confined domain. These types of membranes can easily provide platforms for nanofiltration type separations at pressure < 3 bar and for nanoparticle synthesis (20- 50 nm) for water detoxification. For example, we have demonstrated 90 % separations of arsenic oxyanions with high water flux at pressure of about 1 bar. By taking advantage of helix-coil transitions in the MF membrane pores one can get tunable separations by altering pH. In addition, electrostatic self assembly in pores (layer-by-layer, LbL) can also be achieved through alternate adsorption of cationic and anionic poly-aminoacids or polyelectrolytes under convective flow conditions. The presentation will include various functionalization approaches, LbL assembly, and reactive stacked membranes. This research has been supported by NIEHS – SRP, and NSF-IGERT program.

I&EC 52

Functionalization of membrane surfaces to impart desirable properties

Isabel C Escobar(1), isabel.escobar@utoledo.edu, 2801 W Bancroft St, MS 305, Toledo Ohio 43606-3390, United States . (1) Chemical and Environmental Engineering Department, The University of Toledo, Toledo Ohio 43606-3390, United States

An active area of research involves creating fouling-resistant membranes through post-synthesis surface modifications, which takes existing membranes and changes their surfaces. Some of these modifications reduce fouling by creating a more hydrophilic surface that allows water to flow more easily and prevent the hydrophobic interactions between organic and/or microbial foulants with the membrane surface. Others reduce roughness, change membrane charge, or combinations of these. However, all of the methods involve static membranes surfaces; that is, membrane properties are fixed after modification. On the other hand, a dynamic membrane surface would be able to reduce accumulation and limit the amount of fouling, reduce cleaning frequency, reduce operating cost and extend the life of the membrane. Stimuli-sensitive polymers are a way to create a dynamic membrane surface.

I&EC 53

Perspectives on forward osmosis processes: Yesterday, today, and tomorrow

Tai-Shung Chung(1)(2), chencts@nus.edu.sg, 4 Engineering Drive 4, Singapore 117576, Singapore Singapore 117576, Singapore ; Sui Zhang(2); Kai Yu Wang(1); Jincai Su(1); Ming Ming Ling(1); Qingchun Ge(1); Gary Amy(3). (1) Chemical and Biomolecular Engineering, National University of Singapore, Singapore Singapore 119260, Singapore (2) NUS Graduate School for Integrative Science and Engineering, National University of Singapore, Singapore Singapore 119260,

Singapore (3) Water Desalination & Reuse (WDR) Center, King Abdullah University of Science and Technology Saudi Arabia 23955-6900, Saudi Arabia

Clean water, renewable energy, and affordable healthcare are three major concerns globally due to water scarcity, resource depletion, and high medical cost. Forward osmosis (FO) is one of the unique and emerging technologies that can produce both clean energy and water driven by the osmotic pressure difference across a semi-permeable membrane. FO can also be used for controlled drug release and dehydration of pharmaceuticals during syntheses. Therefore, the purpose of this presentation is to share our perspectives on future R & D for FO processes in order to develop effective and sustainable technologies for water, energy and pharmaceutical production.

I&EC 54

Development of novel forward osmosis hollow fiber membranes

Rong Wang(1)(2), rwang@ntu.edu.sg, 50 Nanyang Avenue, Singapore Singapore 639798, Singapore ; Anthony G. Fane(2). (1) School of Civil and Environmental Engineering, Nanyang Technological University 639798, Singapore (2) Singapore Membrane Technology Centre 639798, Singapore

There has been a resurgence of interest in forward osmosis (FO) for a range of potential applications, which include wastewater treatment, water purification and seawater desalination. However, one of the major challenges to be overcome is the lack of an optimized membrane that can produce a high flux comparable to commercial reverse osmosis (RO) membranes. This paper presents the latest development of novel FO hollow fiber membranes at Singapore Membrane Technology Center. Composite FO hollow fibers with an ultra-thin RO-like skin layer or a nanofiltration (NF)-like skin layer on either the inner surface or outer surface of a porous hollow fiber substrate have been successfully fabricated by a two-step preparation. These novel composite FO hollow fibers have been tested by a series of standard protocols for characterization, and benchmarked against commercially available FO flat sheet membranes and reported NF hollow fiber membranes used for the FO process.

I&EC 55

Novel approaches to the preparation of bimetallic platinum catalysts for the dehydrogenation of light alkanes

Alexis T Bell(1), alexbell@berkeley.edu, 107 Gilman Hall, Berkeley California 94720-1462, United States . (1) Department of Chemical and Biomolecular Engineering, University of California, Berkeley California 94720, United States

Light (C2-C4) alkanes, derived from petroleum cracking or Fischer-Tropsch synthesis, can be used to produce H2 and alkenes by thermal dehydrogentation. This process produces H2 without the co-production of CO2 and light alkenes. The latter products can be oligomerized and converted to longer chain alkanes that can then be blended into gasoline or diesel. While Pt is an effective catalyst for alkane dehydrogenation it also promotes the formation of methane and coke. We have recently shown that highly active and selective catalysts for ethane and propane dehydrogenation can be produced by dispersing Pt nanoparticles onto a hydrotalicte-like support containing Ga or In. Upon reduction at 873 K, Ga or In cations in the support are reduced and the atoms of these elements form bimetallic alloys with the supported Pt. The structure of these bimetallic catalysts will be discussed along with the effects of promoter content on catalyst activity, selectivity and stability.

I&EC 56

Reaction engineering concepts in metabolic modeling

Doraiswamy Ramkrishna(1), ramkrish@ecn.purdue.edu, Forney Hall of Chemical Engineering, 480 Stadium Mall Drive, West Lafayette IN 47907, United States . (1) Department of Chemical Engineering, Purdue University, West Lafayette IN 47907, United States

Modeling of metabolic systems has assumed a premier position in modern applications of reaction engineering concepts established early in the previous century. This talk will highlight reaction engineering features in demonstration of how they have helped to not only understand the behavior of metabolic systems but also pave the way for manipulating them to establish directions for metabolic engineering. Metabolic modeling builds on the basic implements of the analysis of chemical reactions, viz., stoichiometry, chemical kinetics, and thermodynamics, together with mathematical tools of linear and nonlinear analysis to which Arvind Varma, the honoree of this session, has richly contributed. Further, it must also address regulatory processes, which control the levels of catalytic enzymes and their activities necessitating the use of both stochastic and optimization methods. Thus all of the techniques that have made chemical reaction engineering the mature field it is today are coming into play in the modeling of metabolic systems in a manner that not only offer scope for intellectual activity but also the opportunity to address significant societal problems.

I&EC 57

Polymerization reactions for engineering colloid materials

Massimo Morbidelli(1), massimo.morbidelli@chem.ethz.ch, Wolfgang-Pauli-Str. 10, Zurich CH 8093, Switzerland . (1) Department of Chemistry and Applied Biosciences, ETH, Zurich CH 8093, Switzerland

One of the major components in the success of nanotechnology is the polymeric nanoparticles. These can be produced with high precision and monodispersity in sizes, which can be as small as 20 nm, using a variety of materials through emulsion polymerization techniques. In order to go from such colloidal systems to the macroscopic objects for the final users, a number of processes are involved which often determine the success of the entire procedure. These include coagulation, densification, compatibilization, surface modification, post-polymerization and macroscopic shaping processes. In most of these processes polymerization reactions play a crucial role. A number of examples of practical relevance are discussed in order to highlight the needs for future research in the direction of understanding fundamental phenomena and developing innovative processes. This includes the use of aggregation and breakage of polymer colloids for the production of controlled porous materials in the form of micro-particles or monoliths. The use of controlled free radical polymerization for creating thermo responsive surfaces exhibiting hydrophilic and hydrophobic characteristics. The inclusion of magnetic nanoparticles in polymeric colloids for producing highly ordered nanostructures through magnetic gelation. Or the modification of the surface of the same colloids for highly dispersed nanocomposite with unique optical properties. Finally, the possibility of producing biocompatible and biodegradable nanostructure for medical applications is discussed.

I&EC 58

Optimization of CO2-assisted enhanced in-situ combustion in various well configurations

Theodore T Tsotsis(1), tsotsis@usc.edu, 925 Bloom Walk, HED 210, Los Angeles CA 90089, United States ; Kristian Jessen(1); Zhenshuo B Liu(1). (1) Chemical Engineering, University of Southern California, Los Angeles CA 90089, United States

I In-situ Combustion (ISC) is an enhanced oil recovery method where air is injected into the subsurface in order to upgrade and displace heavy oils. While ISC has been shown to be an effective process in the past, it remains a seldom-utilized enhanced oil recovery (EOR) technique. Part of the problem is its inherent complexity, as a result of which ISC has always been viewed as a challenging EOR process. Adding to the challenge is the global attitude shift towards tighter regulation of emissions. Further groundbreaking research in ISC may prove fruitless, if techniques are not developed to reduce the emissions associated with the combustion process. This work addresses CO2 emissions from ISC and proposes an approach to better utilize the produced flue gas. In

this research we study the possibility of using the CO2 produced by the ISC process by recycling it back into the reservoir. This approach accelerates oil recovery and reduces CO2 emissions for a given amount of oil recovered. In this work, we present results from a detailed simulation study for a variety of well configurations: pseudo 2-D, inverted 9-spot, and various 3-D line drive patterns. In all cases, combustion gases breakthrough well before the target oil recovery is reached. Produced CO2 is injected back into the reservoir by replacing a fraction of the injected air. Because CO2 dissolves much more readily into the oil phase than N2 it reduces the viscosity of the heated crude. The upgraded crude is produced faster and a target recovery is reached earlier regardless of the well configuration and the associated reservoir sweep pattern. Upon completion of the displacement process, more CO2 is left in the subsurface, resulting in reduced CO2 emissions. The benefit of the proposed recycling strategy is demonstrated through increased production rates by up to 25%.

I&EC 59

Hot-spots in chemical reaction engineering: Multifunctional reactors, membranes and materials

Benjamin A Wilhite(1), benjamin.wilhite@che.tamu.edu, TAMU 3111, Jack E Brown Engineering Building, College Station TX 77845, United States . (1) Chemical Engineering, Texas A&M University, College Station TX 77845, United States

A rapidly diversifying fuels portfolio, spurred onwards by emerging renewable energy resources and dwindling fossil reserves, has generated renewed interest in the reforming of hydrocarbons to hydrogen and/or syngas – which provides ample opportunities for integrating multiple chemical and/or physical processes, each often operating at unique conditions, within a single monolithic device. My research efforts have focused upon developing strategies capable of realizing synergetic couplings of chemical and/or physical processes that fully exploit the intimate coupling of these unique features. This talk will review recent efforts in my research group in realizing novel integrations of multiple processes via ceramic microreactor designs, multifunctional membrane concepts and discovery of new electroceramic materials.

I&EC 60

Combinatorial complexity, uncertainty, and emergent behavior in the design of catalytic materials

Dion Vlachos(1), vlachos@udel.edu, 150 academy street, Newark Delaware 19716, United States . (1) Chemical Engineering, University of Delaware, Newark Delaware 19716, United States

Multiscale simulation is a rapidly growing scientific field in chemical, materials, and biological sciences. The obvious goal of multiscale modeling is to predict macroscopic behavior of an engineering process from first principles (bottom-up approach). However, the emerging fields of nanotechnology and biotechnology impose new challenges and opportunities (top-down). For example, miniaturization of microchemical systems for portable and distributed power generation imposes new challenges and opportunities than the conventional scale-up. While major progress in multiscale modeling and simulation has recently been achieved, many important problems exhibit combinatorial complexity in parameters and/or an emergent behavior. In addition, the inherent uncertainty in parameter and models makes predictions of multiscale modeling less reliable. In this talk, the synthesis and control of functional materials formed in heteroepitaxy via a bottom-up approach and the first-principle design of catalytic materials will be addressed. Ammonia decomposition will be used as a prototype reaction to illustrated complexity, uncertainty, and emergent behavior in design of materials.

I&EC 61

Spray reactor concept for one-step production of plastic intermediates with reduced C footprint

Bala Subramaniam(1), bsubramaniam@ku.edu, Center for Environmentally Beneficial Catalysis, 1501 Wakarusa Drive, Suite A110, Lawrence KS 66047, United States . (1) Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence Kansas 66045, United States

In the Mid-Century (MC) process for producing terephthalic acid (TPA), the oxidant (air) is dispersed into the stirred liquid phase containing p-xylene and the Co/Mn/Br based catalyst dissolved in acetic acid. At 200 °C and 20 bar, the solid TPA product is approximately 99.5% pure, the notable and troublesome impurity being the 4-carboxybenzaldehyde (4-CBA), a partial oxidation product. The 4-CBA is eliminated in a subsequent processing step to produce a “polymer-grade TPA” with >99.99% purity. We demonstrate a spray reactor in which polymer-grade TPA is obtained in a single step. This is achieved by spraying the liquid solution (containing p-xylene and catalyst dissolved in acetic acid) as fine droplets into a gas phase containing acetic acid vapor, O2 (oxidant) and CO2. The increased O2/liquid interfacial area results in a TPA product with <30 ppm 4-CBA. Each droplet acts as a microreactor in which the heat of reaction is removed by evaporative cooling, thus avoiding temperature excursions and reducing acetic acid combustion. These results, along with the potential of this process for processing renewable feedstocks will be discussed.

I&EC 62

Application of methanol absorption for a biomass to liquid process

See-Hoon Lee(1), donald@kier.re.kr, 71-2 Jang-dong, Yusung-gu Daejeon 305-343, Republic of Korea ; Won-Hyun Eom(1); Doo Il Kim(1); Jae-Ho Kim(1). (1) Gasification research group, Korea Institute of Energy Research, Yusung-gu Daejeon 305-343, Republic of Korea

Biomass such as wood waste, sawdust and agriculture waste can be easily acquired in all parts of the country and may be a most promising renewable resource to make synthetic fuel. In order to convert biomass into liquid fuel, syngas emitted from a circulating fluidized bed gasifier must be cleaned by removing acid gas, such as H2S, COS, and CO2, before going to a F-T(Fischer-Tropsch) process. 0.1Nm3/hr methanol absorption tower were used for simultaneously removing H2S, COS, and CO2 from simulated syngas. The pressure of absorption tower was 0-100psia and the temperature was from 0oC to -25oC. Each concentrations of H2S, COS, and CO2, in a biomass gasifier were 45ppmv, 5ppmv, 18vol%, respectively. In these experiments, H2S, and COS adsorption ratio was up to 99.5%, and CO2 adsorption ratio was 38% to 51% at various operation conditions.

I&EC 63

Gasification of coals using microwave plasma

Sang Jun Yoon(1), yoonsj@kier.re.kr, 71-2 Jang-dong, Daejeon Yuseong, Republic of Korea ; Yong Ku Kim(1); Jae Goo Lee(1). (1) Department of Gasification, Korea Institute of Energy Research, Daejeon 305-343, Republic of Korea

The plasma gasification is widely applied because of its clean syngas production performance and high chemical reactivity accelerated by the free radicals produced by plasma. In the present study, the gasification of four different coals was performed by 2kW microwave plasma unit. The nitrogen and argon are used as a plasma forming gas. Gasification was conducted under an oxygen/fuel ratio of 0 ~ 2.0, and a steam/fuel ratio of 0.5 ~ 1.5. With increasing oxygen/fuel ratio, the H2 composition in the produced gas was decreased while the CO2 content was increased. The CO composition increased until an O2/fuel ratio of approximately 0.6 depending on the coals and decreased thereafter. The CH4 was not observed in a syngas, typical of high temperature plasma gasification. The H2, CO2 contents tend to increase and CO content in the product gas decreased with increasing steam/fuel ratio. Syngas composition produced from plasma gasification at same conditions is affected by the properties of coals such as thermochemical reactivity, coal grade or rank. The Shenhua coal shows highest H2 production than other coals by plasma gasification. Gasification of the coal with high moisture content generates high CO2 composition in the syngas.

I&EC 64

Kinetic study of synthesizing unsymmetrical alkyl sulfide ether under phase-transfer catalysis

Yu-Ming Hsieh(1), ymhsieh@mail2000.com.tw, No.110, Xuefu Rd,, Toufen Miaoli County 35153, Taiwan Republic of China ; Maw-Ling Wang(2); Hong-Kai Lai(3). (1) Department of Biotechnology, Asia-Pacific Institute of Creativity, Toufen,Miaoli county 35153, Taiwan Republic of China (2) Department of Safety, Healthy and Environmental Engineering, Hungkuang University, Shalu,Taichung County 43302, Taiwan Republic of China (3) Department of Chemical Engineering, Tung-Hai University, Taichung City 40704, Taiwan Republic of China

The reaction between sodium sulfide (Na2S) and bromoalkanes to synthesize unsymmetrical alkyl sulfide ether was carried out in an organic solvent/alkaline solution two phase medium under phase transfer catalytic (PTC) condition. In this system, a two-site active catalyst QSQ (Q+: (C4H9)4N+), which was produced from the reaction of sodium sulfide and quaternary ammonium salt, was employed as the active catalyst. This active catalyst was synthesized in aqueous solution, and then transferred to the organic phase. QSR1 (R1:C3H7) and QSR2 (R2:C6H13) from the first reaction of the organic phase, and three products R1SR1, R2SR2, and R1SR2 were produced from the second reaction of the organic solution. Detailed investigation was made for studying the effect of agitation, amount of catalyst, amount of water, and amount of reactant on the reaction rate and conversion. A rational reaction mechanism and a kinetic model were satisfactorily developed.

I&EC 65

Molecular design of silicate rubbers for advanced soft lithograpy

Kyung M. Choi(1), choikm@uci.edu, UCI, Irvine CS, United States . (1) Chemistry, University of California, Irvine CA 92697, United States

We introduce a novel molecular design of silicate rubbers for advanced nanotechnology. The ability to fabricate small patterns on flexible substrates has received a considerable attention due to a potential application in low coat plastic electronics. Soft lithography is an alternative to conventional UV photolithography and also allows us to fabricate small patterns with low cost and easy processability. However, commercially available silicon elastomers often results in collapse and mergence due to its poor mechanical strength, especially in the nano-scale regime (< 100 nm). Since the resolution of soft lithography techniques is rely on stamping materials, we devoted to develop a new version of photocurable silicon elastomers, which satisfy our diverse demands. The new silicon elastomers resulted in high performances in nanofabrication. The relation between silicon rubber structures and resulting functions will be also discussed.

I&EC 66

Sonocatalysed synthesis of 2-phenylvaleronitrile under controlled reaction conditions: A kinetic study

Maw-Ling Wang(1), chmmlw@sunrise.hk.edu.tw, No. 34, Chung Chi Road, Shalu Taichung County 43302, Taiwan Republic of China ; P. A. Vivek(2). (1) Department of Environmental Engineering, Safety and Health, Hungkuang University, Shalu Taichung County 43302, Taiwan Republic of China (2) Department of Environmental Engineering, Safety and Health, Hungkuang University, Shalu Taichung County 43302, Taiwan Republic of China

In the current study, kinetics of synthesis of 2-phenylvaleronitrile (PVN) was successfully carried out by selective C-alkylation of benzyl cyanide (BC) with n-bromopropane (BP) using aqueous KOH and catalyzed by TBAB under ultrasonic (300 W) assisted solvent-free conditions. Selective monoalkylation of benzyl cyanide has been achieved by controlling the reaction conditions and has been followed using gas chromatogram. The effects of various parameters such as agitation speed, catalyst concentration, KOH concentration, benzyl cyanide concentration, volume of water, the frequency of ultrasonic power and temperature were studied systematically to understand their influence on the rate of the reaction. The experimental observations are consistent with an interfacial-type process. Further the kinetic results demonstrate clearly, that ultrasonic assisted phase-transfer catalysis significantly increased the reaction rate when compared to silent reactions.

I&EC 67

Operation performance of a membrane bioreactor in the treatment of deinking wastewater

Dongju Zheng(1), emma.upc@163.com, Haidian District, Beijing Beijing, China ; Jiding Li(1); Lin Qin(1); Xia Zhan(1). (1) Department of Chemical Engineering, Tsinghua University, China

The treatment of deinking wastewater, not only posses of great significance in paper making, but also has environmental protection meaning. Compared to a traditional activated sludge technology, membrane bioreactor (MBR) holds huge potential for industrial effluents, because of its high efficiency, energy-saving advantages. This research was about the dealing with deinking effluent. A submerged membrane bioreactor with flat ultrafiltration membranes was introduced. Through 57days running, the operation conditions were investigated. The aeration intensity, air to water ratio, suction time and non-suction time were the three experimental variables.

I&EC 68

Can a smartphone be a scientific research tool in the field?

Melanie J. Lesko(1), leskom@tamug.edu, PO Box 1675, Galveston TX 77553, United States ; Ashley D. Bradley(1). (1) Department of Marine Sciences, Texas A&M University at Galveston, Galveston TX 77553, United States

The mapping capabilities on two smartphone operating systems were compared to Global Positioning System (GPS) devices. GPS devices are more accurate, but perhaps a cellular phone is adequate. Similar applications were chosen for iPhone and Android operating systems. The applications must produce a list of latitudes and longitudes for way points, or an exportable map with latitude and longitude data. In addition the smartphones can take georectified photos which mapping software can store with the maps. The method of triangulation by smartphones was checked. Data for several routes was collected, mapped using ArcGIS and Google Earth, and layered over actual maps for comparison to GPS data from the same sites. The easily used smartphones are available, portable to field study sites and may be capable of collecting a variety of other data. This project is our first test of smartphones as field instruments.

I&EC 69

Liquid membrane facilitated solvent extraction for Americium separation from spent nuclear fuel: Eliminating the concentration gradient

Melanie Moses-DeBusk(1), mosesmj@ornl.gov, PO Box 2008-6133, Oak Ridge TN 37831, United States ; Ramesh Bhave(1); Laetitia Delmau(2); Guillermo DelCul(3); Chaitanya Narula(1); Stephanie Bruffey(3). (1) Materials Science and Technology Division, Oak Ridge National Laboratory, United States (2) Chemical Sciences Division, Oak Ridge National Laboratory, United States (3) Nuclear Science and Technology Division, Oak Ridge National Laboratory, United States

Americium separation is important for both reducing the heat load to volume issue encountered in geological repository implementation and for reuse in new fuels and reactors envisioned in modified open and fully closed nuclear fuel cycles. In view of this, we have initiated efforts to study the removal of Am241 from spent nuclear fuel by liquid membrane extraction employing inorganic membrane substrates since such substrates are chemically and mechanically robust as compared with traditional organic substrates. In this presentation, we will describe our results which clearly suggest that our process, unlike traditional separation processes for waste treatment, is not equilibrium limited. The effect of system pressure, concentration and cycling on separation efficiency, using UVI as a surrogate, will be presented. We will also highlight how this process is adaptable to both current and future chemical research discoveries related to americium separation. Research sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory (ORNL), managed by UT-Battelle, LLC for the U. S. Department of Energy.

I&EC 70

Influence of support layer on the pervaporation performance of PDMS composite membranes

Xia Zhan(1), zhanxia@tsinghua.org.cn, Centre for Membrane Membrane Technology & Engineering Research Center, Department of Chemical Engineering, Tsinghua University, Beijing 100084, P. R. China., Beijing Beijing 100084, China ; Jiding Li(1); Cheng Fan(1); Xiaolong Han(1); Jian Chen(1). (1) Department of Chemical Engineering, Tsinghua University, Beijing Beijing 100084, China

Four kinds of composite PDMS membranes were prepared by using PVDF, PAN, PSF, CA support layer and used for the pervaporation separation of ethanol/water mixtures. It was found that the support layer had a notable effect on the separation performance of PDMS composite membranes. The Si relative element composition in the cross-section of PDMS composite membrane was recorded by EDX line scan. It was found that Si signals exsited in supported layer and the signal depth was different among the four kinds of support layers. The depth of Si signal followed PSF>CA>PVDF>PAN, and the permeation flux also showed the same tendency. It can be concluded that PDMS composite membranes with PAN and PVDF as support layer exhibited much better pervapoartion performance than that with CA and PSF.

I&EC 71

Modeling of the charge-discharge behaviors of a valve-regulated lead-acid battery

Jeongbin Lee(1), firebin@ajou.ac.kr, San5, oncheon-dong, Yeongtong-gu, Suwon Gyeonggi-do, Republic of Korea ; Ui Seong Kim(1); Chee Burm Shin(1); Sung Tae Kim(2); Jeongwoo Lee(2). (1) Department of Chemical Engineering, Ajou University, Suwon, Republic of Korea (2) Hyundai Motor Company, Republic of Korea

Transportation is one of the largest sources of human-induced greenhouse gas emissions and fossil-fuels consumption. This has led to a growing demand for hybrid-electric vehicles (HEVs) to reduce air pollution and consumption of fossil fuels. But hybrid-electric vehicles demand the battery to be discharged and charged at high rates under partial-state-of-charge condition. At present, candidates for the energy-storage systems in HEV applications are valve-regulated lead-acid (VRLA), nickel–metal-hydride (Ni–MH) and rechargeable lithium batteries. The VRLA battery has advantages in terms of relatively low cost, high charge efficiency and safety compared to the other batteries. In this study, a one-dimensional modeling was carried-out to calculate the charge and discharge behaviors of VRLA battery used in HEVs. The model accounts for electrochemical reaction rates, charge conservation and mass transport. In order

to validate the model, modeling results were compared with the experimental data in various conditions.

I&EC 72

Efficient conversion of fructose to 5-hydroxymethylfurfural catalyzed by sulfated zirconia in ionic liquids

Xinhua Qi(1), qixinhua@nankai.edu.cn, No. 94, Weijin Road, Nankai District, Tianjin Tianjin 300071, China ; Luyang Li(1); Haixin Guo(1); Yingzhao Xu(1). (1) College of Environmental Science and Engineering, Nankai University, Key Laboratory of Pollution Processes and Environmental Criteria (Ministry of Education), Tianjin 300071, China

With the growing interest in developing carbohydrate chemistry for product sustainability, increasing attention has been recently devoted to the transformation of various chemicals from biomass resources. Among the many possible biomass-derived chemicals, 5-hydroxymethylfurfural (5-HMF) is a versatile and key renewable platform from biomass-derived carbohydrates. Herein, we report an efficient process for transforming fructose into 5-HMF quantitatively, where the dehydration of fructose to 5-HMF was catalyzed by using sulfated zirconia as catalyst in ionic liquid 1-butyl-3-methyl imidazolium chloride ([BMIM][Cl]). A fructose conversion of 95.8% with a 5-HMF yield of 88.4% was achieved in 30 min reaction time at 100 oC. The ionic liquid and sulfated zirconia could be recycled and exhibited constant activity for 5 successive trials. The proposed process of using an ionic liquid with sulfated zirconia solid catalyst greatly reduces reaction temperature required over previous works for converting fructose to 5-HMF.

I&EC 73

Study of laser excitation of ethanol and isopropanol via flame front variation

Allen White(1), white@rose-hulman.edu, 5500 Wabash Ave, CM 4010, Terre Haute IN 47803, United States ; Revecca DeVasher(2); Stephen Sakai(1); Adam Standard(1). (1) Department of Mechanical Engineering, Rose-Hulman Institute of Technology, Terre Haute IN 47803, United States (2) Department of Chemistry, Rose-Hulman Institute of Technology, Terre Haute IN 47803, United States

Adding energy directly into the vibrational modes of automotive fuel may reduce the threshold energy required for combustion, without raising the combustion charge temperature. This energy can be supplied either directly via incident laser radiation or indirectly through collision with directly excited molecules. Previous work has shown that the automotive fuel components of isopropanol and ethanol can be excited by a 10.2 um and 9.3 um CO2 lasers, respectively. Previous

studies have been performed on gaseous fuels. In this study, the impact of infrared absorption of isopropanol in ethanol was measured via study of the variation of the flame front velocity after excitation with a CO2 laser. The measurements indicate that the laser absorption and subsequent fuel excitation resulted in an increase in the flame front velocity.

I&EC 74

Ionic liquid-water mixtures for efficient catalytic conversion of glucose to 5-hydroxymethylfurfural

Xinhua Qi(1), qixinhua@nankai.edu.cn, No.94, Weijin Road, Nankai District, Tianjin Tianjin 300071, China ; Haixin Guo(1); Luyang Li(1); Yingzhao Xu(1). (1) College of Environmental Science and Engineering, Nankai University, Key Laboratory of Pollution Processes and Environmental Criteria (Ministry of Education), Tianjin 300071, China

As the monomeric unit in cellulose, glucose is thought to be a good candidate for the preparation of 5-hydroxymethylfurfural (5-HMF), a versatile intermediate for synthesizing biofuel and biopolymers. The most efficient catalyst is chromium chloride, but they are poisonous with high environmental risk. The use of inherently nonhazardous catalysts and solvent systems is needed for application in today's society. We report a green process for glucose conversion to 5-HMF with a non-chromium catalytic system, in which a mixture of an ionic liquid and water was used as the reaction solvent. The combination of IL and water produced an interesting solvent effect, in which both the formation of fructose and 5-HMF were promoted to give relatively high 5-HMF yields. The results reported here can be extended to other fields, where the ratio of IL and water can be used to adjust the acid and base concentrations and promote one-pot reactions.

I&EC 75

Mathematical modeling of the dynamic hydraulic-thermal behaviors of a district heating system

Junyoung Lee(1), qwergyui@ajou.ac.kr, San5, Woncheon-dong, Yeongtong-gu, Suwon Gyeonggi-do 443749, Republic of Korea ; Jeongbin Lee(1); Chee Burm Shin(1). (1) Department of Chemical Engineering, Ajou University, Suwon, Republic of Korea

A district heating system produces thermal energy and supplies it to a large region. District heating systems can provide higher efficiencies and better pollution control than localized boilers. After generation, the heat is distributed to the customer via a network of insulated pipes. For the optimal operation of a district heating system, it is important to predict the distributions of pressure, flow

rate and temperature of heating fluid within the network of pipes at various operating conditions. In this work, a mathematical modeling was performed to predict the dynamic hydraulic-thermal behaviors of heating fluid in the network of pipes for a district heating system. The mathematical model accounts for the conservations of mass, momentum and energy. In order to verify the validity of modeling, the modeling results were compared with the monitoring data of Gangnam Branch of Korea District Heating Corporation.

I&EC 76

Use of boron compounds as synergistic flame retardants in low density polyethylene: Ethylene vinyl acetate blends and nanocomposites

Esin Ibibikcan(1), esin03@gmail.com, Metallurgical and Materials Eng. Dept. Room: D-307, Ankara - TR-06531, Turkey ; Cevdet Kaynak(1). (1) Department of Polymer Science and Technology, Middle East Technical University, Ankara - TR-06531, Turkey

Due to their very low fire retardancy, low density polyethylene (LDPE) and ethylene vinyl acetate (EVA) blends need high amounts of flame retardants when used in cable industry. For this purpose halogenated fire retardants have been used for many years. However because of their toxicity, corrosiveness and smoke production, they should be replaced with non-halogenated counterparts. Thus, the aim of this work is to use aluminum hydroxide (ATH) with boron compounds (e.g. zinc borate, boron oxide and boric acid) and nanoclays as synergistic agents. Specimens were melt-mixed by using a laboratory scale twin-screw extruder. In order to characterize specimens, various flammability (LOI, UL-94 and Cone Calorimetry), thermal, morphological and mechanical tests were conducted. It was generally observed that each three boron compounds had certain levels of synergistic improvement on the LOI, UL-94 and cone calorimeter values.

I&EC 77

Investigation into the kinetic hydrate inhibitors of pyrrolidinium- and morpholinium-based ionic liquids on gas hydrate

Seong-Pil Kang(1), spkang@kier.re.kr, 102 Gajeong-ro, Yuseong-gu, Daejeon Chungnam 305-343, Republic of Korea ; Sangjune Yoon(1), yoonsj@kier.re.kr, 102 Gajeong-ro, Yuseong-gu, Daejeon Chungnam 305-343, Republic of Korea ; Jonghyub Lee(2); Kisub Kim(3). (1) Clean Fossil Energy Research Center, Korea Institute of Energy Research, Daejeon 305-343, Republic of Korea (2) Department of Environmental Engineering, Kyungpook National University, Daegu 702-701, Republic of Korea (3) Department of Chemical and Biological Engineering, Chungju National University, Chungju Chungbuk 380-702, Republic of Korea

Ionic liquids are organic salts that consist of bulky asymmetric organic cations and form hydrogen bonds with water, so that are expected to retard effectively on hydrate nucleation. Xiao and Adidharma announced dialkylimidazolium-based ionic liquids as the kinetic and thermodynamic hydrate inhibitors against methane hydrate formation at the first time. Comparing to the former works, this paper presents the inhibition effect of pyrrolidinium- and methyl morpholinium-based ionic liquids on methane hydrate formation. The induction time of aqueous solution containing low concentration of ionic liquids (0.1~5 wt%) was measured, and the effect of inhibition strength was investigated regarding the composed anions of chlorine, and tetrafluoroborate. Measurements result in the superior inhibition effect of methyl morpholinium and tetrafluoroborate. In particular, methyl morpholinium based ionic liquids show the longer induction time on methane hydrate formation than dialkylimidazolium based ones.

I&EC 78

Modeling of the thermal behavior of a lithium-ion battery pack for electric vehicle applications

Jaeshin Yi(1), regret@ajou.ac.kr, San5, oncheon-dong, Yeongtong-gu, Suwon Gyeonggi-do, Republic of Korea ; Chee Burm Shin(1); Young-jin Hong(2); Chisu Kim(2). (1) Department of Chemical Engineering, Ajou University, Republic of Korea (2) R&D center, EIG Ltd., Republic of Korea

The lithium-ion battery is a preferred candidate as a power source for electric vehicle (EV) due to its outstanding characteristics such as high energy density, high voltage, low self-discharge rate, and good stability among others. However, some safety concerns stll exist. Outside the range of certain temperature thresholds, the temperature of the battery increases uncontrollably and fires can occur. For this reason, thermal modeling is a necessity to guaranteed safety of a lithium-ion battery pack. In this work, a three-dimensional modeling was carried out to investigate the effects of operating conditions on the thermal behavior of a lithium-ion battery pack for EV applications. The operating conditions considered were the discharge rate of a battery pack and the temperature and flow rate of cooling air. Heat generation rate in a cell was calculated using the modeling results of the potential and current density distributions of a battery cell.

I&EC 79

Finite element modeling of the thermal behavior of a lithium-ion battery

Seungmin Ryu(1), rsmin@ajou.ac.kr, San5, oncheon-dong, Yeongtong-gu, Suwon Gyeonggi-do, Republic of Korea ; Ui Seong Kim(1); Chee Burm Shin(1); Taeyoung Han(2); Seongyoung Park(3). (1) Department of Chemical Engineering, Ajou University, Republic of Korea (2) Vehicle Development Research Lab., GM

R&D center, United States (3) Advanced Technology Team, GM Daewoo Auto & Technology, Republic of Korea

The lithium-ion battery has become as a promising power source for electric vehicle (EV) due to its execellent cycle life, high energy density, and high voltage. With an increasing interest in larger lithium-ion battery for EV applications, one of the most important safety considerations for lithium-ion cells is thermal stability. Thermal modeling can play a vital role to maintain the operating temperature and temperature uniformity of lithium-ion battery within a suitable range. In this work, a two-dimensional finite element modeling is performed to calculate the potential and current density distribution on the electrodes of a lithium-ion battery. The modeling of the potential and current density distributions on the electrodes is validated by the comparison between experimental and modeling discharge curves at various discharge rates from 0.5C to 5C. Then, the thermal modeling of the lithium-ion battery is carried out, which accounts for the ohmic heating and the heat generated due to charge transfer at the electrode/electrolyte interface.

I&EC 80

Synergic and antagonistic effects in solvent extraction systems using TBP and DBP

Mikael Nilsson(1), nilssonm@uci.edu, 916 Engineering Tower, Irvine CA 92697-2575, United States ; Timothy L Anderson(1); Leanne C Bautista(1). (1) Department of Chemical Engineering and Materials Science, University of California Irvine, Irvine CA 92697-2575, United States

During treatment of spent nuclear fuel by the PUREX (Plutonium URanium EXtraction) process the main active component tributyl phosphate (TBP) may degrade to dibutyl phosphoric acid (DBP). This degradation and the effects have been extensively studied and observations indicate that DBP result in increased extraction of metal ions in spent nuclear fuel, complicating stripping. Furthermore DBP may cause precipitation in combination with high loading of certain metal ions. TBP is known to aggregate and produce a third phase at high metal loading and high nitric acid concentration causing unwanted effects in process. Compared to TBP the coordination of metals by DBP is not promoted by high acid but by a low acid concentration and similar effects are not anticipated. In this study we have investigated what effect combining TBP and DBP has on metal, acid, and water extraction to observe potential mixed aggregates in systems with both extraction reagents present.

I&EC 81

Modeling of double-pass parallel-plate heat exchangers under asymmetric wall temperatures

Chii-Dong Ho(1), cdho@mail.tku.edu.tw, 151, Ying-chuan Rd., Tamsui, Taipei Taiwan 251, Taiwan Republic of China ; Yi-Chin Chen(1); Chung-Nan Chen(1). (1) Department of Chemical and Materials Engineering, Tamkang University, Tamsui, Taipei Taiwan 251, Taiwan Republic of China

Considerable improvement of the device performance of heat transfer in a parallel-plate heat exchanger is obtained in inserting in parallel an impermeable and resistless sheet to divide an open duct into two channels for conducting double-pass operations under asymmetric wall temperature boundary conditions, as compared to those in the single-pass operations without an impermeable sheet inserted. The heat transfer problem is solved for fully developed laminar velocity profiles in both upper and lower channels with ignoring axial conduction. The analytical solutions to the resultant mathematical formulations for such conjugated Graetz problems were achieved by using the separation of variables, superposition principle and an orthogonal expansion technique in extended power series. The undesirable preheating and desirable convective transfer are the two effects which are in domination of the heat transfer behavior. Analytical predictions show that adjusting the ratio of top and bottom wall temperatures, recycle ratio and impermeable-sheet location can affect the heat transfer efficiency in designing double-pass parallel-plate heat exchangers under asymmetric wall temperatures. The effects of the impermeable-sheet location and ratio of top and bottom wall temperatures on the heat-transfer efficiency enhancement as well as on the power consumption increment have been discussed.

I&EC 82

Novel nanoporous carbon materials prepared from polybenzoxazine: Effect of diluents

Nakarin Nintawee(1)(2), natawee_37@hotmail.com, Soi Chula 12, Phayathai Road, Phatumwan Bangkok 10330, Thailand ; Uthen Thubsuang(1)(2); Sujitra Wongkasemjit(1)(2); Thanyalak Chaisuwan(1)(2). (1) Polymer Science, The Petroleum and Petrochemical College, Chulalongkorn University, bangkok 10330, Thailand (2) National Center of Excellence for Petroleum, Petrochemical and Advanced Materials, Chulalongkorn University, bangkok 10330, Thailand

Recently, a novel nanoporous carbon material prepared from polybenzoxazine through sol-gel process has been reported. Polybenzoxazine is a novel class of phenolic resin which can be easily prepared by the reaction between phenol derivatives, amine derivatives and formaldehyde. In addition to the synthesis parameters such as solvent, catalyst, etc.; the microstructure of this nanoporous carbon can also be controlled by varying different starting materials. The current work, which is a part of the experimental series conducted to fully understand the mechanism of polybenzoxazine sol-gel process which governs the microstructure

of this nanoporous carbon, is focused on the effect of diluents on the microstructure of nanoporous carbon derived from polybenzoxazine.

I&EC 83

Dehydrocyclization of 1,4-butanediol over copper-based catalysts

Jong-Ki Jeon(1), jkjeon@kongju.ac.kr, 182 Budae-dong, Seobuk-gu, Cheonan Chungnam 331-717, Republic of Korea ; Youn Jung Lee(1); Soyoung Yun(1); Young Soo Ko(1); Young-Kwon Park(2); Young-Seek Yoon(3). (1) Department of Chemical Engineering, Kongju National University, Cheonan Chungnam 331-717, Republic of Korea (2) School of Environmental Engineering, University of Seoul, Seoul 130-743, Republic of Korea (3) SK Energy Corp, Taejon 305-712, Republic of Korea

γ-Butyrolactone (GBL) and its derivatives are used as solvents and intermediates for pharmaceuticals. GBL can be manufactured via dehydrogenative cyclization of 1,4-butanediol (BDO). In this study, we investigated the effects of chrome addition on the catalytic activity over copper-based catalyst. Catalyst samples were prepared by a conventional coprecipitation method. Cr2O3 was employed as additives. The properties of the catalyst were analyzed using BET, X-ray diffractometer (XRD), temperature-programmed reduction (TPR), ammonia temperature-programmed desorption (NH3-TPD). The exposed copper surface area was measured by nitrous oxide titration. The reaction of BDO to GBL was performed in a fixed-bed down-flow SUS reactor at 210–280 ◦C in H2 or N2 flow. The GBL yield increased as the content of chrome increased. The catalysis containing 1.0 wt% of chrome showed the highest yield. The addition of 1 wt% of chrome increased the copper surface area and the amount of acid sites of Cu catalysts.

I&EC 84

Synthesis of novel polyimides with side-chain containing fluorine and their pervaporation performances to aromatic/aliphatic hydrocarbon mixtures

Lin Qin(1), qinl08@mails.tsinghua.edu.cn, Department of Chemical Engineering, Tsinghua University, Beijing, P. R. China, Beijing Beijing 100084, China ; Jiding Li(1). (1) Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Two novel aromatic diamines 3,5-Diaminobenzophenone(PDA) and 4-(trifluoromethyl)phenyl 3,5-diaminobenzoate(FPDA) were synthesized through two steps including monoesterification and reduction with hydrazine hydrate. DPA was mixed with 4,4'-diaminodiphenyl ether (ODA) with different ratios and copolymerized respectively with 4,4'-Oxydiphthalic anhydride (ODPA), 3,3',4,4'-Benzophenonetetracarboxylic dianhydride (BTDA) and 4,4'-

(Hexafluoroisopropylidene)-diphthalic anhydride (6FDA) to give poly(amic acid)s which were converted into polyimides (PIs) by thermal imidization. The same steps was carried on FPDA. The structures of these series of PIs were characterized by FT-IR, NMR, and XRD. The effect of side-chain content on the thermal stability and surface energies was investigated by DSC, TGA and contact angle measurement. The membranes of polyimide were employed in pervaporation separation of aromatic/aliphatic mixtures. ODPA-PDA/ODA(1/9) membranes obtained better separation performances having a flux of 5.30 kg·μm·m-2·h-1 and separation factor of 2.1 benzene/ cyclohexane(50/50 wt%) at 50�. The effects of the fluorine group on side-chain polyimides properties and separation performances were investigated. Keywords: polyimide; side-chain; synthesis; pervaporation; aromatic hydrocarbon

I&EC 85

Photocatalytic reduction of carbon dioxide through the use of metal porphyrins: Inspired by chlorophyll

Nathan Barefoot(1), barefonz@westminster.edu, Campus Box 224, New Wilmington Pennsylvania 16172, United States ; Peter Smith(1). (1) Department of Chemistry, Westminster College, New Wilmington Pennsylvania 16172, United States

A greenhouse gas gets its name because when released into the atmosphere it turns the atmosphere into a greenhouse and causes an increase in temperature. Although greenhouse gases, such as carbon dioxide, have a bad reputation, they are vital to life on this planet in low concentrations. The burning of fossil fuels has lead to a dramatic increase in CO2 concentration that could prove environmentally devastating. One possible solution is to photocatalytically reduce carbon dioxide and transform it into a compound of greater value. To this end hematoporphyrin coordinated with a transition metal might be capable of accomplishing this task. Insertion of the metal into the porphyrin will be confirmed by UV/VIS spectroscopy. Completed reactions will be analyzed with gas chromatography to qualitatively and possible quantitatively detect products.

I&EC 86

Investigation into effects of cerium and phosphorous on catalytic efficiency, stability and acidity of HZSM-5 zeolite on cracking of naphtha

Fatemeh Khodadadian(1), khodadadian.maryam@gmail.com, Ale-Ahmad Avenue, tehran tehran 14115143, Iran (Islamic Republic of) ; Jafar Towfighi Darian(1); Kamyar Keyvanloo(1). (1) Department of Chemical Engineering, Tarbiat Modares University, Tehran Tehran 14115143, Iran (Islamic Republic of)

HZSM-5 zeolites are widely used in heterogonous catalysis and cracking. There is a high interest to find new structures with differing topologies and pore dimensions. HZSM-5 is a SiO2/HAlO2 with Si/Al ratio typically ranging from 250-10. Recently attention has focused in catalytic cracking of naphtha to produce light olefins; however overcoming catalyst instability at high temperature in steam caused by dealumination remains a problem. A series of HZSM-5 catalysts with different Si/Al ratios were impregnated with Cerium and phosphorous. The effect of Cerium and phosphorous on the structure and acidity of P,Ce/HZSM-5 catalysts before and after severe hydrothermal treatment were studied and catalytic performance of catalysts for the cracking of naphtha was measured. It was found that cerium and phosphorous impregnation significantly improved both stability and catalytic performance. Also the optimized amount of P and Ce loading on the structure and stabilization of the framework aluminum in HZSM-5 was investigated.

I&EC 87

Stripping crystallization: A new separation technique

Lie-Ding Shiau(1), shiau@mail.cgu.edu.tw, 259 Wen-Hwa 1st Road, Kweishan Taoyuan 333, Taiwan Republic of China . (1) Department of Chemical and Materials Engineering, Chang Gung University, Kweishan Taoyuan 333, Taiwan Republic of China

Stripping crystallization (SC) is a new separation technique which combines distillation and crystallization to separate the mixtures with the close boiling temperatures. Basically, SC is operated at a triple-point condition, in which the liquid is simultaneously vaporized and crystallized due to the three-phase equilibrium. In essence, the process is continued until the liquid phase is completely eliminated and only the pure solid crystals remain in the feed. Thus, crystal washing is not required since only pure solid crystals remain in the feed and no impurities are adhered on the crystal surfaces at the end of SC. In the previous research, SC has been successfully applied to separate p-xylene from the mixed xylenes by Shiau et al. [Shiau et al., 2005; 2006; 2008]. SC is introduced in this work to purify styrene (ST) from the mixture consisting of ST, ethylbenzene, p-xylene, m-xylene and o-xylene. The experiments show that the purity of ST can be purified from 0.85 to 0.98 or from 0.90 to 0.99 in the mixture. Thus, SC provides an efficient separation method to separate ST from the mixture consisting of ST and the mixed xylenes. The recovery rate of ST can be greatly improved by adjusting the operating temperature and pressure during the SC process. 1. Shiau, L. D., Wen, C. C. and Lin, B. S. Separation and purification of p-xylene from the mixture of m-xylene and p-xylene by distillative freezing, Ind. Eng. Chem. Res, 44(7), 2258-2265, 2005. 2. Shiau, L. D., Wen, C. C. and Lin, B. S. Application of distillative freezing in the separation of o-xylene and p-xylene, A.I.Ch.E. Journal, 52(5), 1962-1967, 2006. 3. Shiau, L. D., Wen, C. C. and Lin, B. S. Separation of p-xylene from the multicomponent

xylene system by stripping crystallization, A.I.Ch.E. Journal, 54(1), 337-342, 2008.

I&EC 88

Fundamental aspects of metal ion transfer into room temperature ionic liquids

Mark L Dietz(1), dietzm@uwm.edu, 3210 N Cramer Street, Milwaukee WI 53211, United States ; Cory A Hawkins(1); Sarah L Garvey(1); Alan J Pawlak(1). (1) Department of Chemistry and Biochemistry, University of Wisconsin-Milwaukee, Milwaukee WI 53211, United States

Studies of the partitioning behavior of group 1A and 2A metal ions in systems comprising an acidic aqueous phase and an immiscible ionic liquid (IL) to which is added a suitable extractant have established trends in the predominant modality by which these ions are transferred between phases. Our understanding of partitioning in molecular solvents has been applied to similar studies using a series of ILs in the presence of various extractants. Specifically, by systematically altering the hydrophobicity of the IL ions, the nature and concentration of the acid, and the extractant, it has been shown that the relative importance of cation exchange and neutral complex extraction to the overall ion transfer process can vary considerably. By understanding the extraction selectivity unique to these systems, we can begin to rationally design IL-based extraction systems, thus providing opportunities to develop novel metal ion separations.

I&EC 89

CO2 Reforming of methane by bimetallic Ni-Ru-MCM-41 catalysts prepared by one-pot procedure

Gulsen Dogu(1), gdogu@gazi.edu.tr, Maltepe, Ankara Ankara 06570, Turkey ; Esra Sarıer(1); Nail Yasyerli(1); Sena Yasyerli(1). (1) Department of Chemical Engineering, Gazi University, Ankara Ankara 06570, Turkey

Dry reforming of methane is a promising method of synthesis gas production with a H2/CO ratio suitable for the synthesis of hydrocarbons. Development of active and stable catalysts with low carbon deposition is the key factor in realization of this reaction for industrial applications. In this study, Ru-Ni incorporated MCM-41-like silicate structured mesoporous catalysts having different Ru/Ni ratios were synthesized following a one-pot hydrothermal procedure and activities of these catalysts were tested in dry reforming of methane. Characterization results showed well dispersion of Ni and Ru within the high surface area catalysts having ordered pore structures. Methane dry reforming reaction results showed significant increase of catalyst activity and stability by Ru incorporation. Ru incorporation also increased hydrogen yield and decreased contribution of

reverse water gas shift reaction. Methane conversion values close to equilibrium and CO/H2 ratios close to one were obtained with Ru-Ni incorporated catalysts at a temperature of 600oC.

I&EC 90

Toward green synthesis of engineered nanomaterials for in-vivo human disease detection and drug delivery with application to nanomaterial design for detection and remediation of environmentally distributed ecological and human toxins

Warren W. Layne(1), layne.warren@epa.gov, Mail Code: SR-5J, 77 W. Jackson Boulevard, Chicago IL 60604, United States . (1) USEPA Region 5, Superfund Division, United States Environmental Protection Agency, Chicago IL 60604, United States

Nobel Laureate Gerhardt Ehrlich coined the phrase “magic bullet” for pharmaceuticals to treat specific biological targets in the body. Biochemically modified engineered nanomaterials manufactured from carbon, metals and metal oxides, chemical polymers and synthetically modified biopolymers, when injected into biological systems, have been shown to have the potential to act in this manner. This general overviewwill highlight green syntheses of nanomaterial preparations for targeted drug delivery and in-vivo sensing that may be conceptually useful in the preparation of nanomaterials for pharmaceuticals, remediation, and sensing of persistent environmental human and ecological toxins.

I&EC 91

Functional assays of nanoparticle toxicity

Christy L Haynes(1), chaynes@umn.edu, 207 Pleasant Street SE, Minneapolis MN 55455, United States ; Melissa A Maurer-Jones(1). (1) Department of Chemistry, University of Minnesota, Minneapolis MN 55455, United States

Common in vitro assays of nanoparticle toxicity consider the viability of cells following nanoparticle exposure. While this is valuable information, it is also critical to consider nanoparticle effects on cell function in surviving cells. To gain a deeper understanding of the nanoparticle-cell interaction, this work explores the impact of TiO2 nanoparticles on primary culture mast cells. Specifically, carbon-fiber microelectrode amperometry was employed to monitor the effect of these nanoparticles on the critical cell function of exocytosis, where chemical messenger molecules are secreted from the mast cell granules. The collected data demonstrate that exocytosis is influenced by the presences of TiO2 nanoparticles and that the disruption in cell behavior correlates with TiO2-generated reactive oxygen species.

I&EC 92

Flexible nanostructured polymers that capture, isolate and simultaneously detect engineered nanoparticles

Wunmi Sadik(1), osadik@binghamton.edu, POB 6000, East Vestal Parkway, Binghamton NY 13902, United States ; Nian Du(1). (1) Chemistry, SUNY-Binghamton, Binghamton NY 13902, United States

There is urgent demand for rapid screening methods to isolate, detect, and monitor engineered nanomaterials in the environment. Conventional methods for characterizing nanomaterials such as transmission electron microscopy, scanning electron microscopy and atomic force microscopy tend to be bulky and inadequate for field & rapid screening of free nanomaterials. Our Group has discovered that a new class of flexible, stand-alone polyamic acid (PAA) membranes could be successfully used as both sensors and nanofilters. A new nanofilters device based on PAA membranes is hereby introduced. The nanofilters were derived from phase-inverted, copolymers of PAA and other polymers, with the surface and pore sizes systematically controlled by varying the conditions of the synthesis. This presentation will focus on the use of the PAA membranes for simultaneous removal and electrochemical detection of gold nanoparticles, quantum dots and titanium dioxide nanocrystal from environmental samples

I&EC 93

Characterization of stability and end of life behavior of quantum dot-polymer nanocomposites

John K Katahara(1), john_katahara@brown.edu, 182 Hope Street, Providence RI 02912, United States ; Jingyu Liu(2); Robert Hurt(1)(3). (1) School of Engineering, Brown University, Providence RI 02912, United States (2) Department of Chemistry, Brown University, Providence RI 02912, United States (3) Institute for Molecular and Nanoscale Innovation, Brown University, Providence RI 02912, United States

The unique photonic properties of quantum dots have led to their widespread but small-scale use in biological imaging and their potential large-scale use in emerging electronic and optical devices. The large-scale applications require consideration of their impacts on the environment, especially at end-of-life. Many industrial nano-products do not contain free particles, but rather imbedded particles in polymer matrices. This study investigates the stability and end of life behavior of practical CdSe/ZnS quantum dot-polymer nanocomposites. The nanocomposites are exposed to biological and environmental simulants, and the time dependent release of cadmium is characterized through ICP-AES. We address the key regulatory question whether landfill degradation of the

composites involves liberation of free nanoparticles, or whether the particles remain bound and release only conventional chemical toxicants in soluble form. The degradation mechanisms and environmental implications will be discussed.

I&EC 94

Biofunctionalization of graphene for biosensing and imaging

Yuehe Lin(1), Yuehe.lin@pnl.gov, 902 Battelle Boulevard, PO Box 999, Richland WA 99352, United States . (1) Pacific Northwest National Laboratory, Richland WA 99352, United States

Graphene is single layer carbon crystal that emerged as a novel nanomaterial and demonstrated many exceptional features including excellent conductivity, high surface-to-volume ratio, remarkable mechanical strength and biocompatibility. Graphene has attracted increasing attentions from physics, chemistry and biomedical fields. In this presentation, I will discuss recent progress in functionalization of graphene and their biomedical and bioassay applications. Here, we chose DNA, a core component in many fundamental life processes involving life proliferation, metabolism and evolution, as a target biomolecule, to study the interactions between DNA and functionalized graphene. Besides, exploration of graphene with intracellular analyzing, living cell imaging and in situ monitoring will also be discussed.

I&EC 95

Enhanced microcontact printing of proteins on nanoporous silica surface

Xiaojing (John) Zhang(1), John.Zhang@engr.utexas.edu, 10100 Burnet road, J.J. Pickle Research Campus, Austin TX 78758, United States ; Kazunori Hoshino(1); Ashwini Gopal(1). (1) Department of Biomedical engineering and Microelectronics Research Center, The University of Texas at Austin, Austin TX 78758, United States

We demonstrate porous silica surface modification, combined with microcontact printing, as an effective method for enhanced protein patterning and adsorption on arbitrary surfaces. Compared to conventional chemical treatments, this approach offers scalability and long-term device stability without requiring complex chemical activation. Two chemical surface treatments using functionalization withthe commonly used 3-aminopropyltriethoxysilane (APTES) and glutaraldehyde (GA) were compared with the nanoporous silica surface on the basis of protein adsorption. The deposited thickness and uniformity of porous silica films were evaluated for fluorescein isothiocyanate (FITC)-labeled rabbit immunoglobulin G (R-IgG) protein printed onto the substrates via patterned polydimethlysiloxane (PDMS) stamps. A more complete transfer of proteins was observed on porous silica substrates compared to chemically functionalized

substrates. A comparison of different pore sizes (4–6 nm) and porous silica thicknesses (96–200 nm) indicates that porous silica with 4 nm diameter, 57% porosity and a thickness of 96 nm provided a suitable environment for complete transfer of R-IgG proteins. Both fluorescence microscopy and atomic force microscopy (AFM) were used for protein layer characterizations. A porous silica layer is biocompatible, providing a favorable transfer medium with minimal damage to the proteins. A patterned immunoassay microchip was developed to demonstrate the retained protein function after printing on nanoporous surfaces, which enables printable and robust immunoassay detection for point-of-care applications.

I&EC 96

Green nanotechnology: Its future and implications in medicine and technology

Kattesh V Katti(1), kattik@health.missouri.edu, Allton Bldg Labs, 301 Business Loop 70 W, Columbia MO 65212, United States . (1) Department of Radiology, University of Missouri, Columbia MO 65212, United States

Green nanotechnology has attracted considerable interest because it provides new pathways for the production, fabrication and overall utilization of nonmaterials with minimal/no environmental toxicity. We have discovered that the water soluble peptide: trimeric phopshino alanine P(CH2NHCH(CH3)COOH)3 (TPAL: referred to as 'Katti Peptide'), reduces metal salts to corresponding nanoparticles in aqueous media. The reduction reactions of metal salts to corresponding nanoparticles by TPAL also ensues breaking down of this trimeric peptide into biocompatible and non toxic alanine and phosphoric acid and thus does not leave any toxic trail of chemical byproducts. As representative examples on the tremendous potential of green nanotechnology, this presentation will also provide details on the propensity of cinnamon-phytochemicals coated gold nanoparticles to internalize selectively within prostate tumor cells and their utility in circulating tumor cell detection; the optimum residence profile of Gum Arabic-glycoprotein conjugated gold nanoparticles within tumors and their applications in tumor therapy.

I&EC 97

Planning your job search

John H. Engelman(1), jhengelm@scj.com, 1525 Howe Street, Racine Wisconsin 53403, United States ; Mary K. Moore(1), mkmoore@eastman.com, P.O. Box 1972, Kingsport TN 37662, United States . (1) American Chemical Society, United States

Your success in conducting an effective job search depends on the ability to organize your search and target the job market segment that's right for you. This session will help you plan and execute an effective job search. You'll learn about the changing trends in the employment marketplace for chemical professionals, and carry out a personal assessment to help you identify which jobs will be best suited to your values, skills and motivations. You'll also discover how to find hidden job markets through networking, how to make effective cold calls to employers, and how to find useful information about potential employer organizations.

I&EC 98

Preparing a résumé

John H. Engelman(1), jhengelm@scj.com, 1525 Howe Street, Racine Wisconsin, United States ; Mary Moore(1), mkmoore@eastman.com, P.O. Box 1972, Kingsport TN, United States . (1) American Chemical Society, United States

There is only one purpose of a résumé: to get an interview for the job you want. In this workshop you'll learn what content to include and not include in your résumé and how you should think about organizing that content. We'll also focus on the visual appeal - the length and layout that invites the recruiter to review it. We will also discuss how to send your résumé electronically.

I&EC 99

Effective interviewing

John Engelman(1), jhengelm@scj.com, 1525 Howe Street, Racine Wisconsin 53403, United States ; Mary Moore(1), mkmoore@eastman.com, P.O. Box 1972, Kingsport TN 37662, United States . (1) American Chemical Society, United States

Performing well in a job interview and acing an exam in school have one thing in common: the more prepared you are, the more successful you will be. This workshop provides practical steps to help you prepare for an interview with specific focus on 3 key aspects: 1) becoming familiar with the questioning format used by many interviewers, 2) preparing your responses to some "tough" interview questions, and 3) conducting "due diligence" research on the organization. You will also learn to highlight your unique strengths and the special ways you can contribute to the hiring organization without appearing to be boastful.

I&EC 100

Tailoring ionic liquids for CO2 capture

Sheng Dai(1), dais@ornl.gov, 1 Bethel Valley Rd., Oak Ridge TN, United States . (1) Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge TN 37831, United States

Imidazolium-based ionic liquids continue to attract interest in many areas of chemistry because of their low melting points, relatively low viscosities, ease of synthesis, and good stabilities against oxidative and reductive conditions. However, they are not totally inert under many conditions due to the intrinsic acidity of hydrogen at the C-2 position in the imidazolium cation. In this work, this intrinsic acidity was exploited in combination with an organic superbase for the capture of CO2 under atmospheric pressure. During the absorption of CO2, the imidazolium-based ionic liquid containing an equimolar superbase reacted with CO2 to form a liquid carbonate salt so that the equimolar capture of CO2 with respect to the base was achieved. The effects of ionic liquid structures, types of organic superbases, absorption times, and reaction temperatures on the capture of CO2 were investigated. Our results show that this integrated ionic liquid–superbase system is capable of rapid and reversible capture of about 1 mol CO2 per mole of ionic liquid. Furthermore, the captured CO2 can be readily released by either heating or bubbling N2, and recycled with little loss of its capture capability. This efficient and reversible catch-and-release process using the weak acidity of the C-2 proton in nonvolatile imidazolium-based ionic liquids provides a good alternative to the current CO2 capture methods that use volatile alkanols, amines, or water. This work was supported by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy.

I&EC 101

Ionic liquids for improved liquid-liquid extraction processes

Héctor Rodríguez(1)(2), hector.rodriguez@usc.es, Rúa Lope Gómez de Marzoa, s/n, Santiago de Compostela A Coruña 15782, Spain ; María Francisco(1); Sara Lago(1); Martyn J Earle(2); John D Holbrey(2); Kenneth R Seddon(2); Robin D Rogers(2)(3); Ana Soto(1); Alberto Arce(1). (1) Department of Chemical Engineering, University of Santiago de Compostela, Santiago de Compostela 15782, Spain (2) QUILL Centre, Queen[apos]s University Belfast, Santiago de Compostela 15782, Spain (3) Center for Green Manufacturing and Department of Chemistry, The University of Alabama, Belfast Northern Ireland BT9 5AG, United Kingdom

Ionic liquids exhibit, in general, a very interesting set of properties for their use as solvents. In particular, they look promising in the development of improved liquid-liquid extraction processes. This presentation will show results on the use of several ionic liquids for diverse applications by solvent extraction: concentration of essential oils of plants, separation of aromatic and aliphatic hydrocarbons, desulfurisation of fuels, and removal of metals from petroleum. These separation problems have been modelled by means of ternary systems, and the liquid-liquid

equilibrium data for these systems have been determined. The results allow for an analysis of the suitability of the ionic liquids as extracting solvents in the applications suggested. Since several ionic liquids have been tried, an initial identification of desirable ions or structural features in the ionic liquid can also be made, in order to optimise the choice for a practical separation process.

I&EC 102

Understanding separations through undergraduate research: Applications of ionic liquid based aqueous biphasic systems

Meghna Dilip(1), mdilip@worcester.edu, 486 Chandler Street, Worcester MA 01602, United States ; Keith Dusoe(1); Bradford G Spencer(1); Jonathan Parella(1); Joseph Amissah(1). (1) Department of Chemistry, Worcester State University, Worcester MA 01602, United States

In general, chemistry undergraduate programs do not focus on separations chemistry, although separations are an integral part of industry. In an attempt to bridge this gap, independent-study research projects with a "green" focus are being conducted at Worcester State University. Hydrophilic ionic liquids (ILs) partition into two phases in the presence of kosmotropic salts forming primarily water-based aqueous biphasic systems (ABS). We have used these systems to quantitatively partition indigo dyes having varying degrees of sulfonation as well as, metals like chromium into the IL-rich upper phase. Distribution ratios obtained varied widely depending on conditions such as type and concentration of ionic liquid, concentration and type of kosmotropic salt type used to make the ABS. Preliminary results of solvatochromic studies in ABS will also be presented. These projects build on our understanding of ionic liquid-based ABS vs. traditional solvent systems while providing key opportunities to undergraduates to understand partitioning and separations.

I&EC 103

Biphasic liquid-liquid systems based on ionic liquids and polyethylene glycols

María Francisco(1)(2), maria.francisco@usc.es, Rúa Lope Gómez de Marzoa s/n, Santiago de Compostela A Coruña 15782, Spain ; Héctor Rodríguez(1)(2); Ning Sun(3); Mustafizur Rahman(3); Jorge F B Pereira(4); Mara G Freire(4)(5); Luís P N Rebelo(5); João A P Coutinho(4); Robin D Rogers(2)(3). (1) Department of Chemical Engineering, University of Santiago de Compostela, Santiago de Compostela 15782, Spain (2) QUILL Centre, Queen’s University Belfast, Santiago de Compostela 15782, Spain (3) Center for Green Manufacturing and Department of Chemistry, The Universtiy of Alabama, Tuscaloosa Alabama 35487, United States (4) CICECO, Departamento de Química, Universidade de Aveiro, Aveiro

3810-193, Portugal (5) Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, Aveiro 3810-193, Portugal

Some mixtures of ionic liquids and polyethylene glycols can give rise, at the appropriate composition and over a broad range of temperatures, to totally liquid, immiscible systems. The two liquid phases formed can be potentially useful in separation processes, for example in the combined dissolution and fractionation of hard-to-dissolve, complex solutes (such as biomass). Ionic liquids and polyethylene glycols can also be used as co-solutes in an aqueous medium to produce aqueous biphasic systems at room temperature. These systems, in which the two co-existing phases are aqueous, have potential application in biotechnology separations. Phase diagrams will be presented for these two types of liquid, biphasic systems, and initial attempts for practical application in separation of solutes will also be discussed.

I&EC 104

Extraction of lithium and other valuable minerals from geothermal brines

Stephen Harrison(1), sharrison@simbolmining.com, 6920 Koll Center Parkway, Suite 213, Pleasanton California 94566, United States . (1) Technology, Simbol Mining, Pleasanton California 94510, United States

This paper discuss the potential for the extraction of lithium, potassium, managanese and zinc from Salton sea geothermal brines. It will discuss potential approaches to their extraction and conversion to valuable products.

I&EC 105

Chromium(III) is not an essential element but may have pharmacological relevance

Kristin R Di Bona(1), roger064@crimson.ua.edu, Box 870344, Tuscaloosa Alabama 35487, United States ; Sharifa Love(2); Nicholas R Rhodes(2); DeAna McAdory(2); Sarmistha H Sinha(2); Naomi Kern(2); Julia Kent(1); Jesslyn Strickland(1); Austin Wilson(1); Janis Beaird(3); James Ramage(4); Jane F Rasco(1); John B Vincent(2). (1) Department of Biological Sciences, The University of Alabama, Tuscaloosa Alabama 35487, United States (2) Department of Chemistry, The University of Alabama, Tuscaloosa Alabama 35487, United States (3) Department of Biological and Environmental Sciences, University of West Alabama, Livingston Alabama 35470, United States (4) Animal Care Facility, The University of Alabama, Tuscaloosa Alabama 35487, United States

Chromium(III) has been accepted as an essential trace element for over thirty years. Based on a recent experiment, chromium is likely not an essential trace element. Zucker lean rats were housed in metal-free cages for a period of four

months. Rats were fed a standard AIN-93 G diet with variable levels of chromium; a chromium deficient diet, a chromium sufficient diet, and diets with an additional 200 or 1000 μg Cr/kg body mass. Chromium levels in the diets had no effect on body mass, food intake, or glucose levels in glucose or insulin tolerance tests. A trend of decreased insulin levels with increased chromium content was observed in response to a glucose challenge. This led to the conclusion that Cr is not an essential element, but may have a pharmacological effect at high doses.

I&EC 106

Release of ionic liquid-active pharmaceutical ingredients from biopolymeric beads

Parker D McCrary(1), pmccrary1@crimson.ua.edu, 250 Hackberry Lane, Tuscaloosa Alabama 35487, United States ; Marcin Smiglak(1); Scott K Spear(1); Nicolas S Bates(1); Daniel T Daly(1); Robin D Rogers(1). (1) Department of Chemistry, Center for Green Manufacturing, Alabama Institute for Manufacturing Excellence, The University of Alabama, Tuscaloosa Alabama 35487, United States

This presentation will discuss delivery of pharmaceuticals in the form of ionic liquids (ILs) by encapsulation into biopolymeric beads to increase their bioavailability. Here the strategy will be illustrated by the synthesis of an IL of the active pharmaceutical ingredient (API) ibuprofen in its anionic form (a common model pharmaceutical) paired with cations of several other APIs. The talk will review the incorporation of the new IL-APIs into natural biopolymer beads via dissolution and spray drying and discuss the measured release rates of the ILs when the beads are placed in buffer solutions. Current challenges and opportunities in the selection of biopolymer platforms for the release of IL-APIs will be discussed.

I&EC 107

Energetic ionic liquids

Julia L Shamshina(1), shams002@as.ua.edu, 3016 Shelby Hall, 250 Hackberry Lane, Tuscaloosa AL 35487, United States ; David M Drab(1); Robin D Rogers(1); Marcin Smiglak(2). (1) Center for Green Manufacturing Department of Chemistry, The University of Alabama, Tuscaloosa AL 35487, United States (2) IoLiTec GmbH, Heilbronn, Germany

There exists a high demand for the development of new and improved energetic materials as traditional ones face environmental and safety concerns. Ionic liquids (ILs, salts with melting points below 100 oC) offer several advantages for energetic applications as they often possess desired physical and performance

properties as well as low toxicity characteristics. In this presentation, the focus will not be on the synthesis of EMs per se but, rather, on understanding the science necessary to provide new EMs for propulsion systems and on developing strategies to access targeted properties in a systematic and predictable fashion. The general efforts to be discussed include (i) the development of ILs for hydrazine replacement and (ii) the development of strategies to prepare energetic ions as a synthetic platform in conjunction with azolate, triflate, and other energetic or stabilizing anions.

I&EC 108

Ionic liquids which try to be like hydrazine

Stefan Schneider(1), stefan.schneider@edwards.af.mil, 10 East Saturn Blvd. Bldg 8451, Edwards AFB CA 93524, United States ; Yonis Ahmed(1); Michael Rosander(1); Tom Hawkins(1). (1) Air Force Research Laboratory, Edwards AFB CA 93524, United States

Ionic liquids (ILs) are getting more and more attention because of many remarkable properties such as low volatility, low flammability, high ion mobility, and excellent chemical and thermal stabilities. Due to these properties, ILs are being increasingly investigated for all kinds of liquid applications, including the niche area of energetic materials. Currently, hydrazine and its derivatives are state-of-the-art rocket fuels. Ongoing investigation on energetic ILs in our laboratory led to the first discovery of ILs as hypergolic fuels, and from an environmental perspective, these ILs could provide an alternative to the highly toxic hydrazine fuels used today. Prospective design strategies for ILs which would emulate properties that make hydrazine such a useful propellant fuel are discussed.

I&EC 109

Chemical looping technology and CO2 capture

L.- S. Fan(1), fan@chbmeng.ohio-state.edu, 140 West 19th Avenue, Columbus OH 43210-1180, United States . (1) William G. Lowrie Department of Chemical and Biomolecular Engineering, The Ohio State University, Columbus OH 43210-1180, United States

The concept of chemical looping reactions has been widely applied in chemical industries, e.g., the production of hydrogen peroxide (H2O2) from hydrogen and oxygen using 9,10-anthraquinone as the looping intermediate. However, there are presently no chemical looping processes using fossil fuels in commercial operation. A key factor that hampered the continued use of these earlier processes was the inadequacy of the reactivity and recycleability of the looping particles. This factor led to unsustainable operation of the process. With CO2

emission control now being considered as a requirement, interest in chemical looping technology has resurfaced. In particular, chemical looping processes are appealing due to their unique ability to generate a sequestration-ready CO2 stream. Renewed fundamental and applied research since the early 1980s has emphasized improvement over the earlier shortcomings. New techniques have been developed for direct processing of coal or other solid carbonaceous feedstock in chemical looping reactors. Significant progress is underway in particle design, reactor development, and looping system integration, as demonstrated by the operation of several pilot or sub-pilot scale units worldwide, making it possible that chemical looping technology may be commercially viable in the future for processing carbonaceous fuels. This presentation will describe the fundamental and applied aspects of modern chemical looping technology that utilizes fossil and other carbonaceous feedstock. The presentation will discuss particle synthesis, oxygen ion transfer mechanism, reaction chemistry, thermodynamics, and reactor and system engineering. It will highlight four chemical looping processes developed in the author's laboratory that are at various stages of large-scale demonstrations. Further, the CO2 emission control using the chemical looping technology is illustrated in light of other CO2 capture methods including chemical absorption based MEA scrubbing, and physical absorption based Selexol and Rectisol processes. Opportunities and challenges for chemical looping process commercialization will be discussed.

I&EC 110

Palladium-based membrane reactor process for precombustion CO2

sequestration, hydrogen production, and process intensification

Yi Hua Ma(1), yhma@WPI.EDU, Center for Inorganic Membrane Studies, Goddard Hall, 121, Worcester MA 01609, United States ; Nikolaos K Kazantzis(1); Reyyan Koc(1); Alexander S. Augustine(1). (1) Department of Chemical Engineering, Worcester Polytechnic Institute, Worcester MA 01609, United States

The development of technologies for pre-combustion CO2 sequestration and economical hydrogen production is important to the hydrogen economy and to protecting our environment. Pd-based membrane reactors (MR) can satisfy both requirements and are suited for process intensification by combining reaction, product concentration and separation in a single unit operation, providing high energy efficiency and low capital costs. Membranes with long-term chemical, thermal and mechanical stability at high temperatures and pressures with high hydrogen fluxes and high separation selectivity are required for an integrated catalytic membrane reactor and separator for producing pure hydrogen. Our unique patented technologies for producing composite ultra thin Pd membranes supported on sintered porous metal substrates satisfy all these requirements and provide the long-term thermal stability of composite Pd and Pd/alloy porous metallic substrate membranes. Experimental results showed that between 300 -

450˚C, and 1-6.8 atm, an excellent H2/He selectivity stability was achieved for ~3550 hours (>147 days, membrane thickness ~ 7 µm). The long-term stability was successfully re-produced. Mixed gases with different compositions were used to investigate the effects of CO on the hydrogen permeance and the results showed that the CO effects were negligible for temperatures equal or greater than 450˚C. The water gas shift reaction was carried out for both packed-bed and catalytic membrane reactor at 350, 400 and 450˚C to explore the benefits of a membrane reactor. The results showed that CO conversions exceeded the equilibrium conversion for all three temperatures. Process intensification of the MR was performed with the aid of a reactor model. The integration of MRs into IGCC plants was found to be an economically attractive technology option in cases of regulatory action on carbon emissions compared to traditional pulverized coal-based power plants and IGCC plants using packed-bed reactors.

I&EC 111

Novel membranes, processes and applications

Kamalesh K. Sirkar(1), Sirkar@ADM.NJIT.EDU, University Heights, Newark NJ 07102, United States . (1) Otto York Department of Chemical, Biological and Pharmaceutical Engineering, New Jersey Institute of Technology, Newark NJ 07102, United States

This presentation will focus on a few novel membranes and their novel as well as conventional applications. The membranes to be discussed involves mixed matrix membranes, hydrogel membranes, high free volume glassy membranes, as well as novel stable liquid membranes in a composite support structure. The process applications involve solvent nanofiltration, CO2 separation, solvent recovery from fermentation broths, removal of volatile species from corrosive solutions and other applications of a demanding nature. The performances of such membranes will be presented and discussed.

I&EC 112

Applications of surface modifying macromolecules for various membrane separation processes

Takeshi Matsuura(1), takeshi_mtsr@yahoo.ca, 161 Louis Pasteur St., Ottawa ON K1N 6N5, Canada ; A F Ismail(2); D Rana(1). (1) Department of Chemical and Biological Engineering, University of Ottawa, Ottawa ON K1N 6N5, Canada (2) Advanced Membrane Technology Research Centre (AMTEC),, Universiti Teknologi Malaysia, Johor Darul Ta‘zim, Malaysia

Membrane surface can be modified by blending a small amount of surface modifying macromolecules (SMMs) into the host membrane polymer. During the process of membrane fabrication SMMs migrate to the membrane surface to

lower the surface energy and concentrate at the surface, as evidenced by a number of surface characterization method. Unlike other methods, membrane surface modification is carried out by the phase inversion process without any additional surface modification step. SMMs are synthesized in two steps; i.e. synthesis of a polyurethane or polyurea prepolymer and end-capping of the prepolymer. Depending on the properties of the functional groups in the end-capping agent, SMMs can be either hydrophobic, hydrophilic or charged. SMMs have found applications in the following membrane separation processes. The objective of the paper is to review the fundamental principles, the experimental methods and the results obtained for each application. Oily wastewater treatment: Contributed to fouling reduction Treatment of Ottawa River water: Contributed to fouling reduction Removal of endocrine disrupting compounds (EDCs): Improvement in the separation of EDCs Fouling reduction of TFC nanofiltration membrane: Improvement in mechanical and chemical stability Reduction of biofouling by Ag incorporation: Enhancement of disinfection effect Seawater desalination by membrane distillation: Enhancement of MD flux, reduction in membrane pore size Gas separation membranes: Removal of defective pores in the skin layer Pervaporation membrane: Applied for the removal of VOCs from water Membrane contactor: Applied for CO2 transfer from gas to liquid absorbent phase Membranes for DMFC: Enhancement of proton conduction and reduction in methanol diffusion

I&EC 113

Study on process intensification of pre-combustion CO2 capture

Weiyang Fei(1), fwy-dce@mail.tsinghua.edu.cn, Hai Ding District, Beijing Beijing 100084, China ; Xia Gui(1); ZhiGang Tang(1). (1) State Key Laboratory of Chemical Engineering, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Global warming, caused by greenhouse gases, has become a key environmental problem. The Integrated gasification combined cycle (IGCC) combined with Carbon Capture and Storage (CCS) is supposed to be the best clear coal technology; however, the cost of CO2 capture is still too high using existing technologies. Therefore, it is necessary to study its process intensification in order to reduce the cost significantly. The novel solvents, high efficiency column internals and system optimization were studied systematically. Dimethyl carbonate (DMC), a “green” absorbent, was proposed as a new solvent. The Plum Flower Mini Ring (PFMR) was proposed as the column internal instead of Mellapak. The feasibility to use pervaporation for solvent regeneration was studied. The process optimization based on Pro II was carried out as well. As a result, the cost of pre-combustion CO2 capture might decrease substantially compared with existing technologies. Pilot plant tests are on schedule.

I&EC 114

Rare-earth(III)−crown-ether−polyiodides

Gerd Meyer(1), gerd.meyer@uni-koeln.de, Greinstrasse 6, Cologne NRW 50939, Germany . (1) Department of Chemistry, University of Cologne, Cologne 50939, Germany

Rare-earth(III) cations may be sequestered in various crown ethers and their derivatives in organic solvents yielding a variety of momeric or dimeric large cations with polyiodide anions. For lanthanum, for example, four different cations were observed: [LaI(Db18c6)Dme]2+, [LaI(Db18c6)(H2O)2]2+, [LaI2(B18c6)Thf]+, and [La2(OH)2(B18c6)2(Thf)2]4+ with tri-and pentaiodide anions. Other polyiodide anions may also be incorporated, as the spectacular [Lu(Db18c6)(H2O)3(Thf)6]4(I3)2(I5)6(I8)(I12) attests. All these compounds must be synthesized unter anhydrous conditions, traces of water enter the first coordination sphere. Larger amounts of water dominate the first coordination sphere and may lead to double-shell cations as in [R(H2O)9(Dch18c6)3](I3)3 and [R(H2O)9(Dch18c6)3](I5)3(H2O)4 with a large variety of rare-earth cations, practically through the whole series.

I&EC 115

Design and application of recoverable aqueous-phase catalysts for cross-coupling reactions

Kevin H. Shaughnessy(1), kshaughn@bama.ua.edu, Box 870336, Tuscaloosa AL 35487-0336, United States . (1) Department of Chemistry, The University of Alabama, Tuscaloosa AL 35487-0336, United States

Palladium-catalyzed cross-coupling reactions are powerful methods for forming C—C and C—heteroatom bonds. These reactions are of increasing importance in pharamaceutical and other fine chemical manufacturing. Stringent limits on residual heavy metals and the economic necessity of recovering precious metals makes separation and recovery of thes catalyst a high priority. While a variety of methods are known to remove trace metals, these can be material and energy intensive. Simplified recovery approaches would allow processes to be carried out in a more sustainable manner. Our group is interested in developing hydrophilic catalyst systems based on sterically demanding, electron-rich alkylphosphine ligands. Ligands such as t-Bu-Amphos and DTBPPS give catalysts showing high activity towards cross-coupling of aryl bromides and chlorides under mild conditions. These catalysts can be constrained in the aqueous phase and in some cases are highly recyclable. Application of catalysts derived from these ligands in a variety of metal-catalyzed coupling reactions will be discussed along with strategies to recycle or recover these catalysts.

I&EC 116

From plant to drug: Ionic liquids for the isolation of active ingredients from biomass

Katharina Bica(1), kbica@ioc.tuwien.ac.at, Getreidemarkt 9/163, Vienna Vienna 1060, Austria ; Anna Ressmann(1); Peter Gaertner(1). (1) Institute of Applied Synthetic Chemistry, Vienna University of Technology, Vienna 1060, Austria

The isolation of active ingredients from biomass is mainly performed using extraction processes; however this is always associated with the dangers of handling large volumes of volatile and combustible solvents, human risk and often limited efficiency. While the interest in ionic liquids as solvents for biomass is constantly growing, relatively little attention has been paid to the extraction of valuable ingredients from crude biomass. Facing these issues, we present our investigations towards the direct isolation of the active ingredients such as Shikimic acid, the major precursor for the antiviral drug Tamiflu®

, from biomass. We will not only discuss ionic liquids as alternative extraction media, but present the direct conversion of the active ingredient once dissolved in the ionic liquid to develop a novel and sustainable synthetic strategy towards the final drug.

I&EC 117

Amine-CO2: Tunable approach for ionic liquid supported biomass production and IL recovery

Dan Daly(1), dandaly@ua.edu, 720 2nd Street, Tuscaloosa Alabama, United States ; Robin Rogers(1); Ying Qin(1). (1) Innovation and Mentoring of Entrepreneurs, University of Alabama, Tuscaloosa Alabama 35405, United States

Ying Qin1, Robin Rogers2 and Dan Daly1* 1Alabama Institute for Manufacturing Excellence, The University of Alabama, Tuscaloosa, AL 35487, USA 2The Department of Chemistry, The University of Alabama, Tuscaloosa, AL 35487, USA Ionic liquids (ILs) represent a new-generation in chemistry, their numerous unique properties, making them suitable for various different applications. Even though ILs have found a number of industrial applications on biomass processing, the relatively high cost must be overcome to facilitate the application of the IL technologies into viable commercial process. We have developed a technology that changes the solubility of biomass in IL by introducing selected amines into the IL-biomass system. IL-amine has been used for reversible capture of CO2 based on the facts that some amines are soluble in ILs and the dissolved amine can react with CO2 to form amine-carbamate. We found several carbamates impede the hydrogen bonding between the anion of [C2mim]OAc and hydroxyl groups of cellulose, the solubility of cellulose in [C2mim]OAc therefore decreases and cellulose is then precipitated out of the mixture. In this

paper we will discuss in detail how this technology work on cellulose film/fiber production and how IL is recovered and reused.

I&EC 118

Legal pitfalls to starting a new chemical business: What Little Red Riding Hood should have been told before starting down the path to Grandma's house

Larry G. Canada(1), lcanada@gjtbs.com, 6471 General Haig Street, New Orleans Louisiana 70124, United States . (1) 525 Solutions, Inc., United States

Having a great product or idea is not always enough to guarantee a successful business. This discussion will center on issues that the new business owner should be aware of prior to making the decision to enter the business world. Taxes, IP rights, marketing, accounting and other essential areas will be discussed.

I&EC 119

Ionic liquids as active pharmaceutical ingredients (IL-APIs): The challenges of commercialization

Gabriela Gurau(1)(2), gurau001@as.ua.edu, 720, 2nd Street, AIME 204B, Tuscaloosa AL 35401, United States ; Robin D. Rogers(2). (1) 525 Solutions, Inc., Tuscaloosa AL 35401, United States (2) Department of Chemistry and Center for Green Manufacturing, The University of Alabama, Tuscaloosa AL 35401, United States

Even after two decades of intensive research, ionic liquids (ILs, broadly defined as salts that melt below 100 °C) are still underutilized to their full potential. Nowadays, the roles of ILs include quite diverse areas such as solvents, electrolytes, lubricants, thermal fluids, photovoltaics, etc. We have recently added another: IL forms of active pharmaceutical ingredients (APIs), where the true potential of pure liquid vs. solid forms of the APIs is not yet recognized. A crucial aspect in advancing our research to commercialization is recognizing those areas where direct collaboration with established industry is needed vs. those areas which lend themselves to entrepreneurial start-up companies. This presentation will discuss advances in the IL-API area from scientific, as well as business perspectives.

I&EC 120

Building a career in chemistry: The importance of undergraduate research

John R Canada(1), jrcanada@crimson.ua.edu, 250 Hackberry Lane, Tuscaloosa Alabama 35487, United States ; Parker D McCrary(1); Gabriela Gurau(1)(2); Robin D Rogers(1). (1) Department of Chemistry, Center for Green Manufacturing, University of Alabama, Tuscaloosa Alabama 35487, United States (2) 525 Solutions, Inc., Tuscaloosa Alabama 35487, United States

This presentation will discuss the positive effects of undergraduate research on a student's future from the perspective of a freshman. It will emphasize learning-centered skill sets and values that are essential for the research, but also carry over to the classroom and perhaps any future profession. The talk will be illustrated with the broad range of ionic liquids research undertaken by the undergraduate students in the Rogers Research Group and will encompass how team-centered activities build skill and confidence.

I&EC 121

Structure, solvation, and dynamics in N,N'-dialkylimidazolium ionic liquids: Insights from NMR experiments and molecular modeling

Guillermo Moyna(1)(2), g.moyna@usp.edu, 600 South 43rd Street, Philadelphia PA 19104, United States . (1) West Center for Computational Chemistry and Drug Discovery, University of the Sciences in Philadelphia, Philadelphia PA 19104, United States (2) Department of Chemistry & Biochemistry, University of the Sciences in Philadelphia, Philadelphia PA 19104, United States

NMR spectroscopy and molecular modeling are two of the most important tools available to study structure, solvation, and dynamics in ionic liquids (ILs) and IL based systems. Given their potential as media for the processing and analysis of biomass, this presentation showcases the application of some of these techniques to the investigation of N,N'-dialkylimidazolium ILs and their solutions. The use of 13C and 35/37Cl relaxation and 1H diffusion measurements together with molecular dynamics (MD) simulations in the study of the solvation of carbohydrates and lignols by imidazolium ILs is first described. The application similar methods and 1H and 35/37Cl chemical shift perturbations to the analysis of IL-solvent interactions is also presented. Finally, the study of hydrogen bonding in ILs through the measurement of deuterium isotope effects on 35/37Cl, 19F, 31P, and 11/10B NMR signals of selectively deuterated ILs is discussed.

I&EC 122

Ionic liquids and clean energy

Suojiang Zhang(1), sjzhang@home.ipe.ac.cn, Beier[apos]tiao No.1, Zhongguancun, Haidian, Beijing Beijing, China ; Xiaomin Liu(1). (1) Institute of Process Engineering, Chinese Academy of Sciences, China

Ionic liquids (ILs) are a new class of substance exclusively composed of cations and anions, and it is indispensible for us to study the structure-property relationships and the scale-up principles in the ILs systems. The physical property database has been estabilished and the variation law of ILs was discovered by scientifically classifying ILs and determining ionic segments. Hydrogen bond network structure is found. A series of force fields were developed. A set of novel equipment for in-situ measurement of the transport-reaction coupling performance was established. The dynamic characteristics, such as formation, deformation, coalescence and the movement of CO2 and air bubbles in ILs were directly observed. It is also found that when ILs are used for producing methyl methacrylate and ethylene glycol, it could reduce the environmental pollution, save large quantity of energy and significantly reduce wastewater discharge amount.

I&EC 123

Green engineering design: Combining the benefits of homogeneous and heterogeneous catalysis with tunable solvents

Rani Jha(1)(2)(3), ranijha25@gmail.com, 901 Atlantic Drive NW, Atlanta, Atlanta GA 30332, United States ; Ali Z. Fadhel(1)(2)(3); Wilmarie Medina-Ramos(1)(2)(3); Andy Wu(2); Pamela Pollet(1)(2)(3); Charles L. Liotta(1)(2)(3); Charles A. Eckert(1)(2)(3). (1) Department of Chemistry & Biochemistry, Georgia Institute of Technology, Atlanta GA 30332, United States (2) Department of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta GA 30332, United States (3) Department of Specialty Separations Center, Georgia Institute of Technology, Atlanta GA 30332, United States

We manipulate the phase behavior of homogeneous (monophasic) organic-aqueous mixtures with CO2 pressures to form heterogeneous biphasic liquid-liquid systems. The resulting biphasic system consists of an aqueous-rich phase and an organic-rich phase. The phase separation results from the difference of CO2 solubility between water and the organic solvent; CO2 is insoluble in water but is completely miscible with the majority of organics at moderate pressures (around 3 MPa). We are using these mixtures to carry out homogeneous reactions followed by CO2-induced heterogeneous separations. The model reaction for this work is the hydroformylation of p-methylstyrene catalyzed by a hydrophilic rhodium catalyst. We observe an order of magnitude improvement in the conversion rate of starting material and more than 30% improvement in the yield of the desired product. In addition, we were able to recycle the catalyst for five consecutive reactions without significant loss of catalytic activity.

I&EC 124

Process intensification with ultrasound

Artur Paulo(1), arturmcpaulo@gmail.com, Azurem, Guimaraes Minho 4800, Portugal . (1) Textiles, University of Minho, Guimaraes 4800, Portugal

Ultrasound is a well-known technique of process intensification. Ultrasound intensification is done by mass transfer enhancement and radical production as associated phenomena to cavitation. Low (20 kHZ) and high frequency (850 kHz)�ultrasound experimental set-ups are compared in the enhancement of chemical and enzymatic bleaching power as well on the preparation of emulsions formulations. Both high and low frequencies show a considerable enhancement on the bleaching power and stabilization of emulsions. A discussion on the major reasons for process intensification is done for all case studies presented.

I&EC 125

Dimcarb and ionic liquids as reactive solvents for the Kolbe-Schmitt synthesis

Anne Stark(1), annegret.stark@uni-jena.de, Lessingstr. 12, Jena Thuringia 07743, Germany ; Bernd Ondruschka(1); Dana Kralisch(1); Volker Hessel(2); Ulrich Krtschil(2); Sabine Huebschmann(1). (1) Institute for Technical Chemistry and Environmental Chemistry, Friedrich-Schiller University Jena, Jena 07743, Germany (2) Institut fuer Mikrotechnik Mainz GmbH, Mainz 55129, Germany

The Kolbe-Schmitt synthesis is one of the few industrially relevant reactions in which the relatively inert CO2 is exploited as a building block, conventionally by using aqueous KHCO3. However, high STYs in continuous processing are hampered by low solubilities of the reactants in water. Therefore, two novel reactive solvent systems were investigated: Dimcarb and carbonate-based ionic liquids (ILs). Compared to the ILs, the rate of reaction and equilibrium yield are lower when Dimcarb is used. However, a comparison of the performance over the whole life-cycle (assessed by simplified LCA) showed that the global warming and human toxicity potentials as well as the cumulative energy demand are reduced by 35-50% with Dimcarb. This contribution demonstrates the chemical and ecological optimization of both reactive solvent systems in continuous processing and compares them to the performance of aqueous KHCO3. The manufacture and application of higher dialkylamine-CO2-adducts is likewise discussed.

I&EC 126

Use of microwave heating in organometallic substitution reactions

Stacy A. O[apos]Reilly(1), soreilly@butler.edu, 4600 Sunset Avenue, Indianapolis IN 46208, United States ; Anne M. Wilson(1); Scott Wentz(1). (1) Department of Chemistry, Butler University, Indianapolis IN 46208, United States

Microwave assisted reaction methods have been used to reduce the time required for variety of organic reactions including some catalyzed by organometallic species. These same methods have had more limited application in the synthesis of organometallic compounds. This talk will discuss the benefits and limitations of using microwave heating for Group 6 carbonyl substitution reactions.

I&EC 127

Microwave-enhanced chemical processes

George D. Stefanidis(1), g.stefanidis@tudelft.nl, Leeghwaterstraat 44, Delft - 2628CA, The Netherlands. (1) [quot]Department of Process & Energy[quot], Delft University of Technology, Delft 2628CA, The Netherlands

In recent years, microwave heating has attracted significant academic and industrial attention as an alternative heat transfer mechanism for chemical reactions. Increased yields, better selectivities and product properties, shorter reaction times and energy savings are some of the benefits that have been reported in the literature for various microwave-activated chemical systems. This talk will present the highlights of our research activities on the application of microwave technology to a number of chemical processes including reactive distillation, polycondensation, adsorbents regeneration and steam reforming.

I&EC 128

Synthesis and evaluation of emulsifiers and corrosion inhibitors from an alkenylsuccinic anhydride

Ida Ettehadieh(1), wheelersan@hotmail.com, 3800 Montrose Blvd., Houston TX, United States ; Wheeler Crawford(1); Tammy Huynh(1). (1) Department of Chemistry and Physics, University of St. Thomas, Houston TX 77006, United States

Useful corrosion inhibitors and emulsifiers have been synthesized from a commercially available liquid, alpha-olefin-derived, C16-C18 alkenylsuccinic anhydride (ASA). The corrosion inhibitors were made by reaction of the ASA with two equivalents of a primary alkanolamine amine yielding an amic acid, or by conversion of the ASA to the diacid and neutralizing with a tertiary alkanolamine. The emulsifiers were made by reaction of the ASA with a polyethylene glycol followed by capping of the free carboxyl groups. Both types of compounds were tested and found to give excellent performance when compared with commercially available materials. The synthesis and evaluation will be discussed.

I&EC 129

Probing the adsorption of aminobiphenyl iomers using surface-enhanced Raman spectroscopy

Katrina A. Smith(1), kap3c@mtmail.mtsu.edu, P.O. Box 68, MTSU, Murfreesboro TN 37132, United States ; Ngee-Sing Chong(1); Kiran Donthula(1); Beng Guat Ooi(1). (1) Department of Chemistry, Middle Tennessee State University, Murfreesboro TN 37132, United States

Raman spectroscopy is capable of detecting aminobiphenyl (ABP) isomers at very low concentrations via surface–enhanced Raman scattering (SERS), in which the Raman signal is enhanced by the presence of silver nanoparticles that allow the adsorption of analytes. The shape and size of the silver nanoparticles play an important role in influencing the magnitude of the signal enhancement. Silver colloidal particles prepared under different centrifugation conditions have been characterized by transmission electron microscopy in order to correlate the physical characteristics of particles with the degree of Raman signal enhancement. The spectral differences of the Raman spectra of the neat ABP isomers versus their SERS spectra will be described with regard to the changes in the intensities, positions, and shapes of the peaks. The dependence of the adsorption characterisctics upon pH is also investigated.

I&EC 130

Production of FCCU light gas through a green plant energy design and inherently via a safe process

Sepehr Seyedi(1), john.galiotos@hccs.edu, 555 Community College Drive, Houston Texas 77013, United States ; Spiros Bamiatzis(1); John Galiotos(1). (1) Houston Community College-NE Energy Institute, United States

In the Plant design, the project includes a Solar Photovoltaic (PV) Park that provides part of the plant's energy demand and needs cfor consumption. Furthermore, an inherently safety system is used in the production of light gas, which includes: fire controls, inherent safe process, and equipment. Data associated with this effort reveals that PV power generation can benefit the overall plant operations.

I&EC 131

How can sustainable chemicals be integrated into a refinery? Specifically the integration of chemicals to minimize corrosion of piping

Ernest Paight(1), john.galiotos@hccs.edu, 555 Community College Drive, Houston Texas 77013, United States ; Chris Bedoya(1); Bankole ` Oni(1); John Galiotos(1). (1) Houston Community College-NE Energy Institute, United States

Typically, raw crude oil has little of no industrial value until it is sent through a refining process. A petroleum refinery takes the crude oil and refines it into more useful and valuable products, such as gasoline, diesel fuel, asphalt, and specialty chemicals for other chemical industries. Refineries are very large complex that run on a cost effective continuous basis. A significant problem to refineries efficiency is corrosion of the myriad of pipes running throughout the refinery. Corrosion is the degradation of material into its constituent atoms due to chemical reactions with the environment. Corrosion can cause pipe failure, clogging of pipe, and unpredictable costly cleaning schedules. The cost of corrosion in the petroleum industry has been estimated at 3.7 billion dollars annually, which include processing and water handling (1). It is therefore the purpose of this research identify and explore alternatives to develop cleaner, greener and safer chemicals which would be cost effective and also minimize corrosion in the pipes and these are expected to meet different quality standards.

I&EC 132

Isolation and characterization of secondary metabolites with antioxidant activity from Stereocaulon alpinum

Courtney J Meason(1), measonc@stthom.edu, 3800 Montrose Blvd., Houston TX 77006, United States ; Joanne G. Romagni(2); Juan Carlos G. Galindo(3). (1) Department of Chemistry and Physics, University of St. Thomas, Houston TX 77006, United States (2) Bucknell University, Lewisburg PA 17837, United States (3) Department of Organic Chemistry, University of Cadiz, Cadiz, Spain

S. alpinum is a lichen found in mountainous regions throughout the world. This lichen is comprised of a symbiosis between a fungus and a photobiont trebouxioid. It is normally found at high altitudes under adverse climatic conditions; in Antarctica, this lichen is also exposed to extreme conditions, especially UV radiation. During the campaigns 2005-2006 and 2006-2007 the Allelopathy Group of Cádiz obtained samples of S. alpinum at different locations and latitudes along the Antartic Peninsula and surrounding archipelagos. In accordance with current chemical ecological theories S. alpinum harvested from Antarctica should produce secondary metabolites in response to these environmental stressors. The main objectives of this project were to isolate, characterize and test the bioactivity of secondary metabolites extracted from S. alpinum. These secondary metabolites may be used in the future as biomarkers for environmental stress. Results of the project and the antioxidant activity determined from a bioautography bioassay using 2,2-diphenyl-1-picrylhydrazyl are presented.

I&EC 133

Students use pipeline flow automation software to simulate wastewater treatment plant

Tom L. Masney(1), john.galiotos@hccs.edu, 555 Community College Drive, Houston Texas 77013, United States ; Homer Stewart(1); John Galiotos(1). (1) Houston Community College-NE Energy Institute, United States

This project directly addresses the Construction of a Tank Farm that typically is found in an Oil & Gas Terminal. Students conducted a feasibility study of building a farm with 5 tanks of known volume, implementing a pipeline configuration that allows for different piping configurations that allow for individual or multiple tank lineup depending on product contained therein, or just conducting recycling for fiscalization and tank strapping procedures. This project has been approved by industry engineers, who are members of the program advisory committee. Among other technical results, this project reveals that students were better prepared to meet the needs of the local Oil & Gas, Chemical and Petrochemical Companies

I&EC 134

Modifying reaction conditions in the synthesis of Dibenzanthrone

Megan McConnell(1), diraddop@ferris.edu, 901 South State Street, Big Rapids MI 49307, United States ; Bill Killian(1); Pasquale Di Raddo(1); Gary Hiel(1); James Weaver(1). (1) Department of Physical Sciences, Ferris State University, Big Rapids MI 49307, United States

As part of their capstone laboratory experience for the associates degree in industrial chemistry technology, our students have been required to synthesize the beautiful dye compound dibenzanthrone (also named violanthrone). This two-week macroscale experiment involves an acid-promoted cyclization step to give benzanthrone, followed by dimerization to yield the polycyclic dye product. In this presentation we will discuss several modifications to this experiment which involve significantly scaling down the amounts of compounds used, purifying the benzanthrone made by sublimation as well as recrystallization and using greener acids such as polyphosphoric acid for the initial cyclization step. The results of these trials in terms of reaction yields obtained will be reported.

I&EC 135

Which feedstock gives the greatest ethanol yield?

Yolanda Sloan-Toliver(1), john.galiotos@hccs.edu, 555 Community College Drive, Houston Texas 77013, United States ; Homer Stewart(1); John Galiotos(1). (1) Houston Community College-NE Energy Institute, United States

This project explored which feedstock (sugar cane, apples, corn, or plums) gave the greatest yield of ethanol. Students conducted controlled experiments on different feedstock using a modified and engineered ethanol generation unit. The

methodology of production and concentration of each end product was evaluated and tested along with yields and quality controlled and assurance during each process.”

I&EC 136

Effects of water vapor on gas separation properties of MFI-type zeolite membranes

Jerry Y. S. Lin(1), Jerry.Lin@asu.edu, School for Engineering of Matter, Transport and Energy, Tempe AZ 85287, United States ; H B Wang(1); Jessica O’Brien(1). (1) Department of Chemical Engineering, Arizona State University, Tempe AZ 85287, United States

Microporous, thermally stable MFI-type zeolite membranes offer potential uses in membrane reactors at high temperatures for chemical reactions involving water vapor. The effects of the presence of the water vapor on gas permeation and separation properties of the zeolite membranes are important to the membrane reactor applications, but these have not been studied. In this work, the effects of H2O vapor on H2 and CO2 permeation through silicalite (high Si/Al ratio) and ZSM-5 (low Si/Al ratio) zeolite membranes was studied by comparing the permeation and separation properties of the zeolite membranes with H2/CO2/H2O ternary feed and H2/CO2 binary feed in 573-823 K. The presence of water vapor suppresses the permeation rate of both H2 and CO2. The suppression effect of water vapor on H2 and CO2 permeation through MFI-type zeolite membranes is stronger at lower temperatures and higher H2O vapor partial pressures. The hindrance of water vapor on H2 and CO2 permeation through the ZSM-5 membrane is stronger than that on H2 and CO2 permeation through the silicalite membrane due to the hydrophilic nature of the ZSM-5 zeolites. The H2/H2O permeance ratios for the permeation of equimolar H2/CO2/H2O ternary system through the silicalite membrane are found between 40 and 101 as temperature increased from 573 K to 823 K. While the H2/H2O permeance ratios for the permeation of equimolar H2/CO2/H2O ternary system through the ZSM-5 membrane are between 5.5 and 12.2 as temperature increases from 573 K to 823 K. The silicalite zeolite membranes with high H2/H2O permeance ratios may find applications in water electrolysis for hydrogen production at high temperatures.

I&EC 137

Membranes: From zeolites to polymers

Yushan Yan(1), Yushan.Yan@ucr.edu, Bourns Hall A235, Riverside CA 92521, United States . (1) Department of Chemical & Environmental Engineering, University of California, Riverside, Riverside CA 92521, United States

In celebrating Dr. Norman Li's seminal contributions to membrane science and technology, my presentation will focus on the membrane work that I have been involved in the past eighteen years. More specifically I will start with a very brief introduction of my PhD thesis work on polycrystalline zeolite membranes for gas separation, followed by a briefly description of our polymer-zeolite nanocomposite membranes for sea water desalination. I will spend most of my time discussing our most recent work on hydroxide exchange membrane (HEMs) for fuel cells (HEMFCs). In a HEMFC, it is possible to replace platinum catalysts with inexpensive non-platinum-group-metals such as nickel and silver and the most commonly used fluorinated Nafion membrane with a hydrocarbon membrane, thus drastically reducing their cost and thus making them economically viable. The HEMFCs can also expand the fuel source much beyond hydrogen and methanol. Toward the end of this presentation, I will discuss the potential application of HEMs for wind and solar electricity storage and solar hydrogen generation.

I&EC 138

Permeability upper bound predictions from transition state theory using the nonequilibrium lattice fluid model

Glenn Lipscomb(1), glenn.lipscomb@utoledo.edu, MS 305, 2801 Bancroft Street, Toledo OH 43606, United States ; Yuecun Lou(1); Maria Coleman(1). (1) Department of Chemical Engineering, The University of Toledo, Toledo OH 43606, United States

An upper bound on the permeability and permeability selectivity combination possessed by known polymeric materials confounds the development of industrial membrane gas separation processes. First reported in the literature by Robeson (Journal of Membrane Science, 62, 165-185, 1991, Journal of Membrane Science, 320 390-400, 2008), changes in primary and secondary chain architecture that increase permeability also tend to decrease permselectivity and vice versa. Freeman proposed a theoretical explanation for this upper bound (Macromolecules, 32, 375-380, 1999). The theory provides good estimates of the location of the upper bound but predicts all materials fall on this line, contrary to experiment, and fails to capture the dependence of transport on the identity of the specific chemical species present. Recently, we demonstrated how the non-equilibrium lattice fluid theory predicts the existence of an upper bound for solubility selectivity. The theory clearly captures how solubility and solubility selectivity depend on gas and polymer material properties. Moreover, it demonstrates how the upper bound arises from limitations on the maximum bulk modulus possessed by available polymeric materials. This theoretical analysis is used to predict diffusivity and diffusivity selectivity using transition state theory. Following the analysis of Gray-Weale et al. (Macromolecules, 30, 7296-7306, 1997), the energy change associated with forming the diffusion transition state is calculated using non-equilibrium lattice

fluid theory to provide the required material parameters. The results indicate an upper bound exists on diffusivity and diffusivity selectivity which when combined with the solubility upper bound provides an a priori prediction of the permeability upper bound.

I&EC 139

Insight into the growth of phase-separated domains during membrane formation

Da-Ming Wang(1), daming@ntu.edu.tw, No.1, Roosevelt Road sec. 4, Taipei Taiwan 10617, Taiwan Republic of China ; Juin-Yih Lai(2). (1) Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan Republic of China (2) R&D Center for Membranes, Chung Yuan University, Chung Li Taoyuan 32023, Taiwan Republic of China

In the presentation, two membrane formation systems are demonstrated to show that the growth of phase-separated domains needs to be considered to account for the final membrane morphology. They are preparation of polysulfone (an amorphous polymer) and polyvinylidene fluoride (PVDF, a semi-crystalline polymer) membranes by vapor-induced phase separation. For the preparation of polysulfone membranes, we will show that the domain growth can bring about a collapse of nascent interconnected pores into isolated cellular pores, and it determines the size of macrovoids when they occur. The underlying mechanism will be explained in terms of the competition between the rate of the domain growth and that of the gelation of polymer-rich phase. We will also demonstrate how we can alter the solvent-polymer interaction to change the competition, to inhibit the collapse of nascent interconnected pores and the growth of macrovoids. For the preparation of PVDF membranes, we will show how the crystallization-induced gelation interferes with the domain growth to determine the final membrane morphology. We will also present a method to prepare highly porous PVDF membranes with interconnected pores based on adjusting the rate of the crystallization-induced gelation. And, it will also be discussed how a PVDF membrane with superhydrophobic property can be prepared by properly balancing the rates of domain growth and polymer crystallization.

I&EC 140

CO2 capture/biofixation and lipid extraction by membrane contactors for enhancing microalgal cultivation

Huan Lin Chen(1), chenhl@zju.edu.cn, Engineering Research Center of Membrane & Water Treatment Technology, 38 Zheda Road, Hangzhou . 310027, China ; Fang Zhang(1); Li Hua Cheng(1); Lin Zhang(1). (1) Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China

Recent soaring oil prices and diminishing world oil reserves, coupled with the increased emission of greenhouse gases and the predicted threat of climate change, have generated renewed interest in using algae as an alternative and renewable feedstock for energy production. Aimed at intensifying microalgal CO2 fixation and lipid production enhancement, membrane contactors have been applied to capture CO2 from air, enhance microalgal cultivation and extract lipid from algae. In order to capture CO2 from air, three kinds of membrane contactors with absorption agents, Carbonic Anhydrase (CA)-hydrogel and ionic liquid, were designed. The photo-bioreactor integrated with a hollow-fiber membrane module to supply CO2 has been designed for Chlorella vulgaris cultivation. Using a membrane contactor, the residence time of CO2 in the photo-bioreactor can be prolonged to enhance CO2 biofixation. The biofixation rate has reached 0.38 g/(L·h), which is more than 2 – 3 times those in conventional reactors. In order to increase lipid productivity, the effects of cultivation conditions, including KNO3-level, CO2 concentration and irradiance, on the cell growth, chlorophyll content and lipid accumulation of Chlorella vulgaris are systematically investigated. The lipid productivity has reached 40 mg/(L·d) under select cultivated conditions, which is more than 2.5-fold of that reported. Finally, to simplify the algal lipid production process and thus to reduce costs, microalgal lipid extracted in situ and continuously produced in the bioreactor integrated with membrane-based extraction has been investigated in this study.

I&EC 141

Ionic liquids vs. liquid clathrates

Jerry L. Atwood(1), atwoodj@missouri.edu, 601 S. College Avenue, Room 125, Columbia MO 65211, United States . (1) Department of Chemistry, University of Missouri-Columbia, Columbia MO 65211, United States

There exists a class of ionic liquids in which the ionic liquid consists of a salt and an aromatic solvent. This discussion will focus on the answer to the question: Are liquid clathrates a subset of ionic liquids or are ionic liquids a subset of liquid clathrates? Ionic liquids will be placed in historical context.

I&EC 142

Metal-organic material platforms for small molecule separations and ion exchange

Michael J. Zaworotko(1), xtal@usf.edu, CHE205, 4202 E. Fowler Avenue, Tampa Florida 33620, United States ; Patrick Nugent(1); Padmini Kavuru(1); Tien T. Ong(1); Jason A. Perman(1). (1) Chemistry, University of South Florida, Tampa Florida 33620, United States

Metal-Organic Materials, MOMs, are a class of materials comprised of metals or metal clusters (i.e. the “node”) coordinated to multi-functional organic ligands (i.e. the “linker”). It has been realized that MOMs offer unprecedented levels of permanent porosity in the context of crystalline materials and their modular nature offers an enormous diversity of structures and properties. For example, the pore environment in a MOM can be modified to optimize interactions with a target adsorbate whereas the geometry and dimensions of the linker and the coordination geometry of the node imparts control over the resulting connectivity and scale of the material. In this contribution we will address principles of MOM design with particular emphasis upon which MOMs can be regarded as platforms that can be optimized for small molecule separation and ion exchange.

I&EC 143

Crystallization of ionic liquids

Anja V Mudring(1), anja.mudring@rub.de, NCDF 04/398, Bochum NRW 44780, Germany . (1) Anorganische Chemie I - Festkoerperchemie und Materialien, Ruhr-Universitaet Bochum, Bochum NRW 44780, Germany

Ionic liquids (ILs) have lately become an important class of solvents and soft materials. Despite being salts built by discrete cations and anions, many of them are liquid at room temperature and below. ILs have been used in a wide variety of applications and it has been realized that the true advantage of ILs is their modular character. Each specific cation–anion combination is characterized by a unique, characteristic set of properties. Although ILs have been known for roughly a century, still a vast number of possible ion combinations has to be exploited and one fundamental question remains inadequately answered: why do ILs have such a low melting point and do not crystallize readily? Practical techniques, strategies and methods for crystallization of ionic liquids will be discussed and the formation of ideal crystals but also of plastic crystals and liquid crystals by ionic liquid compounds will be discussed.

I&EC 144

Research and development of energetic ionic liquids

Tom Hawkins(1), tommy.hawkins@edwards.af.mil, AFRL/RZSP, 10 East Saturn Blvd, Edwards AFB CA 93536-7680, United States ; Adam Brand(1); Milton McKay(1); Michael Tinnirello(1). (1) Space & Missile Propulsion Sciences, US Air Force Research Laboratory, Edwards AFB CA 93536-7680, United States

Current research programs are aiming to develop ionic liquids (ILs) as energetic materials for various applications. Such applications for ILs include both propulsion and explosives. Within the propulsion arena, a focus is to replace hydrazine (a highly toxic compound) as a fuel. The approach to replacing

hydrazine is the synthesis and development of ILs with substantially less vapor toxicity and superior energy density. Hazardous characteristics, undesirable physical and chemical properties of such ILs must be identified before further development by a potential user. IL-based fuels and their properties will be discussed (including limited safety and sensitivity, and thermophysical properties). In the development of advanced explosives, an effort is underway to produce material replacements for 2,4,6-trinitrotoluene (TNT). Energetic ILs have been synthesized and characterized as explosive ingredients. Physical and chemical property characterizations and initial performance evaluations of these molecules indicates ionic liquids are a promising material approach to high performance explosives.

I&EC 145

Ionic liquid gas absorption of pollutants in flue gases

Rasmus Fehrmann(1), rf@kemi.dtu.dk, Department of Chemistry, Kgs. Lyngby DK-2800, Denmark ; Johannes Due-Hansen(1); Søren Kegnæs(1); Anita Godiksen(1); Anders Riisager(1). (1) Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, Kgs. Lyngby DK-2800, Denmark

Combustion of fossil fuels during energy production generates pollutants in the flue gases which have to be effectively removed to avoid emission. In this work, we demonstrate how ionic liquids (ILs) can be tuned by design to perform as selective, high-capacity absorbents of environmentally problematic gases like, e.g. SO2 and in a pioneering project also for NO. Reversible absorption performance has been tested for several different ILs at different temperatures, pressures and flue gas compositions. Furthermore, different porous, high surface area carriers have been applied as supports for the ILs to obtain Supported Ionic Liquid-Phase (SILP) absorber materials. The use of solid SILP absorbers with selected ILs were found to significantly improve the absorption capacity and sorption dynamics at low flue gas concentration, thus making the applicability of ILs viable in temperature or pressure swing processes eventually turning the pollutants to useful mineral acids by separate catalytic conversion.

I&EC 146

Separate, store, retrieve: Designing ionic liquids for the manipulation of gases and highly volatile liquids

James H. Davis(1), jdavis@jaguar1.usouthal.edu, Chemistry Bldg. Room 223, Mobile Alabama 36688, United States ; Kevin N West(2). (1) Departments of Chemistry and Chemical & Biomolecular Engineering, University of South Alabama, Mobile Alabama 36688, United States (2) Department of Chemical and

Biomolecular Engineering, University of South Alabama, Mobile Alabama 36688, United States

Over the past decade, the interaction of gases with ionic liquids has emerged as a subject of considerable practical significance. Early on, studies on IL-gas interactions were commonly limited to measurements of Henry's constants, since the basis for IL-gas interactions were generally physicochemical in nature. This changed, however, as the capture and sequestration of CO2 emerged as a global socio-political objective and ILs were introduced that are capable of chemically reacting with this gas. We will discuss our role in the development of CO2 reactive ILs, and how we have now come full circle to develop new ILs with enhanced capacities for the physical solvation of select gases and highly volatile liquids.

I&EC 147

Toughest separations task of them all: Separating robin from his red jacket

Kenneth R Seddon(1), k.seddon@qub.ac.uk, David Keir Building, Stranmillis Road, Belfast Co Antrim BT9 5AG, United Kingdom . (1) Quill Research Centre, Queen[apos]s University, Belfast BT9 5AG, United Kingdom

The title says it all.

I&EC 148

Award Address (ACS Award in Separations Science and Technology sponsored by Waters Corporation). Ionic liquids from there to here

Robin D. Rogers(1), rdrogers@as.ua.edu, Box 870336, Tuscaloosa AL 35487, United States . (1) Department of Chemistry and Center for Green Manufacturing, The University of Alabama, Tuscaloosa AL 35487, United States

Over the last fifteen years, one aspect of the Rogers' Group research has focused on ionic liquids (ILs), investigating both the application, and fundamental understanding, of how ILs can be used as separations media. This research has included advances in their preparation and studies on toxicity through applications in reaction and separations processes for organic molecules, radionuclides, metal cations and complexes and biomolecules, to the development of IL energetic materials and active pharmaceutical agents. However, the story of this work would not be complete without discussion of its roots in undergraduate and graduate research projects on liquid clathrates with Jerry Atwood at The University of Alabama, its manifestation into liquid separations in faculty sabbatical research in radiochemistry and separations with Phil Horwitz at Argonne National Laboratory, its re-emergence with the IL

phenomenon developed in collaboration with Ken Seddon of Queen's University of Belfast, and the many students and collaborators.

I&EC 149

Study of the oxidation reaction of benzyl alcohol to benzaldehyde in multiphase membrane reactor

Maria Giovanna Buonomenna(1), mg.buonomenna@itm.cnr.it, via P.Bucci, Rende (CS) Italy 87030, Italy ; Giovanni Golemme(1)(2); Enrico Drioli(1)(2). (1) Department of Chemical Engineering and materials, Univeristy of Calabria, Rende (CS) Italy 87030, Italy (2) ITM-CNR, Rende (CS) Italy 87030, Italy

Green technologies in the synthesis of fine chemicals and pharmaceuticals intermediates require the highest possible selectivity, minimal production of byproducts, wastes and separation costs. In this work, we report a novel method for selective oxidation of benzyl alcohol to benzaldehyde. Neither solvent nor promoters are needed: a polymeric microporous membrane acts as a barrier to “keep in contact” the two phases: the organic phase containing the substrate and benzaldehyde, and the aqueous phase with the oxidant, H2O2, are kept apart with no mix of them and dispersion phenomena. This system showed a high selectivity to benzaldehyde (>98%), minimizing over-oxidation in over-oxygenated by-products. The effect of axial flow velocity, reaction temperature, type of membrane was investigated. Membranes based on hydrophobic polymers were used as membrane contactors. The influence on the reaction conversion and extraction capability by the membrane in the organic compartment of the product benzaldehyde has been investigated.

I&EC 150

Novel Process Windows and superheated processing at model reactions

Volker Hessel(1)(2), hessel@imm-mainz.de, Carl-Zeiss-Str. 18-20, Mainz Rhineland-Palatinate, Germany ; Ulrich Krtschil(2); Patrick Löb(2); Sonja Rothstock(2); Ramon Canela(3); Marc Escribà(3); Mart de Croon(1); Bruno Cortese(1). (1) Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven 5612 AZ, The Netherlands (2) Institut für Mikrotechnik Mainz GmbH, Eindhoven 5612 AZ, The Netherlands (3) Department of Chemistry, University of Lleida, ETSEA, Lleida 191 25198, Spain

Using novel process windows is one possibility to achieve process intensification. Superheated processing of the aqueous Kolbe-Schmitt synthesis of 2,4-dihydroxybenzoic acid from resorcinol led to drastically reduced reaction times, affiliated with the suppression of by-product formation from up to 15 % to less than 1 % at a nearly constant yield. A 25-fold productivity improvement up to 225 g/h was achieved by applying an electrically heated microstructured device

and maintaining the advantages of small capillaries. More powerful reagents as compared to conventionally used KHCO3 (aq). are reactive ionic liquids. The best yield could considerably be increased by 12 % using 1-butyl-3-methyl-imidazolium. For the synthesis of 3-chloro-2-hydroxypropyl pivaloate the reaction time could also be decreased (240-fold) compared to batch processing. Similarly as for the Kolbe-Schmitt synthesis the yield of the consecutive formation of a by-product could be reduced here. Results of generic modelling to NPW effects will round the picture.

I&EC 151

Novel process windows and superheated processing: Toward sustainable chemistry

Dana Kralisch(1), dana.kralisch@uni-jena.de, Lessingstr. 12, Jena Thuringia 07743, Germany ; Sabine Huebschmann(1); Volker Hessel(2); Ulrich Krtschil(2). (1) Institute of Technical Chemistry and Environmental Chemistry, Friedrich-Schiller-University Jena, Jena Thuringia 07743, Germany (2) Institut für Mikrotechnik Mainz GmbH, Mainz Hessen, Germany

Microreaction technology has turned out to be a suitable tool to improve conventional chemical engineering, but it has to come off with significant benefits, e.g., in yield, selectivity, heat management, safety and / or production costs, to become a sustainable alternative. Currently, process intensification by microprocess technology is proven under rigorous reaction conditions for several applications. Due to the improvements obtained in synthesis performance, a positive effect on environmental impacts is expected. But, harsh process conditions probably require added energy input and effort concerning process control and safety. The question whether the ratio of effort and benefit is less than for alternative approaches or not has been addressed by (Simplified) Life Cycle Assessment. Results will be discussed on the example of superheated processing of the aqueous Kolbe-Schmitt synthesis and current processes investigated within the collaborative EU project COPIRIDE.

I&EC 152

(S)-2,3-dihydro-indole-2-carboxylic acid: Catalytic process concepts enabling sustainable manufacturing route

Quirinus B. Broxterman(1), rinus.broxterman@dsm.com, P.O. Box 18, Geleen - 6160 MD, The Netherlands. (1) DSM Innovative Synthesis B.V., Geleen 6160 MD, The Netherlands

(S)-2,3-dihydro-indole-2-carboxylic acid is an enantiopure unnatural amino acid used as an advanced pharmaceutical intermediate. It has been manufactured in classical, stoichiometric 7 step process. In a route scouting project a 3 step

catalytic process was identified. A homogeneous metal catalyzed as well as a biocatalytic step were developed for the 2 last key steps. This process was then scaled up. In parallel a number of parameters measuring the 'sustainability' of the process were determined (PMI, C-footprint, Eco-footprint etc) These sustainability parameters will be shown and explained, and are found to be consistently better for the catalytic process as compared to the stoichiometric process. This is one of the first examples brought to the public domain where this correlation is shown and explained explicitly.

I&EC 153

Viedma ripening: Attrition enhanced complete deracemization

Hugo Meekes(1), H.Meekes@science.ru.nl, Heyendaalseweg 135, Nijmegen Gld. 6525AJ, The Netherlands; Wim L. Noorduin(1); Bernard Kaptein(2); Richard M. Kellogg(3); Geert Deroover(4); Willem J.P. van Enckevort(1); Elias Vlieg(1). (1) Institute for Molecules and Materials, Radboud University Nijmegen, Nijmegen Heyendaalseweg 135, 6525AJ, The Netherlands (2) DSM Innovative Synthesis BV, Geleen PO Box 18, 6160MD, The Netherlands (3) Syncom BV, Groningen Kadijk 3, 9747AT, The Netherlands (4) Agfa-Gevaert NV, Mortsel Septestraat 27, B-2640, Belgium

Routes to enantiomerically pure compounds are of paramount importance, especially for many pharmaceutical products. Recently we developed a technique, based on seminal work by Viedma, to deracemize a racemic mixture of a chiral compound by grinding the crystals in contact with a saturated solution in which racemization oc-curs, leading to an enantiomeric excess of 100 % and a quantitative yield in the solid phase. The term Viedma ripening was introduced for the method, which can be easily scaled up using industrial mills. The mechanism behind this process is the competition between crystal growth as a result of Ostwald ripening and secondary nucleation due to abrasive grinding in the slurry. The details of this competition, however, are still subject of discussion. Besides an overview of the surprising experimental results obtained, a Monte Carlo study of the process will be presented that has led to an optimization of the practical deracemization time.

I&EC 154

In-line monitoring for the accurate control of segmented flow processes

Catherine F Carter(1), cc541@cam.ac.uk, Lensfield Road, Cambridge Cambridgeshire CB2 1EW, United Kingdom ; Steven V Ley(1). (1) Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom

IN-LINE MONITORING FOR THE ACCURATE CONTROL OF SEGMENTED FLOW PROCESSES Catherine F. Carter and Steven V. Ley Department of

Chemistry, University of Cambridge, Lensfield Road, Cambridge, UK Flow chemistry and other machine-assisted processing techniques are continuing to make an impact upon organic synthesis. As the technology advances, more methods and techniques for in-line monitoring are required to gain control over multi-step sequences. Both UV and IR detection have been used in-line to measure dispersion, monitor reactive intermediates and elucidate mechanisms.1 It has also been possible to telescope reaction processes with in-line IR control, using the live data from the detector to control a third pump and perform a second reaction in a controlled and precise fashion.

References 1 C.F. Carter, H. Lange, I.R. Baxendale, S.V. Ley, J. Goode, N. Gaunt, B. Wittkamp, Org. Process Res. Dev. 2010, 14, 393-404.

I&EC 155

Nanofiber composite fuel cell membranes

Peter Pintauro(1), peter.pintauro@vanderbilt.edu, PMB 351604, 2301 Vanderbilt Place, Nashville Tennessee 37235, United States ; Jason Ballengee(1); Andrew Park(1). (1) Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville Tennessee 37235, United States

Proton conducting membranes for hydrogen/air fuel cells and hydroxyl ion conducting membranes for alkaline fuel cells must meet stringent performance standards in terms of high ionic conductivity, controlled swelling, and thermal/mechanical/chemical stability. The most obvious way to achieve high conductivity is to increase the concentration of membrane fixed-charge sites, but this approach leads to problems with membrane dimensional/mechanical stability (the polymer swells excessively when wet and is brittle when dry). An entirely new approach for fabricating membranes has been developed recently by Pintauro and co-workers, based on polymer nanofiber electrospinning and forced assembly. In this talk, methods for fabricating nanofiber-based proton conducting and hydroxyl ion conducting fuel cell membranes will be described and membrane properties will be presented. For proton conducing membranes, H2/air fuel cell performance and durability results will be contrasted with data collected with a commercial Nafion® membrane.

I&EC 156

Electrochemically-mediated separation processes

T. Alan Hatton(1), tahatton@MIT.EDU, 77 Massachusetts Avenue, Cambridge MA 02139, United States ; Fritz Simeon(1); Mike Stern(1); Abhinav Akhoury(1);

Howard Herzog(1). (1) Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge MA 02139, United States

The efficient separation of products from the milieux in which they are produced during traditional chemical processing is a problem facing all sectors of the chemical and biochemical industries, and is a particularly acute problem in environmental remediation and control. The range of separation processes that have been developed to meet these needs is wide, and includes extraction, absorption, adsorption, distillation, filtration and crystallization. In recent years, there has also been a burgeoning interest in micro-scale separations for the purification of products from micro-reactors used in, e.g., combinatorial chemistry, and for the pre-treatment of compounds to be analysed in micro-scale total analysis systems. In all cases there is a need for high specificity and capacity of the separations process, and for the efficient regeneration of the separation aids and recovery of the solutes. Electrochemically-mediated processes can, in principle, meet these needs in both large- and small-scale operations, provided inherent transport limitations, ohmic losses and unwanted electrochemical side reactions can be minimized. Two such processes will be discussed: (i) butanol extraction from aqueous solution using redox-responsive gels to mediate product inhibition in fermentation systems, and (ii) CO2 capture from dilute gas mixtures by exploiting the significant changes in molecular affinity of certain sorbents for CO2 molecules as they undergo redox cycles. Such processes have the potential for reducing the parasitic energy of the current solvent-based extraction and absorption processes since they do not require significant temperature swings to regenerate the sorbents. Molecular optimization of the redox sorbents is required to enhance their chemical stability, and implementation requires efficient electron transfer operations for rapid redox switching. We conclude with a discussion of the general concepts and the advances needed in both the chemistry and the technology for their successful implementation as chemical separation process technologies of the future.

I&EC 157

Responsive membranes for water treatment

S. Ranil Wickramasinghe(1), wickram@engr.colostate.edu, 1370 Campus Delivery, Fort Collins CO 80523, United States ; Heath H. Himstedt(1); Mathais Ulbricht(2); Xianghong Qian(3). (1) Department of Chemical and Biological Engineering, Colorado State University, Fort Collins CO 80523, United States (2) Lehrstuhl für Technische Chemie II, Universität Duisburg-Essen, Essen 45117, Germany (3) Department of Mechanical Engineering, Colorado State University, Fort Collins CO 80523, United States

Numerous membrane processes such as reverse osmosis, nanofiltration, ultrafiltration, microfiltration and membrane distillation find applications in water treatment. Membrane processes often require far less energy than alternative

unit operation, making them particularly attractive for water treatment applications. Unfortunately, membrane fouling often limits the use of membrane separations for water treatment. Development of advanced antifouling membranes will be essential if the potential for low energy membrane separations is to be realized for water treatment. Our research focuses on the development of new multifunctional membranes, i.e., membranes that carry out two or more functions cooperatively to achieve desired per formance. Here results will be presented for surface modification of commercially available nanofiltration membranes in order to render them responsive to an oscillating magnetic field. Commercially available nanofiltration membranes (NF 270) have been modified using atom transfer radical polymerization to grow poly(2-hydroxyethyl methacrylate) chains from the surface of the membrane. Next a Gabriel synthesis reaction was used to convert the alkyl halide end group of the polymer chains to primary amines. Carboxylic acid coated iron oxide nanoparticles were then attached to the chain ends through an amide linkage. Movement of the magnetically responsive brushes has been visualized using particle image velocimetry. In an oscillating magnetic field, the magnetic nanoparticles attached to the polymer chain ends move like the cilia of microorganisms which induces mixing at the membrane-fluid interface at low Reynolds number. Our data indicate that this motion is sufficient to cause mixing up to a distance of 0.5 mm from the membrane surface. Dead end filtration experiments have been conducted using feed streams consisting of MgSO4 and CaCl2. Our results indicate improved fluxes and rejection for modified membranes in the presence of an oscillating magnetic field. Further, the movement of the polymer chains induces mixing at low Reynolds number and suppressing fouling.

I&EC 158

Facilitated transport membranes for energy and biochemical applications

W.S. Winston Ho(1), ho@chbmeng.ohio-state.edu, 2041 College Road, Columbus OH 43210-1178, United States ; Kartik Ramasubramanian(1); Michael E. Vilt(1); Yanan Zhao(1). (1) William G. Lowrie Department of Chemical and Biomolecular Engineering and Department of Materials Science and Engineering, The Ohio State University, Columbus OH 43210-1180, United States

This presentation covers recent advances in facilitated transport membranes in two areas: (1) fuel processing with carbon dioxide-selective membranes for fuel cells and (2) the extraction and recovery of antibiotics from aqueous solutions by supported liquid membranes (SLMs) with strip dispersion. We have synthesized carbon dioxide-selective membranes by incorporating amino groups into polymer networks for hydrogen purification for fuel cells. The membranes have shown high carbon dioxide permeability and selectivity vs. hydrogen, carbon monoxide and nitrogen up to 180oC. Hydrogen sulfide permeates through the membrane much faster than carbon dioxide. This allows the removal of hydrogen sulfide in

the treated synthesis gas before water-gas-shift (WGS) reaction. Our initial experiments have shown a nearly complete removal of hydrogen sulfide from 50 ppm in syngas to about 10 ppb in the hydrogen product. Using the membrane, we have obtained <10 ppm carbon monoxide in the hydrogen product in WGS membrane reactor experiments via carbon dioxide removal. The data have been in good agreement with our modeling prediction. We also removed carbon dioxide from a syngas containing 17% carbon dioxide to <30 ppm and obtained >98% carbon dioxide in the acid gas stream for sequestration. On SLMs, their stability has been ensured by a modified SLM with strip dispersion, where the aqueous strip solution is dispersed in the organic membrane solution. The SLMs with strip dispersion have potential for extraction and recovery of antibiotics and biochemicals from fermentation broths and aqueous solutions. For example, Cephalexin has been extracted and concentrated significantly with a very high recovery; typical results have shown > 99% extraction and high recovery rates of 96 – 98%. A mass transfer analysis has shown that the resistance from the extraction reaction is dominant. Initial results from 4-component feed mixtures have shown selective Cephalexin recovery possible.

I&EC 159

Continuous flow processing of inorganic materials

Steven L. Suib(1), Steven.Suib@uconn.edu, Unit 3060, 55 N. Eagleville Rd., Storrs CT 06269-3060, United States ; Naftali Opembe(1). (1) Chemistry, The University of Connecticut, Storrs CT 06269-3060, United States

Continuous flow methods have been developed for the synthesis of various nano-size inorganic materials. Porous octahedral molecular sieve (OMS) nanomaterials have been made via continuous flow microwave activation in a mixed aqueous-organic solvent system. Multi-kilogram amounts of nanomaterials can be made with such methods. Other materials like mixed metal oxides, metal oxides, and supported metal oxides have been made with similar methods. Besides microwave activation, photolysis, ultrasonic activation, and thermal activation methods can be used to produce materials with different properties. Several characterization methods like X-ray diffraction (XRD), electron microscopy (SEM and TEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), nitrogen sorption experiments, and potentiometric titrations have been used to characterize these nanomaterials. Applications of such materials include adsorption, catalysis, sensors, batteries, and others.

I&EC 160

Continuous flow chemistry in supercritical fluids

Richard A Bourne(1), richard.bourne@nottingham.ac.uk, University Park, Nottingham Nottinghamshire NG7 2RD, United Kingdom ; Michael W George(1); Martyn Poliakoff(1). (1) School of Chemistry, University of Nottingham, Nottingham NG7 2RD, United Kingdom

Within the framework of Green Chemistry, there is considerable interest in replacing conventional solvents with environmentally more acceptable solvents. Supercritical fluids such as scCO2 offer potentially important processing advantages as well as being totally non-toxic and non-flammable. These advantages include lower viscosity and enhanced diffusivity as well as total miscibility with permanent gases such as H2 and O2. This lecture will focus on some of our recent work at Nottingham with scCO2 including photocatalytic oxidations, real-time product switching and self-optimising reactor systems. The photocatalytic oxidation research is particularly appealing from the perspective of Green Chemistry since, both atoms of the O2 molecule are incorporated into the reaction product without any waste. The advantages of scCO2 in this context are similar to those for other oxidation reactions and due to the removal of mass transfer limitations an increase in space-time yield of ca. two orders of magnitude can be achieved.

I&EC 161

Microwave-assisted polycondensation: Development of the first commercial plant for lactic acid polymerization

Kazuhiko Takeuchi(1), takeuchi-kazuhiko@aist.go.jp, AIST Tsukuba Central 5, Higashi 1-1-1, Tsukuba Ibaraki 305-8565, Japan ; Ritsuko Nagahata(1); Takashi Nakamura(1); Yukie Mori(1); Katsuyuki Kunii(2); Hirofumi Soga(2); Shoji Sugimoto(2). (1) National Institute of Advanced Industrial Science and Technology, Tsukuba Ibaraki 305-8565, Japan (2) Shikoku Instrumentation Co., Ltd., Takamatsu Kagawa 761-0301, Japan

Chemical processes assisted by microwave (MW) heating are attractive energy-saving processes. We applied MW heating to the polycondensation of lactic acid, which conventionally is known as a high-energy-consuming process. We herein studied the MW-assisted reaction at scales ranging from several tens of milliliters to several tens of liters; SMW-087 (volume of the reaction vessel: 70 ml, max. MW power: 700 W), SMW-101 (300 ml, 1.5 kW), and SMW-114 (30 l, 6.0 kW). Poly(lactic acid) polymers with average molecular weights (Mw) of 18,000 were obtained. Analysis of the consumed MW power also showed that the energy used by the polycondensation per mole of substrate was saved by scaling up the reaction. In 2009, we developed and put a new MW synthesis reactor designed based on SMW–114 with a 6.0 kW magnetron of 2.45 GHz and a 37 l glass vessel to ptactical use for polycondensation of LA.

I&EC 162

Approaches to the scale-up of microwave-assisted organic synthesis

Nicholas E Leadbeater(1), nicholas.leadbeater@uconn.edu, 55 North Eagleville Road, Storrs CT 06269, United States . (1) Department of Chemistry, University of Connecticut, Storrs CT 06269, United States

Microwave heating is a tool that is widely usedfor small-scale synthesis. For it to be a technology that is useful from an industrial standpoint, the methodologies developed on a small-scale need to be able to be scaled up to make more significant quantities of material. The objective of this presentation is to show how this can be achievedby means of some case studies from our laboratory. Our work will be placed in context with other reports in the area.

I&EC 163

Intensified processes from laboratory to production using novel micro structured reactors

Samrat Mukherjee(1), samrat.mukherjee@bayer.com, 8500 W Bay Road, MS 52, Baytown Texas, United States ; Bharat Marwaha(1); Maria Krusche(2); Frank Schael(2). (1) Bayer Technology Services, Bayer Business and Technology Services, LLC, Baytown Texas, United States (2) Ehrfeld Mikrotechnik BTS GmbH, Wendelsheim, Germany

Ehrfeld Mikrotechnik BTS GmbH has developed micro and milli structured reactor systems that achieve the advantages of process intensification, but in addition provide an easy route to scale-up. These systems also retain the flexibility found in batch production units. The Ehrfeld microreactor system effectively employs the strategy of equaling up (see attached figure). Process development can be done efficiently and quickly in the laboratory scale unit. At the point of scale-up a module with more channels is employed. Identical process results are assured in the pilot and production stage as the physical condition in each channel is still the same. In the pharmaceutical and fine chemical industries, Ehrfeld microreactors are playing an increasingly important role in research, development and production because of its decisive advantages over conventional technology

The presentation will introduce microreactors, discuss their advantages and limitations, present the Ehrfeld microreactor system and share examples of its application.

I&EC 164

Novel high free-volume membranes based on poly(bis-SiMe3-tricyclononene) for the pervaporation of ethanol/water mixtures

Maria Giovanna Buonomenna(1), mg.buonomenna@itm.cnr.it, via P.Bucci, Rende (CS) CS 87030, Italy ; M.V. Bermeshev(2); Alberto Figoli(3); Francesco Galiano(3); Giovanni Golemme(1). (1) Department of Chemical Engineering and materials, University of calabria, Rende CS 87030, Italy (2) Topchiev Institute of Petrochemical Synthesis, Moscow 119991, Russian Federation (3) ITM-CNR, Rende (CS) 87030, Italy

Pervaporation (PV) demonstrates unique advantages over conventional techniques in separating heat-sensitive, close-boiling azeotropic and isomer mixtures. A typical application of organophilic PV is the treatment of fermentative production of bio-alcohols. Removal of the ethanol from the fermentation broth through selective PV membrane represents an effective solution to overcome product inhibition and to shift the production from a batch to a semi-continuous process. In the present work, membranes based on a novel polymer, i.e. poly(bis-SiMe3-tricyclononene) (Ad-PTCN-2Si) are for the first time used for the ethanol/water PV. The highest ethanol selectivity was observed at the ethanol concentration of 5% (a=4.92) with a permeability of 9.0 mm kg/h m2. These values are interesting if compared with those reported in literature for pure and/or mixed matrix membranes based on PDMS [1]. References [1] L.M. Vane et al, J. Membr. Sci, 308 (2008) 230 Acknowledgements This work was supported by 7th Framework Programme (Project NMP3-SL-2009-228631)

I&EC 165

Controlling selectivity to primary amines in the Pd catalyzed liquid-phase hydrogenation of multi-functional aromatic nitriles: Hydroxybenzyl cyanide as a model compound for the agrichemicals industry

Liam McMillan(1), liammc@chem.gla.ac.uk, C4-14 Joseph Black Building, University Avenue, Glasgow Lanarkshire G12 8QQ, United Kingdom ; David Lennon(1); Colin Brennan(2). (1) School of Chemistry, University of Glasgow, Glasgow G12 8QQ, United Kingdom (2) Process Studies Group, Jealott[apos]s Hill Reseacrh Centre, Syngenta, Bracknell Berkshire RG42 6EY, United Kingdom

The hydrogenation of hydroxybenzyl cyanide (p-OH-C6H4CH2CN) over a Pd/C catalyst to produce tyramine (p-OH-C6H4CH2CH2NH2) via an imine intermediate (p-OH-C6H4CH2CH=NH) is a reaction of generic interest in the agrichemicals

industry. This presentation will demonstrate how an awareness of reagent and product interactions with the catalyst surface can be used to optimise selectivity and minimise catalyst deactivation issues.

I&EC 166

New technologies in chemical scale-up: The application of microwaves and flow reactors in a kilolab

Hansjoerg Lehmann(1), hansjoerg.lehmann@novartis.com, Klybeckstrasse 191, CH-4002 Basel --, Switzerland . (1) Novartis Institutes for BioMedical Research, Novartis Pharma AG, CH-4002 Basel 4002, Switzerland

Microwave-assisted heating has proven to be ideal for small scale applications in drug discovery and has become an invaluable technology for medicinal chemistry. The routinely use of microwave reactors on small scale created an increasing demand to use this technology also on larger scale and led to the implementation this technology into our early scale-up process. Based on our experience, the impact of using microwaves in the scale-up process will be illustrated by various examples and some case-studies. Several examples of reaction optimization and scale-up to multi-hundred gram scale will be presented in detail. A second part of the presentation will illustrate how continuous flow chemistry was applied and integrated into our scale-up process. Various case studies will focus on the adaption of hazardous nitrations to flow conditions which could not be scaled-up in batch due to severe safety issues or problems with selectivity.

I&EC 167

Making diazomethane accessible for R&D and industry: Production of the diazomethane precursor N-methyl-N-nitroso-p-toluenesulfonamide (Diazald) and direct conversion in a continuous micro-reactor set-up

Anne Stark(1), annegret.stark@uni-jena.de, Lessingstr. 12, Jena Thuringia 07743, Germany ; Michael Struempel(1); Bernd Ondruschka(1). (1) Institute for

Technical Chemistry and Environmental Chemistry, Friedrich-Schiller University Jena, Jena 07743, Germany

A safe and flexible continuous multi-step synthesis for the preparation of Diazald® was developed making use of microreaction technology (MRT). Diazald is an important precursor for diazomethane, a highly reactive and selective reagent for the production of pharmaceuticals and fine chemicals. Starting from preliminary batch investigations, optimum parameters were transposed into the MRT set-up. Hence, the amidation of p-toluenesulfonyl chloride to N-methyl-p-toluenesulfonamide as first reaction step results in > 90% yield and a STY of up to 75 kg L-1 h-1. Due to salting-out effects, the product separates nearly quantitatively in high concentrations in organic solution from the saline waste stream, and therefore be continuously converted to Diazald by addition of NaNO2 with quantitative conversions, yields of > 90% and STY of up to 9 kg L-1 h-1. The strategy allows for the direct connection of the Diazald preparation stage to the diazomethane liberation and conversion stage.

I&EC 168

Microfluidic synthesis of biofunctional molecules: Application to glycan synthesis

Koichi Fukase(1), koichi@chem.sci.osaka-u.ac.jp, Machikaneyama 1-1, Toyonaka Osaka 560-0043, Japan . (1) Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka Osaka 560-0043, Japan

A continuous flow microreactor, which realizes efficient mixing and fast heat transfer, is recognized as an innovative technology in recent organic synthesis. The flow system also allows the reaction to be quenched immediately after the formation of the unstable product. Much effort has been devoted to the efficient and stereoselective synthesis of sialylated glycans in order to investigate their biological functions. We have developed an efficient α-sialylation by utilizing the highly reactive sialyl donors having C5-cyclic imides or azide, by virtue of the “fixed dipole effect”. The scale-up in batch process, however, decreased the yield and selectivity, since the reaction control was difficult due to the high reactivity of the sialyl donor. The scale-up problem has now been circumvented by featuring the efficient mixing and fast heat transfer of the microfluidic system, providing the α-sialosides in excellent yields and selectivity

A saturated isoprene natural product, pristane, has been widely used as an adjuvant for antibody production. The availability from natural source is now very limited owing to the protection of several shark species. We have established a multi-kilogram synthesis of pristane, by applying the acid-mediated microfluidic dehydration of the allylic alcohol as the key step. The present protocol was generally useful for dehydration of β-hydroxyketone, simple alkanol, and allylic alcohols, giving corresponding olefins quantitatively.

I&EC 169

Fluidic carbon precursors for facile ionothermal synthesis of microporous and mesoporous carbons

Je Seung Lee(1)(2), leejs70@gmail.com, 1 Hoegi-dong, Dongdaemoon-gu, Seoul Seoul, Republic of Korea ; Xiqing Wang(2); Huimin Luo(2); Sheng Dai(2). (1) Department of Chemistry, Kyung Hee University, Seoul 130-701, Republic of Korea (2) Oak Ridge National Laboratory, Seoul 130-701, Republic of Korea

Porous carbon materials are widely applied to separation, catalysis support, energy storage, and energy conversion for their huge surface areas, high physical and chemical stability, and high electric conductivity. A new synthetic strategy of porous carbon materials, which does not need any template, has been developed because conventional hard or soft template methods are suffering the difficulty of post-treatments or the limitation of surfactants and the difficulty of carbon coating on various substrates. Task-specific ionic liquids containing cross-linkable functional groups on cation or anion were successfully carbonized under ambient pressure for their negligible vapor pressure and high thermal stability. The surface area could be controlled by the counter ion and various shaped substrates were carbon-coated for the fluidity of monomers.

I&EC 170

Evaluation of greenhouse gas emissions (GHG) from a cryogenic gas processing plant

Richard U Edgehill(1), richard.edgehill@valleyair.org, 34946 Flyover Court, Bakersfield CA 93308, United States . (1) Permit Services, San Joaquin Valley Air Pollution Control District, Bakersfield CA 93308, United States

Greenhouse Gas Emissions (GHG) from a cryogenic gas processing plant were evaluated. Direct GHG occur with combustion of natural gas and ethane in IC engines driving compressors and in heaters, flaring of process waste gas, storage tank and piping component emissions, and construction activities. Indirect GHG result from electricity generation. The above is considered as Business as Usual (BAU) design. Electrification of gas-fired equipment, injection into oil production strata (sequestration) and/or use of ethane and process waste gas as fuel eliminates greater than 70% of GHG compared to BAU. By contrast, venting of ethane and process waste gas to the atmosphere results in significantly higher GHG than BAU.

I&EC 171

Membranes for bioseparations: Recent advances and new opportunities

Andrew L. Zydney(1), zydney@engr.psu.edu, 160 Fenske Lab, University Park PA 16802, United States . (1) Department of Chemical Engineering, The Pennsylvania State University, University Park PA 16802, United States

Membrane systems are used for the purification and formulation of literally hundreds of important biotherapeutic producs. Over the last two decades, new membranes, modules, and systems have been developed specifically to meet the requirements of the biotechnology industry. These developments have been facilitated by an improved understanding of the factors governing biomolecule transmission through semipermeable membranes, including both electrostatic interactions and concentration polarization. This presentation highlights some of the key work in this area and provides insights into possible future improvements in membrane technology for the purification of recombinant therapeutic products. Specific examples are discussed for the purification of PEGylated proteins and plasmid DNA.

I&EC 172

Investigation of a spark ignition internal combustion engine via step-scan FTIR spectroscopy

Allen R. White(1), white@rose-hulman.edu, 5500 Wabash Ave, CM 4010, Terre Haute IN 47803, United States ; Stephen Sakai(1); Revecca DeVasher(2). (1) Department of Mechanical Engineering, Rose-Hulman Institute of Technology, Terre Haute IN 47803, United States (2) Department of Chemistry, Rose-Hulman Institute of Technology, Terre Haute IN 47803, United States

In order to pursue In Situ measurements in an internal combustion engine, a MegaTech Mark III transparent spark ignition engine was modified with a sapphire combustion chamber. This modification allowed the transmission of infrared radiation for time-resolved spectroscopic measurements by an infrared spectrometer. By using a Step-scan equipped Fourier transform spectrometer, temporally resolved infrared spectral data were acquired and compared for combustion in the modified Mark III engine

Measurements performed with the FTIR system provide insight into the energy transfer vectors that precede combustion as well as provide an in situ measurement of the progress of combustion. Excitation of the intensity increase in the hydrocarbon stretch that precedes combustion was measured as was the appearance and subsequent excitation of species resulting from combustion.

I&EC 173

Permeability control in stimulus-responsive colloidosomes

Sven H Behrens(1), sbehrens@gatech.edu, 311 Ferst Drive NW, Atlanta GA 30332-0100, United States ; Adriana San Miguel(1). (1) School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta GA 30332-0100, United States

Self-assembly of colloidal particles in the liquid interface of double emulsion droplets can be used to fabricate “colloidosome” microcapsules, which have great potential as vehicles for the controlled delivery of drugs or other cargoes. Here we present a novel class of aqueous core colloidosomes that combine the benefit of low capsule permeability (good cargo retention) with the option of a stimulus-triggered fast release in a target environment. Complete or partial dissolution of the capsule walls in response to a mild pH change is achieved in each case through the use of responsive particles made from polymers with pH-switchable solubility. We demonstrate three methods of controlling the capsule permeability prior to release while maintaining the intended response to the release trigger.

I&EC 174

Development of separation process for 99Mo medical isotope from aqueous homogeneous reactor solution

Dominique C. Stepinski(1), dstepinski@anl.gov, 9700 S. Cass Ave, Argonne IL 60439, United States ; Pei-Lun Chung(2); Amanda J. Ziegler(1); Elizabeth O. Krahn(1); Artem V. Guelis(1); Scott B. Aase(3); Daniel E. Glenn(3); Nien-Hwa L. Wang(2); George F. Vandegrift(1). (1) Chemical Sciences and Engineering, Argonne National Laboratory, Argonne IL 60439, United States (2) School of Chemical Engineering, Purdue University, West Lafayette IN 47907, United States (3) Technical Services Group, Babcock & Wilcox Company, Lynchburg VA 24504, United States

Most of the world's supply of 99Mo is produced from fissioning of 235U in targets of high-enriched uranium (HEU). The use of HEU causes worldwide concerns over the use and transport of this weapon grade material. Efforts are being made to develop a domestic 99Mo radioisotope production that uses low enriched uranium (LEU) targets. These efforts are supported by the Global Threat Reduction Initiative (GTRI), whose mission is minimization and, to the extent possible, elimination of the use of high enriched uranium (HEU) in civilian nuclear applications throughout the world. Babcock & Wilcox Company is developing large-scale production of 99Mo using an LEU based aqueous homogeneous reactor, the Medical Isotope Production System (MIPS). Argonne National Laboratory in collaboration with School of Chemical Engineering, Purdue University, is working to develop a chromatographic separation process to recover 99Mo from the concentrated uranyl nitrate fuel solution of the MIPS. To facilitate MIPS column design, the VErsatile Reaction SEparation (VERSE) rate model simulator was engaged. Batch, pulse, and frontal tests were utilized to estimate system, isotherm and mass transfer parameters for each sorbent under consideration. Once intrinsic model parameters and intraparticle diffusivities for each sorbent were determined, VERSE simulations were carried out to estimate mass-transfer-zone lengths for various sorbents at different linear velocities. A column for separating Mo from 200 L of uranyl nitrate solution in 2 h was designed and verified at bench prototype scale.

I&EC 175

2D modeling the transfer phenomena in the radial adsorber

xingang zheng(1), zxg8181@163.com, 30 xueyuan road, Beijing Beijing 100083, China ; Yingshu Liu(1), ysliu@ustb.edu.cn, 30 xueyuan road, beijing beijing 100083, China ; Wenhai Liu(1); Yongling Li(1); Hui Zhang(1). (1) School of mechanical engineering, University of science and technology beijing, Beijing Beijing 100083, China

In this study, a two-dimensional model is used to study the transfer phenomena occurred in the radial adsorber with consideration of heat effect, gas compressibility and dead volumes. The distributions of concentration, temperature and velocity in four possible configurations, CP-z, Cp-π, CF-z, and CF-π of a radial flow adsorber are investigated. As expected, the results visually show the evolution of process variables and their distribution. Some discussions of the effect of different configurations on variables distribution are made. The two-dimensional simulation is found to be very useful for a better understanding of the dynamic sorption and separation process in the radial adsorber.

I&EC 176

Multiple linear regression analysis of NOx and PM10 emissions from plasma cutting operations

Richard U Edgehill(1), richard.edgehill@valleyair.org, 34946 Flyover Court, Bakersfield CA 93308, United States . (1) Permit Services, San Joaquin Valley Air Pollution Control District, Bakersfield CA 93308, United States

NOx and PM10 emissions from plasma cutting of stainless steel were estimated using statistical models based on multiple linear regression (MLR) of merged sets of literature and industrial data. Predictor variables included plate thickness, cutting speed, and current. Literature data were ill-conditioned and over-determined with design matrix redundant columns. Industrial data were underdetermined. Models based on each data set alone were compared with the merged data model for prediction of emissions from an industrial operation.

I&EC 177

Study on the glycerol carbonate synthesis from glycerol and dimethyl carbonate

Tao Wang(1), taowang@tsinghua.edu.cn, Dept.Chem. Eng., Tsinghua University, Beijing Beijing 100084, China ; Jiabo Li(1). (1) Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

The chemical equilibrium constants were determined for the reactions to produce glycerol carbonate from glycerol. Transesterification of glycerol with cyclic carbonates or alkyl carbonates is thermodynamically favorable for producing glycerol carbonate from glycerol according to the equilibrium constant Increasing temperature can increase the chemical equilibrium constant for the reaction of glycerol with dimethyl carbonate. For the reaction of glycerol with ethylene carbonate, increasing temperature can decrease the chemical equilibrium constant. The reaction of glycerol with carbon dioxide is thermodynamically limited. High temperature and low pressure are favorable to the reaction of glycerol and urea. The deactivation of the alkali solid catalysts, calcium oxide,

calcium hydroxide and calcium methoxide was investigated. When the catalysts were recycled, the yield of glycerol carbonate all decreased dramatically. The alkali solid catalyst was converted to the basic calcium carbonate Cax(OH)y(CO3)z, which was the cause for the decrease of glycerol carbonate yield. It was found that the chemical interactions of the alkali solid catalyst with glyceol and glycerol carbonate leaded to the formation of the basic calcium carbonate Cax(OH)y(CO3)z, for which the mechanism was proposed.There were dissolution losses of the catalysts in the reaction medium. A new method, coupling reaction and azeotropic distillation was proposed for the synthesis of glycerol carbonate (GC) from glycerol (G) and dimethyl carbonate (DMC). The high yield of glycerol carbonate can be obtained at a low molar ratio of dimethyl carbonate to glycerol with the method of coupling reaction and azetropic distillation. Glycerol carbonate yield can be as high as 98%. By continuously removing methanol from reaction system with the method of coupling reaction and azeotropic distillation, the yield of glycerol carbonate can be retained at high level using the recycled catalyst.

I&EC 178

Quantification of trace crystallinity in an organic powder by nonlinear optical imaging: Investigating the effects of mechanical grinding on crysallinity loss

Debbie Wanapun(1), d.wanapun@gmail.com, 560 Oval Drive, West Lafayette IN, United States ; Umesh S Kestur(2); Lynne S Taylor(2); Garth J Simpson(1). (1) Department of Chemistry, Purdue Univerity, West Lafayette IN 47907, United States (2) Department of Industrial and Physical Pharmacy, Purdue University, West Lafayette IN 47907, United States

The effect of mechanical grinding under cryogenic condition (cryomilling) on crystallinity reductions of organic compounds was investigated using powder x-ray diffraction (PXRD), thermal analysis and second harmonic generation (SHG). Griseofulvin, an antifungal therapeutic was used as a model compound. The crystallinity of griseofulvin demonstrates the first order reduction upon cryomilling with the trace crystallinity as low as 0.05% after 3 hr of milling. In addition to macroscopic crystallinity, microscopic information can also be obtained from SHG which shows that the residual crystallinity after exhaustive milling is arising primarily from a small fraction of well localized crystalline domains; rather than a uniform distribution of weakly SHG generated centers. Recrystallizaitons of cryomilled griseofulvin were analyzed and compared with those of melt-quenched griseofulvin (true glass state material). The results show that disordering state obtained by exhaustive cryomilling contains ordered domains that are larger than critical size of nucleation. The presence of such domains provides the barrier-less nucleation sources and result in rapid crystallization depending only on crystal growth.

I&EC 179

Ammonoxidation meets biorefinery: A promising approach for valorizing ligneous materials and combating global desertification

Falk Liebner(1), falk.liebner@boku.ac.at, Muthgasse 18, Vienna Vienna A-1190, Austria ; Georg Pour(1); Karl Klinger(1); Michael Schrems(1); Luvuyo Tyhoda(2); Antje Potthast(1); Thomas Rosenau(1). (1) Department of Chemistry, BOKU University Vienna, Vienna Vienna A-1190, Austria (2) Department of Forest and Wood Science, University Stellenbosch, Stellenbosch Western Cape 7599, South Africa

Desertification is one of the world's most alarming processes of environmental degradation. Bare topsoils are prone to wind and water erosion which leads to a far-reaching loss of the accumulated organic carbon in terms of humic substances and thus to decreasing productivity of formerly arable land. In view of the increasing importance of renewable sources and activities in the biorefinery sector, enhanced attention should be paid for closing nutrient and carbon cycles in the future. Ammonoxidation has been established some time ago as a suitable chemical process for enriching technical lignins (pulping industry) or ligneous materials (biorefineries, even low-grade coal) with nitrogen and for converting such materials into artificial humic substances that act as a slow-nitrogen-releasing organic fertilizer due to its content of different types of N-binding form. The current paper will impart the current state of research in lignin ammonoxidation and critically discuss the application potential and unresolved issues.