Dr. Bala Subramaniam
- Director, Center for Environmentally Beneficial Catalysis (CEBC)
- Dan F. Servey Distinguished Professor<br><br>
- Chemical & Petroleum Engineering
Subramaniam's research interests are in catalysis, reaction engineering and crystallization. In particular, his research harnesses the pressure-tunable physicochemical properties of unconventional solvents such as supercritical fluids and gas-expanded liquids in multiphase catalysis to develop resource-efficient technologies with reduced environmental footprint. He has authored nearly 220 refereed research publications and 34 issued patents, edited 2 books, presented invited seminars at nearly 100 academic institutions and companies, and given keynote/plenary lectures at nearly 60 conferences.
Subramaniam is the Director of the Center for Environmentally Beneficial Catalysis (CEBC), initiated as a National Science Foundation Engineering Research Center (NSF-ERC), and now a successful center known for its unique industry collaboration model and multi-scale approach to delivering innovations. In partnership with member companies (including ADM, BASF Catalysts, BP, ConocoPhillips, Chevron Phillips, DuPont, Eastman Chemicals, Evonik, ExxonMobil, Grace, Invista, Procter&Gamble, Reliance Industries, SABIC, Solvay and UOP), the CEBC is developing and providing licensing opportunities for novel sustainable technologies related to fuels and chemicals. Subramaniam is also a co-founder of CritiTech, Inc., a pharmaceutical company with a mission to commercialize the production of fine-particle compounds based on his group's inventions.
Subramaniam is the executive editor of ACS Sustainable Chemistry and Engineering and chair of the 2018 Gordon Research Conference on Green Chemistry. He serves on the editorial boards of Industrial and Engineering Chemistry Research, Applied Catalysis B: Environmental, Canadian Journal of Chemical Engineering and Chemical Engineering Technology. He has also been on the scientific and organizing committees of several international symposia in catalysis and reaction engineering, co-chairing the Eighteenth International Symposium on Chemical Reaction Engineering (ISCRE-18, Chicago, 2004) and the Joint India-U.S. Chemical Engineering Conference on Energy and Sustainability (Mumbai, 2013). He has also served as the President of ISCRE, Inc., and served on the Board of Directors of the Organic Chemical Reactions Society (ORCS). Subramaniam currently serves as President of the Great Plains Catalysis Society.
Subramaniam has received several awards for teaching and research, including the Dow Outstanding Young Faculty Award from the American Society for Engineering Education (ASEE); a Silver Anniversary Teaching Award and H.O.P.E. (Honor for the Outstanding Progressive Educator) award finalist recognitions from KU; the Henry Gould Award for Teaching and a Sharp Teaching Professorship from the KU School of Engineering; Higuchi Research Achievement Award, the highest recognition for research given by KU; a "Distinguished Catalyst Researcher" lectureship from the Pacific Northwest National Laboratory; and a "Chemcon Distinguished Lectureship Award" from the Indian Institute of Chemical Engineers. Subramaniam is a Fellow of the AIChE, the ACS Industrial & Engineering Chemistry Division, and the National Academy of Inventors.
Some of the projects listed here involve collaborations with researchers affiliated with the Center for Environmentally Beneficial Catalysis. The collaborators are reflected in the list of representative publications.
Catalysis with Gas-Expanded Liquids: We have exploited the pressure-tunable properties of gas-expanded liquids (GXLs) in a variety of catalytic systems. At ambient temperatures, gases such as carbon dioxide (CO2) and light hydrocarbons (such as propylene and ethylene) are close to their critical temperatures. When mildly compressed (to tens of bars) at such temperatures, they dissolve in most conventional solvents and volumetrically expand them. The increased free volume of the GXL phases accommodates permanent gases such as O2, H2 and CO in unusually high concentrations. We have harnessed these unique properties to demonstrate several novel GXL-based catalytic reaction engineering concepts. These include (a) highly selective hydroformylations at mild conditions;(b) inherently safe ethylene epoxidation process that eliminates CO2 formation as a byproduct; (c) formation of high purity terephthalic acid with reduced solvent burning and carbon footprint; and (d) Facile CO2 electrochemistry in CO2-expanded electrolytes.
Engineering Micronization and Coating Applications with Dense Phase Carbon Dioxide: Particle micronization with supercritical carbon dioxide (scCO2) allows for reproducible crystal formation with the potential for increased surface area (hence enhanced dissolution rates) and concomitant sterlization. Coating with dense phaseCO2 allows the use of traditional organic soluble coatings with complete solvent recovery and virtually no atmospheric emissions. Specific products developed using these processes include taxol nanoparticles (Nanotax®), insulin nanoaggregates, polymer-coated stents, lyophilized drugs, etc.). These technologies have been licensed to a startup company (CritiTech, http://www.crititech.com/). The Nanotax® anticancer drug produced using this technology is now undergoing clinical trials in the U. S. to treat a variety of cancers.
Metal-exchanged Mesoporous Silicates with Tunable Properties: Emerging feedstocks from biomass and natural gas liquids (NGLs) provide unique opportunities for catalyst development. For example, catalysts that are composed of earth-abundant materials are desirable to process feedstock molecules ranging from NGLs (C1-C5) to bulky biomass-based molecules (C18+). We have synthesized metal-exchanged mesoporous silicates that are highly tunable with respect to acidity and may be synthesized to accommodate a wide range of pore sizes (2-9 nm). We have incorporated metals such as Ce, Zr, W and Nb, into mesoporous silicates such as MCM-48, KIT-5, KIT-6, SBA-16 and TUD-1 using single-pot techniques. The metal-exchanged silicates show remarkable activity for a variety of chemical transformations, including Friedel-Crafts alkylation, Meerwein–Ponndorf–Verley (MPV) reduction, Prins cyclizations, olefin metatheses and lignin depolymerization.
Intensified Processes with Ozone: Ozone is apowerful oxidant that can activate C=C and C-H bonds at ambient temperatures to produce valuable chemical intermediates. The main challenges in ozone-based chemical transformations are to (a) manage energetic intermediates safely, (b) stabilize the intermediate products from over-oxidation, and (c) develop solvents that are relatively inert to ozone and promote reaction pathways that do not form energetic intermediates. We have demonstrated novel media (such as liquid CO2) and reactors (including spray reactors) to enable safe and intensified chemical transformations with ozone to produce value-added intermediates and materials. Examples include continuous ozonolysis of fatty acid methyl esters in liquid CO2, spray ozonolysis of lignins to produce flavoring agents (vanillin and 4-hydroxybenzaldehyde) and highly selective alkane oxidations. We are developing modular ozonolysis reactors for distributed manufacturing involving biomass and shale gas feedstocks.
- Exploiting Tunable Solvents in Catalysis and Materials Processing
- Multiphase Reactor Engineering for Safe and Intensified Oxidations
I believe that the laboratory courses provide a vital forum for not only reinforcing theoretical concepts but also developing essential experimental, data analysis, troubleshooting, team work and communication skills. The analysis/interpretation of experimental data form the basis for the preparation of various types of written reports (journal-type, memos, etc.) and oral presentations. Prior to each laboratory session, I require student teams to make concise presentations about their planned work and to rigorously defend their work plan. Besides providing training in oral and written communication skills, this process also helps students to solidify their understanding of theory.
Clear statement of course goals and expectations, effective lectures and notes, challenging yet fair assignments and tests, and accessibility to students are all essential to a positive learning experience -- one that motivates students' desire to learn and to excel. My teaching methods continue to evolve as I have learned more about teaching tips and techniques from student/peer feedback and from periodicals such as the Teaching Professor and Chemical Engineering Education, especially those that use modern technology-based classrooms to deliver instruction in novel ways.
My major teaching interests are in the areas of chemical engineering kinetics, reactor design, industrial development of sustainable catalytic processes, transport phenomena, mathematical methods in chemical engineering, and supercritical fluid technology.
- Chemical engineering kinetics and reactor design
- mass transfer
- mathematical methods in chemical engineering
- industrial development of sustainable catalytic processes
- chemical engineering unit operations laboratories
- undergraduate and graduate courses.
Selected Publications —
J. S. Silverman, A. M. Danby and B. Subramaniam, “Facile Prepolymer Formation with Ozone-pretreated Lignin Containing Endogenous Aromatics,” ACS Sustainable Chemistry and Engineering. 8(46), 17001-17007 (2020)https://dx.doi.org/10.1021/acssuschemeng.0c03811
M. Rajamanickam, A. Ramanathan, H. Zhu,A. Araújo do Nascimento,C. Chapman, Y. Tang, F. Tao and B. Subramaniam, “Enhanced Friedel-Crafts Benzylation Activity of Bimetallic WSn-KIT-6 Catalysts,” Journal of Catalysis, 389, 657-66 (2020). https://doi.org/10.1016/j.jcat.2020.07.001
C-C. Ma, D. Butler, V. Milligan, A. B. A. Hammann, H. Luo, J. F. Brazdil, D. Liu, R. V. Chaudhari and Bala Subramaniam, “Continuous Process for the Production of Taurine from Monoethanolamine,” Industrial and Engineering Chemistry Research, 59 (29), 13007-13015 (2020). https://dx.doi.org/10.1021/acs.iecr.0c02277
D. J. Sconyers, C. I. Shaughnessy,H-J. Lee,B. Subramaniam,J. D. Blakemore and K. C. Leonard, “Enhancing Molecular Electrocatalysis of CO2 Reduction with Pressure-Tunable CO2-Expanded Electrolytes,” ChemSusChem, 12, 2004-2013(2020). https://doi.org/10.1002/cssc.202000390
D. Liu, R. V. Chaudhari and B. Subramaniam, “Enriching Propane/Propylene Mixture by Selective Propylene Hydroformylation: Economic and Environmental Impact Analyses,” ACS Sustainable Chemistry and Engineering, 8(13), 5140-5146 (2020). DOI:https://dx.doi.org/10.1021/acssuschemeng.9b07224
X. Chen, D. B. Rice, A. M. Danby, M. D. Lundin, T. A. Jackson and B. Subramaniam, “Experimental and Computational Investigations of C-H Activation of Cyclohexane by Ozone in Liquid CO2,” Reaction Chemistry and Engineering, 5, 793-804(2020). DOI: https://doi.org/10.1039/C9RE00442D
C. I. Shaughnessy,D. J. Sconyers, H-J. Lee,B. Subramaniam,J. D. Blakemore and K. C. Leonard, “Insights into Pressure-tunable Reaction Rates for Electrochemical Reduction of CO2 in Organic Electrolytes,” Green Chemistry, 22, 2434-2442 (2020). DOI:https://doi.org/10.1039/D0GC00013B
A. Uchagawkar, A. Ramanathan, Y. Hu and B. Subramaniam, “Highly Dispersed Molybdenum Containing Mesoporous Silicate for Olefin Metathesis,” Catalysis Today (Reaction Engineering & Catalysis Issue in Honor of Professor Dragomir Bukur), 343, 215-225 (2020). DOI:https://doi.org/10.1016/j.cattod.2019.03.073
K. Y. Nandiwale, A. M. Danby, A. Ramanathan, R. V. Chaudhari, A. H. Motagamwala, J. A. Dumesic and B. Subramaniam, “Enhanced Acid-Catalyzed Lignin Depolymerization in a Continuous Reactor with Stable Activity,” ACS Sustainable Chemistry and Engineering, 8 (10), 4096-4106(2020). DOI: https://dx.doi.org/10.1021/acssuschemeng.9b06556
S. Yu, W. K. Snavely, R. V. Chaudhari and B. Subramaniam, “Butadiene hydroformylation to adipaldehyde with Rh-based catalysts: insights into ligand effects,” Molecular Catalysis, 484, 110721 (2020). DOI: https://doi.org/10.1016/j.mcat.2019.110721
J-F Wu, A. Ramanathan, R. Kersting, A. M. Jystad, H. Zhu, Y. Hu, C. P. Marshall, M. Caricato and Bala Subramaniam, “Enhanced Olefin Metathesis Performance of Tungsten and Niobium Incorporated Bimetallic Silicates: Evidence of Synergistic Effects,” ChemCatChem, 12, 1-11 (2020).DOI:https://doi.org/10.1002/cctc.201902131
M. J. Tenorio-Serrano, R. V. Chaudhari and B. Subramaniam, “Rh-Catalyzed Hydroformylation of 1,3-butadiene and pent-4-enal to Adipaldehyde in CO2-expanded Media,” Industrial & Engineering Chemistry Research, 58(50), 22526-22533 (2019) DOI: https://doi.org/10.1021/acs.iecr.9b05184
S. K. Maiti, A. Ramanathan and B. Subramaniam, “110th Anniversary: Near-total Epoxidation Selectivity and Hydrogen Peroxide Utilization with Nb-EISA catalysts for Propylene Epoxidation,” Industrial & Engineering Chemistry Research, 110th Anniversary Issue, 58 (38), 17727-35 (2019).DOI: 10.1021/acs.iecr.9b03461
C. Shaughnessy, D. Sconyers, T. Kerr, H-J. Lee, B. Subramaniam, K. Leonard, J. Blakemore, “Enhanced Electrocatalytic CO2 Conversion in Pressure-Tunable CO2-Expanded Electrolytes,” ChemSusChem, 12(16), 3761-3768 (2019). DOI: 10.1002/cssc.201901107
J. S. Silverman, A. M. Danby and B. Subramaniam, Ozonolysis of Lignins in a Spray Reactor: Insights into Product Yields and Lignin Structure,” Reaction Chemistry and Engineering, 4, 1421-1430 (2019). DOI: https://doi.org/10.1039/C9RE00098D
Z. Song, B. Subramaniam and R. V. Chaudhari, “Transesterification of Propylene Carbonate with Methanol using Fe-Mn Double Metal Cyanide Catalyst,”ACS Sustainable Chemistry and Engineering, 7(6), 5698-5710 (2019). DOI: 10.1021/acssuschemeng.8b04779
S. K. Maiti, W. K. Snavely, P. Venkatasubramanian, E. Hagberg, D. H. Busch and B. Subramaniam, “Kinetics of Selective Methyl Oleate Epoxidation with Venturello Complex Using Controlled Hydrogen Peroxide Addition,” Industrial and Engineering Chemistry Research, 58(7), 2514-2523 (2019). DOI: 10.1021/acs.iecr.8b05977
K. Y. Nandiwale, A. M. Danby, A. Ramanathan, R. V. Chaudhari and B. Subramaniam, “Dual Function Lewis-acid Catalyzed Depolymerization of Corn Stover Lignin into Stable Monomeric Phenols,” ACS Sustainable Chemistry and Engineering, 7, 1362-1371 (2019). DOI: https://doi.org/10.1021/acssuschemeng.8b05077
J-F Wu, A. Ramanathan, A. Biancardi, A. M. Jystad, M. Caricato, Y. Hu and B. Subramaniam, “Insights into Active Site Precursors for Olefin Metathesis in W-incorporated Silicates,” ACS Catalysis, 8, 10437-10445 (2018). DOI: https://doi.org/10.1021/acscatal.8b03263
D. Liu, Z. Xie, W. K. Snavely, R. V. Chaudhari and B. Subramaniam, “Enhanced hydroformylation of 1-octene in n-butane expanded solvents with Co-based Complexes,” Reaction Chemistry & Engineering, 3, 344-352 (2018). DOI: 10.1039/C8RE00034D
D. Liu, R. V. Chaudhari and B. Subramaniam, “Homogeneous catalytic hydroformylation of propylene in propane-expanded solvent media,” Chemical Engineering Science, 187, 148-156 (2018). DOI: 10.1016/j.ces.2018.04.071
H. Zhu, A. Ramanathan, J-F. Wu and B. Subramaniam, “Genesis of Strong Brønsted Acid Sites in WZr-KIT-6 Catalysts and Enhancement of Ethanol Dehydration Activity,” ACS Catalysis, 8, 4848-4859 (2018). DOI: https://doi.org/10.1021/acscatal.8b00480
A. M. Danby, M. D. Lundin and B. Subramaniam, “Valorization of Grass Lignins: Swift and Selective Recovery of Pendant Aromatic Groups with Ozone,” ACS Sustainable Chemistry and Engineering, 6(1), 71-76 (2018). DOI: https://doi.org/10.1021/acssuschemeng.7b02978
A. Ramanathan, H. Zhu,R. Maheswari and B. Subramaniam, “Remarkable Epoxidation Activity of Neat and Carbonized Niobium Silicates Prepared by Evaporation-Induced Self-Assembly,” Microporous and Mesoporous Materials, 261, 158-163 (2018). DOI: 10.1016/j.micromeso.2017.10.049
D. Liu, R. V. Chaudhari and B. Subramaniam, “Enhanced Solubility of Hydrogen and Carbon Monoxide in Propane- and Propylene-Expanded Liquids,” AIChE Journal, 24(3), 970-980 (2018). DOI. 10.1002/aic.15988
C. J. Bode, C. Chapman,A. Pennybaker and B. Subramaniam, “Developing Students’ Understanding of Industrially Relevant Economic and Life Cycle Assessments,” Journal of Chemical Education, 94 (11), 1798–1801 (2017). DOI: 10.1021/acs.jchemed.6b00548
K. Y. Nandiwale, A. M. Danby, A. Ramanathan, R. V. Chaudhari and B. Subramaniam, “Zirconium Incorporated Mesoporous Silicates Show Remarkable Lignin Depolymerization Activity,” ACS Sustainable Chemistry and Engineering, 5(8), 7155-7164 (2017). DOI: 10.1021/acssuschemeng.7b01344
H. Zhu,A. Ramanathan,R. V. Chaudhariand B. Subramaniam, “Effects of Tunable Acidity and Basicity of Nb-KIT-6 Catalysts on Ethanol Conversion: Experiments and Kinetic Modeling,” AIChE Journal, 63(7), 2888–2899 (2017). DOI: 10.1002/aic.15648
M. D. Lundin,A. M. Danby,G. R. Akien,P. Venkitasubramanian,K. J. Martin,D. H. Buschand B. Subramaniam, “Intensified and Safe Ozonolysis of Fatty Acid Methyl Esters in Liquid CO2 in a Continuous Reactor,” AIChE Journal, 63(7), 2819-2826 (2017). DOI:10.1002/aic.15630
J-F. Wu,A. Ramanathanand B. Subramaniam, “Novel Tungsten-incorporated Mesoporous Silicates Synthesized via Evaporation-Induced Self-Assembly: Enhanced Metathesis Performance,” Journal of Catalysis, 350, 182-188 (2017). DOI: 10.1016/j.jcat.2017.02.014
A. Ramanathan,J-F. Wu, R. Maheswari, Y. Hu and B. Subramaniam, “Synthesis of Molybdenum-Incorporated Mesoporous Silicates by Evaporation-Induced Self-Assembly: Insights into Surface Oxide Species and Corresponding Olefin Metathesis Activity,” Microporous and Mesoporous Materials, 245, 118-125 (2017). DOI: 10.1016/j.micromeso.2017.03.001
X. Zuo, A. S. Chaudhari, K. W. Snavely, F. Niu, H. Zhu, K. J. Martin and B. Subramaniam, “Kinetics of 5-Hydroxymethylfurfural Oxidation to 2,5-Furandicarboxylic Acid with Co/Mn/Br Catalyst,” AIChE Journal, 63(1), 162-171 (2017). DOI 10.1002/aic.15497.
B. Subramaniam, R. K. Helling and C. J. Bode, “Quantitative sustainability analysis: A powerful tool to develop resource-efficient catalytic technologies,” ACS Sustainable Chemistry and Engineering (Invited Feature Article), 4, 5859-5865 (2016) DOI: 10.1021/acssuschemeng.6b01571.
J-F Wu, A. Ramanathan, W. K. Snavely, H. Zhu, A. Rokicki and B. Subramaniam, “Enhanced metathesis of ethylene and 2-butene on tungsten incorporated ordered mesoporous silicates,” Applied Catalysis A. 528, 142–149 (2016). DOI: 10.1016/j.apcata.2016.10.004.
X. Zuo, P. Venkitasubramanian,D. H. Busch and B. Subramaniam, “Optimization of Co/Mn/Br-catalyzed oxidation of 5-hydroxymethylfurfural to enhance 2,5-furandicarboxylic acid yield and minimize substrate burning,” ACS Sustainable Chemistry and Engineering, 4(7), 3659–3668 (2016).DOI: 10.1021/acssuschemeng.6b00174.
W. Yan, A. Ramanathan, P. D. Patel, S. K. Maiti, B. B. Laird, W. H. Thompson and B. Subramaniam, “Mechanistic Insights for Enhancing Activity and Stability of Nb-incorporated Silicates for Selective Ethylene Epoxidation,” Journal of Catalysis, 336, 75-84 (2016). DOI: 10.1016/j.jcat.2015.12.022
H. Zhu, R. Maheswari, A. Ramanathan and B. Subramaniam, “Evaporation-Induced Self-Assembly of Mesoporous Zirconium Silicates with Tunable Acidity and Facile Catalytic Dehydration Activity,” Microporous & Mesoporous Materials, 223, 46–52 (2016). DOI: 10.1016/j.micromeso.2015.10.026
M. D. Lundin, A. M. Danby, G. A. Akien, T. J. Binder, D. H. Busch and B. Subramaniam, “Liquid CO2 as a Safer and Benign Solvent for the Ozonolysis of Fatty Acid Methyl Esters,” ACS Sustainable Chemistry and Engineering. 3(12), 3307–3314 (2015). DOI: https://doi.org/10.1021/acssuschemeng.5b00913
I have served as graduate advisor of the chemical and petroleum engineering (C&PE) department to streamline graduate advising, curricular and graduate recruitment activities. Later on, I served as department chair when the C&PE faculty implemented a five-year strategic plan with positive outcomes including the creation of a NSF engineering research center [the Center for Environmentally Beneficial Catalysis, CEBC], increased external research funding, the addition of five new faculty lines for interdisciplinary initiatives in the areas of catalysis and bioengineering, and the successful mentoring and nominations of several faculty for teaching and research awards.
As CEBC director, a unique industry partnership program was implemented. In partnership with member companies (that have included ADM, BASF Catalysts, BP, ConocoPhillips, Chevron Phillips, DuPont, Eastman Chemicals, Evonik, ExxonMobil, Grace, Invista, Procter&Gamble, Novozymes, Reliance Industries, SABIC, SI Group, and UOP), the CEBC is developing and providing licensing opportunities for novel sustainable technologies related to fuels and chemicals.
Since its inception, the CEBC has launched several multidisciplinary research initiatives dealing with sustainable catalysis for producing fuels and chemicals with funding from federal, state and industry sources. The total funding from these sources is nearly $60 million since 2003, resulting in ~450 publications, 60 inventions, 18 patents, 6 licensed technologies, nearly 70 advanced graduate degrees, >50 postdoctoral researchers mentored and >50 undergraduate researchers trained. These successes have also resulted in the addition of several faculty members in the chemistry and C&PE departments. I chaired the recruitment of several of the current C&PE faculty members in the areas of catalysis, reactor engineering and materials science. I serve as mentor to several of the young faculty members recruited as part of these initiatives.
For nearly two decades, I have been active in external professional service focused on facilitating sustainable practices in the chemical process industries, including the use of biomass as a renewable feedstock to produce chemicals and fuels. I have served on several national and regional technical panels including the NSF/EPA panels on environmentally benign processing, and the Midwest Biomass Research & Development Initiative Roadmap panel. I served as the President of the International Symposia for Chemical Reaction Engineering (ISCRE, Inc.) during 2011-2012, and on the Board of Directors of the Organic Reactions Catalysis Society (ORCS) from 2010-2018. I am one of the founding members of the Great Plains Catalysis Society (GPCS) initiated in 2017 and currently serve as the Secretary of the organization.
I have served on the scientific and organizing committees of several international symposia in catalysis and reaction engineering, co-chairing the 18th International Symposium on Chemical Reaction Engineering (ISCRE-18, Chicago, 2004), the 2nd North American Symposium on Chemical Reaction Engineering (NASCRE-2, Houston, 2007) and the 2nd and 3rd Joint India-U.S. Chemical Engineering Conference on Energy and Sustainability (Chandigarh, 2008; Mumbai, 2013). In 2018, I chaired the Gordon Research Conference on Green Chemistry held in Barcelona, Spain.
I currently serve as Executive Editor of ACS Sustainable Chemistry and Engineering, a relatively new ACS journal launched to archive research advances in sustainability-related research in the chemistry and chemical engineering disciplines. I also serve on the editorial boards of Industrial and Engineering Chemistry Research (past), Applied Catalysis B, Canadian Journal of Chemical Engineering, and Chemical Engineering Technology.