Faculty contact:
Susan Kemper
skemper@ku.edu
785-864-4131
Technical contact:
RGS web master
rgs_web_dl@mail.ku.edu
785-864-7778
1501 Wakarusa Dr. Suite A-110
Lawrence, KS 66047
Telephone: 785-864-2903
Fax: 785-864-6051
Chemical & Petroleum Engineering
Sustainable catalysis and reaction engineering through solvent engineering Current projects include exploiting green solvents such as carbon dioxide and water in catalytic oxidations, hydroformylations and alkylations; and pharmaceutical processing with near-critical carbon dioxide.
Our research group has demonstrated at a fundamental level how the pressure-tunable physicochemical and transport properties of near-critical gases may be exploited for developing sustainable catalytic process concepts and novel materials. Through complementary experimental and theoretical investigations, we have shown that these unique properties of near-critical media are not only optimal but also better suited than those of either conventional gas or liquid phase media for enhancing the performance of heterogeneous catalytic reactions as follows: (a) facile desorption and transport of heavy molecules (such as coke precursors) in mesoporous catalysts, alleviating pore-diffusion limitations and improving catalyst effectiveness; (b) enhancing product selectivity; and (c) exploiting the heat capacity maxima exhibited by near-critical media to ameliorate the problem of parametric sensitivity in exothermic fixed-bed catalytic reactors. We have demonstrated these features for several classes of reactions such as isomerizations, hydrogenations, Fischer-Trøpsch synthesis and alkylations.
In the area of homogeneous catalysis, we are exploiting the tunable properties of gas-expanded liquids (GXLs) to intensify the rates (from several fold to 1-2 orders of magnitude) while enhancing selectivity in a variety of liquid phase oxidations and hydroformylations catalyzed by transition metal complexes. The expansion gas is either an inert medium such as CO2 or a light olefin (such as ethylene or propylene) that could be a reactive substrate. In each case, the high compressibility of the expansion gas is exploited to dramatically enhance the solubility of the limiting reactant (such as O2 or syngas and/or substrates such as light olefins) in the liquid phase while also improving the transport properties that are of relevance in reaction engineering. In addition to process intensification, the demonstrated process concepts are characterized by substantial reduction in the use of organic solvents, mild operating conditions (tens of bars and <100°C), reduced flammability hazards (inherently safe) and facile catalyst separation. Quantitative sustainability analyses point toward much broader applications of GXLs in CO, O2, H2O2 and H2-based chemistries, including biomass-based substrates.
Our group has also been exploiting dense CO2 to form nanoparticles of polar compounds from solution, including pharmaceutical compounds (such as insulin, and taxol) and novel catalytic materials. We have synthesized nanoparticles of transition metal complexes with unique function. For example, Co(salen) based nanoparticles provide stoichiometric O2 storage capacity and room temperature NO disproportionation activity. This discovery has led to the possibility of bottom up design of metal nanoparticles with targeted functional property.Subramaniam serves on the editorial boards of Industrial and Engineering Chemistry Research & Applied Catalysis B: Environmental. He has served on several national and regional technical panels including the NSF/EPA panels on environmentally benign chemicals & fuels processing and nanotechnology initiatives, the Midwest Biomass Research & Development Initiative Roadmap panel and the Kansas Bioscience Authority Bioenergy Working Group. He has also been on the scientific and organizing committees of several international symposia in catalysis and green engineering, and co-chaired the Eighteenth International Symposium on Chemical Reaction Engineering (ISCRE-18, Chicago, 2004), the Second North American Symposium on Chemical Reaction Engineering (NASCRE-2, Houston, 2007) and the 2nd Joint India-U.S. Chemical Engineering Conference on Energy and Sustainability (Chandigarh, India, 2008). He is also the President-Elect of ISCRE.
Subramaniam has also held visiting professorships at the University of Nottingham, United Kingdom (2007); Institute of Process Engineering, ETH, Zürich, Switzerland (1999); and at the University of California, Davis (1992).
The Center for Environmentally Beneficial Catalysis (CEBC) (https://rhodium.cebc.ku.edu) at the University of Kansas was initiated under the prestigious National Science Foundation Engineering Research Centers (NSF-ERC) program. The mission of the CEBC is to develop novel, leading-edge technologies that bring about revolutionary and sustainable transformations in the chemical end energy industries. In partnership with a growing base of 15 member companies (including ADM, BASF Catalysts, BP, ConocoPhillips, Chevron Phillips, DuPont, Eastman Chemicals, ExxonMobil, Procter&Gamble, Novozymes, SI Group and UOP), the CEBC researchers are performing cutting-edge catalysis research aimed at developing novel sustainable technologies related to fuels and chemicals. The member companies value CEBC as a regional/national resource for research and education related to energy and the environment.
CEBC students (postdoctoral, graduate and undergraduate) receive unique training in multidisciplinary systems-based research involving collaborations between academic and industrial researchers, including industrial internships. Students have the opportunity to perform cutting edge science and technology research under nationally and internationally recognized researchers and in a diverse community of fellow graduate students and postdoctoral researchers.
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