Theodore T. Tsotsis - US grants

This grant is to provide funds for the purchase of a Cahn TG 121 thermogravimetric system to be utilized in studies of diffusion and sorption of large organic molecules in pillared clays. Pillared clays are catalytic materials consisting of very regular porous structures with uses in for example, gas oil cracking, methanol conversion to olefins and toluene ethylation. The equipment will be used to study the diffusivity of various organic molecules in pillared clays by low pressure sorption experiments in a Perkin-Elmer TGS-2 UHV thermogravimetric system. The procedure will consist of placing small amounts of finely ground pillared clay in the quartz microbalance, introducing gas into the apparatus and then measuring the uptake. There are no other thermogravimetric systems in the Chemical Engineering Department at USC and this will be of great benefit to the PI's research effort in preparing new pillard materials and for improving the catalytic and sieving properties of pillared clays already in existence. He has already made valuable contributions in this area and this equipment will greatly benefit his experimental efforts.

Ceramic membranes have good pore size uniformity, and good thermal and mechanical properties. They can be used at high temperatures (1000 C) and in the corrosive environments often found in the chemical industry. They have the additional advantage that they can be thermally treated (500 C), steam cleaned and sterilized. Many industrial catalytic reactions show low conversion and/or yields due either to unfavorable thermodynamics, product inhibition or undesirable side reactions. This in turn necessitates more severe operating conditions (which in turn require higher catalyst replacement rates) and costly separation operations. Catalytic membrane reactors, units in which the membrane is an integral part of the reactor, combine reaction and separation in a single unit operation. Such units have the advantage that the membrane provides for selective removal of one or more products and/or stable intermediates in parallel with the reaction, thus driving the reaction continuously towards the product side and resulting in higher conversions. With higher conversion, the process can be run at lower pressure and temperature, resulting in longer catalyst life, reduced recycle, and reduced downstream separation requirements. The membrane also enables control of surface concentrations and therefore selectivity and product distribution. It is the primary goal of this Industry University Cooperative Research (IUCR) project to test the applicability of ceramic membrane reactor technology in the area of oil and asphaltene hydro processing. Two types of alumina ceramic membranes will be studied, membranes prepared by anodic oxidation of aluminum and membranes prepared by the Sol-Gel technique. Both kinds of membranes have a virtually unimodal pore size distribution and show excellent separatory functions. They have different surface properties and different pore structures and could therefore have different capabilities and/or uses.

Abstract - Tsotsis Inorganic membranes have been the subject of research for liquid and gas separations. The interest in such membranes is due to their unique thermal and mechanical properties and their chemical and microbiological resistance. Inorganic membranes are today finding applications in areas like the food and pharmaceutical industries, in waste water treatment and in catalysis. Membrane reactors combine reaction and separation in a single unit operation. The membrane selectively removes from the reaction zone species, which would otherwise thermodynamically or kinetically limit the reaction progress. This, in turn, increases the reactor yield and results in diminished downstream separation requirements and smaller operational costs. The goal of this project is to gain a better understanding of how liquid macromolecules diffuse and react in small pores (typical of those found in membranes and catalysts). The principal invetigators' interests are in petroleum liquids. They plan to investigate the applicability of ceramic membrane reactor technology in the area of oil and asphaltene hydroprocessing and to study, in depth, the relevant technical questions and issues. Two types of alumina ceramic membranes will be studied, membranes prepared by anodic oxidation of aluminum, primarily for fundamental transport and reaction investigations, and membranes prepared by the Sol-Gel technique, for similar investigations, but also for testing the catalytic membrane reactor concept. Both kinds of membranes have a virtually unimodal pore size distribution and show excellent separatory functions, but have di stinctly different surface properties and unique pore structures. \& 1z CONTROL INI d `3 WINTUTORDAT @ j CALC EXE @ j !@ SOLID2 BMP 1vX ANALYSTSBMP P :.vX CHITZ BMP @ j " M PBRUSH EXE @ j 'P DING WAV @ j "N- EGYPT BMP @ j #v SQUARES BMP @ j 4v Abstract - Tsotsis Inorganic membranes have been the subject of research for liquid and gas separations. The interest in s 0 2 } 2 ! ! ! F 2 2 ( Times New Roman Symbol & Arial " h ?% ?% ?% 6 / Maria K. Burka Maria K. Burka

Abstract - Tsotsis - 9714377 Chemical Reaction Engineering (CRE) is the field which deals with the design and engineering aspects of chemically reactive systems. It first arose in the 1940s and 1950s to meet the technical needs of the petroleum and chemical industry. The objective of CRE is to relate chemical reactor performance to feed materials characteristics and operating variables. From the catalytic hydrocracking of heavy petroleum fractions to produce gasoline and other fuels, to the chemical vapor deposition of thin films for microelectronics applications, CRE is an active, productive research area. The primary meetings for the international CRE community are the biennial International Symposia in Chemical Reaction Engineering (ISCRE) conferences. The location of these meetings alternates between Europe and North America. These conferences bring together for three days international practitioners of the field from both academia and industry. ISCRE 15 is slated to take place in Newport Beach, CA on September 13-16, 1998 and its theme is "Chemical Reaction Engineering for a Cleaner Environment, Advanced Materials Processing and Increased Profitability." Though ISCRE 15 will emphasize the fundamentals, of equal importance will be the technological advances that are currently shaping the future of the field. Topical areas will include: o Reactors for Materials Processing o Waste Minimization and Remediation o Environmentally Benign Processing o Reactor Dynamics o Reactor Control and Safety o Reactor Scale-up and Economic Evaluation o Computational and Modeling Aspects of Reaction/Reactor Engineering o Fluid-Solid Catalytic and Non-Catalytic Reaction Systems o Catalytic, Polymerization and Biochemical Reactors

ABSTRACT

Proposal No: 9615754
Proposal Type: GOALI
Principal Investigator Theodore T. Tsotsis
Affiliation: University of Southern California


This grant is awarded through the Interfacial, Transport and Separations Processes Program of the Chemical and Transport Systems Division, and the NSF Grant Opportunities for Academic Liaison with Industry (GOALI) Program. The Principal Investigator is Dr. Theodore Tsotsis of the University of Southern California. An academic and industrial collaborative research program is to be implemented aimed at developing a better fundamental understanding of the phenomena involved during the preparation of carbon molecular sieve (CMS) membranes. These membranes show excellent promise for many reactor and separation applications and are made via the carbonization in inert and/or reactive atmospheres of polymeric thin films which are either self-supported or coated on various porous substrates. The emphasis in this project is the understanding of the factors in the preparation procedure which are critical to the ability of these materials to effect separation of mixtures based on differences in molecular mobility within the membrane.

Carbon molecular sieve membranes have tremendous potential in the separation of hydrocarbon and reformate mixtures. The ability to tailor the structure of a particular membrane to fit a particular separation and /or reactor application will greatly enhance the technological significance of these systems and expand their use into many new applications. A key requirement here is the development of predictive models of the pore structure and of transport and sorption characteristics of reactant mixtures. This is a main area of emphasis in the project, which will significantly advance the technological base in this area.

ABSTRACT


This project is a collaborative academic/industrial research (GOALI) project to investigate the transport of supercritical hydrocarbon/CO2 mixtures in microporous carbon molecular-sieve membranes. The study will proceed in two parts: (1) preparation and experimental characterization of the membrane along with computational modeling of the evolution of its structure during synthesis; and (2) measurement and simultaneous computer simulation of the sorption and transport of supercritical mixtures within the membranes. The systems under study are supercritical mixtures composed of CO2 and one or more of the following hydrocarbons, butane, isobutane, benzene, and toluene. These hydrocarbons were selected to represent typical aliphatic and aromatic compounds and to permit exploration of factors such as molecular shape. Non-equilibrium grand canonical molecular dynamics (NEGCMD) simulation techniques are being used to study the transport of these mixtures in microporous materials. The objective of the molecular calculations is to relate and correlate the membrane's molecular structure with experimentally observed transport properties and separation efficacy. The long-term goal is to achieve reliable engineering and design of improved materials for molecular sieves and catalytic-membrane reactors.

The results of these studies will contribute to applications such as the regeneration of adsorbents by supercritical CO2 and the use of membranes under supercritical conditions. Carbon molecular- sieve membranes are capable of withstanding the high pressures and temperatures associated with supercritical conditions. They can be prepared with well-controlled porosity and pore size and a very narrow pore-size distribution. Understanding the factors determining the ability of these materials to effect separations of supercritical mixtures based on differences in molecular mobility within the membranes will promote their use in the removal of various contaminants from water, sludges, soils, spent catalysts, and adsorbents like granular activated carbon. The ability to remove solutes continuously from supercritical carbon dioxide would produce significant reductions in operating costs compared with the energy-intensive expansion/re-compression cycle normally used to separate solutes from supercritical solvents.

The field of Chemical Reaction Engineering is key in the development of efficient, environmentally friendly and effective manufacturing. Promoting the exchange of ideas among leading researchers in this field will not only favorably impact the future growth of the Chemical Reaction Engineering discipline but should ultimately result in more efficient and cleaner technologies and an improved way of life for the society as a whole. The international symposium in Chemical Reaction Engineering (ISCRE) is the premier meeting in the field, which takes place every two years and sets the tone for progress in the field. Its impact has been without any doubt tremendous as measured by the number of citations the ISCRE proceedings have received, the increased industry-university interactions that is has fostered, and the improved education and exposure of young researchers in the field. With the Asia Pacific region hosting the upcoming ISCRE 17, it is hoped that this premiere event for Chemical Reaction Engineering (CRE) researchers will provide a step-jump for the participation of researchers in that region, taking a historic step towards the globalization of ISCRE. The meeting of US academic and industrial researchers with an insight into the fast growing CRE community in that region an opportunity that was not available in previous ISCRE's.

NSF's travel support for ISCRE 17 will make it possible for up to twenty five young researchers from the US to attend the meeting covering registration and defraying some of the travel and lodging expenses. NSF funding will allow these researchers to profit by listening to state-of-the-art review talks and research papers and from the opportunity to interact with their fellow researchers in the area. The public at large will significantly benefit by the advancement of the Chemical Reaction Engineering field as a whole and the use of the new ideas generated for the development of more efficient and environmentally friendlier technologies for the production of fuels, materials and chemicals.

Abstract: Nanoporous carbon molecular sieve membranes (CMSM) have been the focus of much previous research for separation of mixtures. Though CMSM exhibit improved properties over polymeric membranes, they are themselves unstable in the presence of O2 and steam at temperatures higher than 300 oC; these are the conditions typically encountered in reactive separations for H2 production, and in fuel-cell applications. Other inorganic membranes, like ceramic (e.g., alumina, silica, and zeolite) and metal (Pd, Ag, and their alloys) have, so far, also proven unstable, in these high-temperature applications, particularly in the presence of steam and CO. In this project we propose the study of SiC membranes that show the potential to overcome some of these difficulties. SiC is a promising material that has high fracture toughness, good thermal shock resistance, and is capable of withstanding high temperatures and corrosive environments. The preparation of SiC nanoporous membranes involves two key steps. First, the preparation of appropriate SiC supports, and second the deposition on these supports of crack- and pinhole-free, thin nanoporous SiC films. Previous research focused on the preparation of appropriate macro and mesoporous SiC membrane supports. In this project, the University of Southern California will deposit thin nanoporous films on these substrates by the pyrolysis of pre-ceramic polymeric precursors. As with the CMSM, the researchers emphasis will be on understanding the factors determining the ability of these SiC materials to separate gas mixtures, based on differences in molecular mobility and molecule-pore surface interactions. Research will proceed along two paths: (1) the preparation and characterization of SiC membranes, and the computational modeling of their molecular structure; and (2) the measurement and simultaneous computer simulation of sorption and transport of mixtures through these membranes. Coupling experiments and simulations will facilitate efforts to relate the membrane's molecular structure with its transport properties, and separation efficacy. This, in turn, will enable progress toward the long-term goal of first-principle molecular engineering and design of improved materials for adsorption and separation. This research project will provide a valuable educational experience and training for the graduate and undergraduate students involved, by training them to prepare and characterize a novel class of new materials, and to learn a host of state-of-the-art computational and experimental techniques. The urban setting of USC affords the opportunity to work with a variety of 2-4 year colleges in the area. The researchers will recruit qualified undergraduates as summer interns, and potentially as incoming graduate students. The experimental results will be disseminated through peer-reviewed publications, presentations at technical meetings, and by makings all reports available on the Web. The PIs envision integrating research findings and aspects of their work as the degree projects in the Reactor Analysis, Transport Phenomena, and Separation courses. The proposed novel SiC membranes show good potential for reactive applications for the production of hydrogen and for fuel-cell applications. In addition to focusing attention on an important class of materials, this project will also generate fundamental insight, which will impact the knowledge-base of the broader field of transport and reaction in nanoporous media, and is likely to catalyze new thinking and rapid new advances in the area.

Engineering - Chemical (53)

Chemical Engineering education is facing a growing disconnect between a curriculum focused primarily on unit operations and faculty research that has increasingly emphasized nano- and bio-technology. This discrepancy has been recognized by an NSF-sponsored Frontiers in Chemical Engineering Education initiative, recommending a move from the macroscopic, unit-operations educational approach to one in which teaching is done from the molecular point of view in a bottom-up fashion. The challenge, however, is to continue to serve the more conventional chemical and petroleum industries while instituting this change. This project team is developing a two-pronged approach of utilizing (1) a recently-created nanotechnology course-work emphasis within the Department of Chemical Engineering and Materials Science, and (2) vertically- and horizontally-integrated degree projects. The degree projects consist of emphasis-specific laboratory modules in successive Chemical Engineering courses that build upon a student's growing knowledge in their chosen emphasis, while at the same time relate the degree project to traditional areas of Chemical Engineering. Students in the Nanotechnology Emphasis, for example, synthesize nanoparticles in the Mass Balance course, examine nanoparticle interactions in Thermodynamics, fractionate nanoparticles in Separations, investigate nanoparticle catalysts in Kinetics, and examine the thermal conductivity of nanocolloids in Heat Transfer, all culminating with an independent research project in the senior year. A comprehensive assessment strategy, including an observation rubric, an efficacy scale, and a success scale, allows evaluation of how the merger of traditional Chemical Engineering subjects with advanced nanotechnology and biotechnology topics may better prepare students for today's increasingly molecular-oriented workplace.

CBET-0816330
Tsotsis

This Small Grant for Exploratory Research (SGER) project is aimed at developing a catalytic reactor to remove toxic components of landfill gas (LFG) so that it can be used as an alternate source of energy.

Intellectual Merit: Nationwide about ~1 MM ftP3P/min of LFG is generated. LFG is potentially an important renewable fuel, as it typically contains more than 50% CHB4B. At the present time a large fraction of LFG is flared. The rest is utilized for electric power generation, and for medium BTU gas-type (e.g., use in boilers) applications. One of the major roadblocks to the utilization of LFG is its miscellaneous corrosive contaminants, e.g., halogen and sulfur containing compounds, which necessitate frequent energy producing equipment servicing, and may lead to eventual failure. Worst of all, halogen and sulfur containing contaminants are emitted to the atmosphere, during flaring or energy production, contributing significantly to air pollution, particularly to acid rain. The removal of these contaminants from LFG prior to combustion is a difficult problem, because of their wide concentration range, and their presence at trace amounts. These factors present difficulties for conventional clean-up technologies, which have proven ineffective for LFG clean-up. The PIs plan to evaluate a catalytic oxidation technology appropriate for LFG clean-up, based on the concept of a "pore-flow reactor" (PoFR) endowed with an oxidation nanocatalyst. This is an important goal as economical, environmental, and energy advantages can be realized, if a process is developed that cost-effectively removes the LFG toxic contaminants. The emphasis in this project is on fundamental investigations of the complex reaction and transport processes that occur in such a reactor; a major fundamental scientific advance will be understanding and modeling the catalytic combustion of the complex heteroatom compounds encountered in LFG. It is such better fundamental understanding that will lead to the main technological advances needed for the further technical development of the PoFR concept. The project will be developed with collaboration with industrial partners M&P and GCE. M&P is an inorganic membrane manufacturer dedicated to the development and application of these novel materials. GCE is an Engineering Company specializing in LFG collection and utilization.

Broader Impact: This research project will provide students with the opportunity to prepare and characterize novel new materials, and to learn a host of state-of-the-art computational and experimental techniques. The project will also provide the students involved with the opportunity to interact with industrial researchers. The urban setting of USC affords the opportunity to work with a variety of 2-4 year colleges in the area, several of which are predominantly minority Institutions. The PIs plan to recruit qualified undergraduates as summer interns, and potentially as incoming graduate students. They will also take advantage of the ever-evolving undergraduate curriculum program at USC, which emphasizes vertically- and horizontally-integrated "degree projects" consisting of emphasis-specific experimental/laboratory modules associated with each core Chemical Engineering course. The PIs envision integrating research findings and aspects of their work as the "degree projects? in the Reactor Analysis, Transport Phenomena, and Separation courses. This catalytic reactor technology will cost-effectively remove the toxic contaminants from LFG, offer significant economical, environmental, and energy advantages, and will allow LFG (and biogas in general) to gain its full potential as a valuable renewable fuel.

This award is funded under the American Recovery and Reinvestment Act of 2009 (Public Law 111-5).

0854427
Tsotsis

This NSF award by the Chemical and Biological Separations program supports work by Professors Theodore Tsotsis and Muhammad Sahimi at the University of Southern California to systematically investigate and further improve the technique of pre-ceramic polymer pyrolysis to produce nanoporous SiC membranes and films, which are both cost-efficient and industrially viable.

In this project we propose the study of SiC membranes which show the potential to overcome some of the difficulties other membranes face, which have proven unstable in the presence of O2 and steam at temperatures higher than 300C; these are the conditions typically encountered in reactive separations for H2 production, and in fuel-cell applications. SiC is a promising material that has high fracture toughness, good thermal shock resistance, and is capable of withstanding high temperatures and corrosive environments. Our current research with these materials focuses on the preparation of appropriate SiC membrane supports, and the deposition on these substrates of thin nanoporous films by the pyrolysis of pre-ceramic polymeric precursors. Our preliminary studies have shown that using new types of PCS materials leads to the preparation of hydrogen-permselective membranes. However, significant progress must still be made before these SiC membranes become appropriate for practical applications. In this project we will, therefore, systematically investigate and further improve the technique of pre-ceramic polymer pyrolysis to produce nanoporous SiC membranes and films, which are both cost-efficient and industrially viable. Our emphasis will be on understanding the factors determining the ability of these SiC materials to separate gas mixtures, based on differences in molecular mobility and molecule-pore surface interactions. We will proceed along two paths: (1) the preparation and characterization of SiC membranes, and the computational modeling of their molecular structure; and (2) the measurement and simultaneous computer simulation of sorption and transport of mixtures through these membranes. Coupling experiments and simulations will facilitate efforts to relate the membrane's molecular structure with its transport properties, and separation efficacy. This, in turn, will enable progress toward the long-term goal of first-principle molecular engineering and design of improved materials for adsorption and separation.

This research project will provide a valuable educational experience and training for the graduate and undergraduate students involved, in that it will provide them with the opportunity to prepare and characterize a novel class of new materials, and to learn a host of state-of-the-art computational and experimental techniques. The urban setting of USC affords the opportunity to work with a variety of 2-4 year colleges in the area. Our plan is to recruit qualified undergraduates as summer interns, and potentially as incoming graduate students. We plan to disseminate the results of our work through peer reviewed publications, presentations at technical meetings, and by makings all reports available on the Web. We will also take advantage of the ever evolving undergraduate curriculum program at USC, which emphasizes vertically- and horizontally-integrated degree projects consisting of emphasis-specific experimental/laboratory modules associated with each core Chemical Engineering course. The PI?s envision integrating research findings and aspects of their work as the degree projects in the Reactor Analysis, Transport Phenomena, and Separation courses. The proposed novel SiC membranes show good potential for reactive applications for the production of hydrogen and for fuel-cell applications. In addition to focusing attention on an important class of materials, this project will also generate fundamental insight, which will impact the knowledge-base of the broader field of transport and reaction in nanoporous media, and is likely to catalyze new thinking and rapid new advances in the area.

0968159
Tsotsis

Intellectual Merit
Nationwide about ~2.5 MM ft3/min of landfill gas (LFG) is generated. LFG is potentially an important renewable fuel, as it typically contains more than 50% methane (CH4). Unfortunately, today a large fraction of the LFG is flared. The rest is utilized for electric power generation, and for medium BTU gas-type (e.g., use in boilers) applications. One of the major roadblocks to the utilization of LFG is its miscellaneous corrosive contaminants, e.g., halogen and sulfur containing compounds, which necessitate frequent energy producing equipment servicing, and may lead to eventual failure. Worst of all, halogen and sulfur containing contaminants are emitted to the atmosphere, during flaring or energy production, contributing significantly to air pollution, particularly to acid rain. The removal of these contaminants from LFG prior to combustion is a difficult problem, because of their wide range, and their presence at trace amounts. These factors present difficulties for conventional clean-up technologies, which have proven ineffective for LFG clean-up. The PIs plan to develop a novel catalytic oxidation technology appropriate for LFG clean-up, based on the concept of a pore-flow reactor (PoFR) endowed with an oxidation nanocatalyst. Thus economical, environmental, and energy advantages can be realized, if a process is developed that cost-effectively removes the LFG toxic contaminants. The emphasis in this project is on fundamental investigations of the complex reaction and transport processes that occur in such a reactor; a major fundamental scientific advance will be understanding and modeling the catalytic combustion of the complex heteroatom compounds encountered in LFG. It is such better fundamental understanding that will lead to the main technological advances needed for the further technical development of the PoFR concept. The project will be developed with collaboration with industrial partners M&P and GCE. M&P is an inorganic membrane manufacturer dedicated to the development and application of these novel materials. GCE is an Engineering Company specializing in LFG collection and utilization.

Broader Impacts
This research project will provide educational experiences and training for the graduate and undergraduate students as they will prepare and characterize novel new materials and learn a host of state-of-the-art computational and experimental techniques. The project will also provide the graduate and undergraduate students with the opportunity to interact with industrial researchers. The urban setting of USC affords the opportunity to work with a variety of 2-4 year colleges in the area, several of which are predominantly minority Institutions. The PIs plan to recruit qualified undergraduates as summer interns, and potentially as incoming graduate students. They plan to disseminate the results of our work through peer reviewed publications, presentations at technical meetings, and by making all reports available on the Web. They will also take advantage of the ever-evolving undergraduate curriculum program at USC, which emphasizes vertically- and horizontally-integrated degree projects consisting of emphasis-specific experimental/laboratory modules associated with each core Chemical Engineering course. The PIs envision integrating research findings and aspects of their work as the degree projects in the Reactor Analysis, Transport Phenomena, and Separation courses. This catalytic reactor technology will cost-effectively remove the toxic contaminants from LFG, offer significant economical, environmental, and energy advantages, and will allow LFG (and biogas in general) to gain its full potential as a valuable renewable fuel. In addition to focusing attention on an important novel reactor concept, this project will also generate fundamental insight, which will impact the knowledge-base of the broader field of transport and reaction in nanoporous media, and is likely to catalyze new thinking and rapid new advances in the area.

This project is being supported by the Chemical, Bioengineering, Environmental, and Transport Systems Division (CBET) and the Division of Industrial Innovation and Partnerships (IIP).

This PFI: AIR Technology Translation project focuses on translating novel catalytic oxidation technology based on the "pore-flow reactor" (PoFR) concept together with an ultra-violet (UV)-photodecomposition-based (PhoR) technology for the removal of siloxanes, a particularly problematic class of impurities found in biogas and landfill gas (LFG). This technology addresses the need for the development of a novel clean-up method to remove toxic contaminants from these important renewable fuels. The project will result in the completion and the validation of the proof-of-concept both at the lab-scale and the field-scale of this landfill gas and biogas clean-up technology. This LFG and biogas clean-up system has the following unique features: (i) it completely destroys the toxic contaminates rather than transfer them into a different medium; (ii) it does not require the use of adsorption media and their regeneration or the flaring of desorbed contaminants; (iii) it is a continuous process. These features provide process performance, reliability, safety, environmental and cost savings advantages when compared to the leading competing adsorption/absorption technologies in this market space.

The preliminary results, so far, with the LFG/biogas clean-up technology are promising. This project addresses technology gaps as it translates from research discovery toward commercial application, specifically: (i) gaining a better insight about the characteristics of each individual technology subsystem (PoFR and PhoR), but also how they potentially function together as an integrated technology; (ii) acquiring a better understanding of the reaction/transport processes that occur during contaminant destruction; (iii) developing an effective process model to be able to optimize performance without the need of extensive and costly experimentation; (iv) field-testing of the technology to validate its ability to function with real LFG and biogas; (v) process modeling to demonstrate process feasibility

The project engages three principal partners, the University of Southern California (USC) and two small US companies, Media and Process Technology, Inc. of Pittsburgh, PA (M&PT), and GC Environmental, Inc. of Anaheim, CA (GCE) working as a team to develop this novel cost-effective clean-up method to remove toxic contaminants from LFG and biogas. The project will engage three additional broader-context partners, namely the EISGTTP Program at San Diego State University (guiding commercialization aspects), and a small business (BENA) and Southern California Gas Company (SoCalGas), both providing test environments, all working together towards a common goal of the translation of this technology from research discovery toward commercial reality.

This novel clean-up technology is important because it will allow LFG and biogas to gain their full potential as renewable fuels; it also shows promise for widespread application, beyond the LFG/biogas market, for volatile organic compounds (VOC) destruction in contaminated gas streams, encountered in many energy and industrial applications. This technology will contribute to the U.S. competitiveness in the renewable energy and environmental fields by providing superior treatment capability allowing engines, combustion and process equipment to experience longer life with less maintenance.

The conversion of distributed biomass resources from agricultural waste into liquid transportation fuels can have significant potential economic benefits to rural communities and also can improve global environmental sustainability. The proposed project aims to develop a novel process for converting waste biomass to alcohol fuels that is suitable for small-scale operations, employs fewer processing steps than existing methods, and produces higher yields with improved energy efficiency and inherent safety. The team of researchers collaborates with an industrial partner, Sheeta Global Technology Co., to develop and test the proposed biomass to alcohol conversion technology.

This research project focuses on the development of a novel membrane contactor reactor that integrates methanol synthesis with in situ separation of the product using an inorganic membrane and an ionic liquid stream. The main research objective is to develop a simple, safer, high-yield alcohol synthesis process that utilizes biomass as a feedstock and has the advantage of using fewer processing steps than existing methods, minimizing product separation requirements, needing less expensive reactors, managing heat more effectively, and requiring less expensive feed gas. The design of the membrane contactor reactor prevents direct contact of the ionic liquid with the catalyst by separating the two components with an inorganic membrane. The membrane is designed to allow only the product methanol to pass through while preventing passage other gaseous compounds. Therefore, any potential loss of the ionic liquid through reaction with the catalyst is minimized, and the liquid stream that carries the product is not contaminated with catalytic particle fines. Successful completion of the project may lead to pilot-plant scale testing in collaboration with the industrial partner. In addition to training graduate and undergraduate students in research, there is a plan to engage undergraduate students in the development of hands-on teaching modules that will be used for outreach to middle schools. These outreach activities would serve students from underrepresented and disadvantaged groups in collaboration with USC's Mathematics, Engineering, Science Achievement (MESA) program.

The Planning Grants for Engineering Research Centers competition was run as a pilot solicitation within the ERC program. Planning grants are not required as part of the full ERC competition, but intended to build capacity among teams to plan for convergent, center-scale engineering research.

Development of continuous membrane-enabled manufacturing of pharmaceuticals will open hitherto nonexistent opportunities for both conventional and reactive separations in the chemical, fine chemicals and petrochemical industries. Membrane technologies are compact, modular, easily scalable, highly energy efficient and are capable of extraordinary separations in a continuous fashion. Membrane reactors can achieve a synthesis level not achievable by conventional tubular reactors and are now well-established as a process intensification tool. To overcome many deficiencies of batch manufacturing, we propose an ERC for Continuous Membrane-Enabled Manufacturing of Pharmaceuticals (CMMP) using membrane technologies. The proposed ERC has three goals: (1) Develop, adapt and transition new membranes, novel membrane technologies and membrane reaction-separation concepts developed by the CMMP team and others into individual steps of continuous manufacturing of active pharmaceutical ingredients (APIs) in the molecular weight range of about 150-1000 Da; (2)Integrate the individual membrane-based steps into a multistep API production process and demonstrate the feasibility of a primarily membrane-based continuous process equipped with process analytical technology (PAT) to synthesize APIs economically with high efficiency, quality, and safety;(3) Develop an educational program and foster an environment that transforms education relevant to pharmaceutical production as well as influences fine chemicals manufacturing processes with the program-developed innovations.

In this Planning Grant, academic stakeholders from six universities will work with stakeholders from major pharmaceutical companies, contract manufacturing organizations, membrane manufacturers, and process system developers to identify key pharmaceutical systems with synthesis-cum-separation steps ready for introduction of new membrane technologies. During this grant, stakeholders will deliberate on potential membrane-based demonstration systems for multistep synthesis of select APIs. These systems will form the basis of the ERC pre-proposal. A stakeholder community will be formed to guide progress of CMMP and creation of a strong academic program to assist high school, undergraduate and graduate students learn the paradigm change when transitioning from batch production into continuous membrane-based API manufacturing. Membrane technologies have very limited footprint in pharmaceutical manufacturing due to perceived concerns regarding reduced solvent resistance and limited selectivities in organic solvent-based systems. New dense membranes are emerging with very high solvent resistance (HSR) and exquisite selectivities that can separate mixtures of smaller molecules and organic solvents via processes such as, organic solvent reverse osmosis, organic solvent nanofiltration and membrane pervaporation. Their further development will usher in a new era of membranes with extraordinary performance and understanding of how to design them. Microporous HSR membranes can be used for nondispersive solvent extraction, gas-liquid membrane contactors and reactors for hydrogenation, dehydrogenation, ozonation, membrane mixing, crystallization and adsorption. Dense, nanoporous membranes may be used in membrane reactors to achieve high selectivity and yield. Introduction of such membranes operating continuously into each step of the API synthesis train will radically transform pharmaceutical production introducing high efficiencies with compact/scalable membrane modules. This grant will allow stakeholders to identify membrane processes for API production that substantially enhance performances of reaction and separation steps. This grant will also guide an ERC pre-proposal in selecting API synthesis examples having a train of continuously operated membrane-based reaction and separation steps thereby demonstrating the capability of membrane devices to operate with high efficiency and reduced cost.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

This grant supports research toward the development of membranes for energy applications. Increasing access to energy sources is very important for advancing the U.S. economy. As the demand for energy continues to increase, hydrogen has been increasingly considered as a viable alternative energy source for engines, turbines and fuel cells. To make this a realistic option, hydrogen must be efficiently separated from other gases and, therefore, it is crucial to manufacture robust inorganic ceramic membranes that can operate at high temperatures and pressures. Current methods to fabricate these membranes are costly, time-consuming and produce toxic waste. This award supports fundamental research that leads to the development of a solvent-free, one-pot or single step manufacturing process to fabricate inorganic membranes for hydrogen separation. This new manufacturing process leads to a more cost-effective and environmentally-friendly way to provide clean energy sources, which leads to national prosperity and security. This award supports the education of future scientists and engineers through outreach to K-12 students and mentorship of undergraduate researchers. This manufacturing technology can also lead to the development of membranes for other applications such as water purification. Hands-on modules demonstrating the use of membranes for water purification are developed to educate middle and high school students on the lack of access to clean water in many parts of the world.

Traditional processes for making inorganic membranes require multiple steps and organic solvents, leading to higher cost and toxic waste. This research gains scientific insights that allow for the development of solventless, one-pot manufacturing of inorganic membranes. Pre-ceramic polymers are deposited in a reactor using a solvent-free process that requires very low energy and mild reactor conditions and employs a broad range of monomers to generate a variety of polymer films. Deposition of a dense, thin polymer layer on top of a macroporous silicon carbide support is ideal for creating high-quality nanoporous ceramic membranes for efficient hydrogen separation. A low vapor pressure liquid barrier layer, which itself serves as a ceramic precursor, is placed on the support before polymer deposition in order to prevent infiltration of the monomer into the support and thus avoid negatively impacting the permeation characteristics of the resulting membrane. Pyrolysis of these films is conducted in the same reactor, hence one-pot, to produce reliable ceramic membranes with lower risk of contamination. The research generates understanding of mechanistic insights on bond cleavage and formation during pyrolysis. Experimental efforts are coupled to multi-scale modeling studies to understand the fundamental reaction and transport processes.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.