(2cs) New Catalytic Pathways Towards Waste to Chemicals Conversion and Sustainable Manufacturing

Economic growth and societal development so far were inherently intertwined with pollution and the creation of waste. My research is focused on using catalysis and reaction engineering to reuse, upgrade and repurpose this “waste” into more useful feedstocks such as lubricants, adhesives and fine chemicals. Progress in this area will bring circular economy closer to reality and ensure sustainable production-consumption balance.

Doctoral Research.

My doctoral research was centered on design of advanced acidic heterogeneous catalysts and development of new spectroscopic tools to characterize them.

Fine tuning of coordination environment of Zr atoms in various zeolite frameworks (1-3) enable me to improve their activity in aldol condensation by factor of 3 (4). We show the role of solvent in Zr and Sn-zeolite systems in transforming Lewis acid sites into protic sites under reaction conditions (5). I developed new sustainable way of manufacturing butadiene via Prins condensation over polyoxometalate clusters (6). In fruitful collaboration, we discovered that probe molecule diffusion monitored by TEM can dissect (a) facile for molecular transport mesopores and (b) dead-end mesopores in real world zeolite catalyst (7). Using fluorescence spectroscopy, we selectively monitored coking in micropores and on external surface of zeolite catalysts (8).

Post-Doctoral Research.

My current post-doctoral research at University of Delaware (advisor Dr. Dion Vlachos) is focused on advanced plastic waste upcycling methods.

Two tackle this issue we employed several strategies. We developed a low-temperature energy efficient bifunctional hydrocracking process which converts polyolefins from the waste to valuable fuels (9). Catalyst tuning and mechanistic studies revealed that we can selectively produce highly branched wax in addition to jet and diesel (10). Another pathway, that I developed, involves catalytic hydrogenolysis of waste polypropylene to lubricants equivalent to group I base oil (11). Analysis of catalyst dynamic behavior in presence of hydrogen allowed to propose catalyst with improved performance (12). Ongoing work is related to further catalyst development, LCA/TEA assessments and expansion of our approaches to real world mixed plastic waste.

Proposed Research Overview.

Research in my lab will focus on adapting heterogeneous catalysis and standard tools of process intensification to a new type of feedstock. Waste coming from agriculture, packaging plastic, biomass processing, and the chemical industry is a complex and diverse mix of compounds. The conventional approach to catalysis as a mean to convert A to B hardly can apply in this case. Previously, complexity has been created staring from simple molecules all the way to fine chemical and polymers. New sustainable manufacturing should deal with complexity and broad range of functionalities in the feedstock at the starting point.

To deal with waste feedstock we need to explore catalysts that can adapt and self-organize in a constantly changing reaction environment. These properties of the catalyst will allow to maintain high activity and tune the selectivity of the reaction. Solid catalyst's responsivity and dynamic behavior under reaction conditions are documented for a set of traditional substrates like CO₂, H₂, etc. This knowledge should be expanded and translated to more complex cases like plastic waste hydrocracking, food waste hydrogenolysis, and many others. The discovery of fundamental principles of catalysts adaptivity and reorganization in a reactive atmosphere will enable more targeted catalyst design and boost the performance of existing processes.

I show examples from my previous work where catalysts adaptivity helped active sites to survive in harsh reactive environments in butadiene synthesis and plastic waste hydrocracking. In detailed research program spitted into three Thrusts I outline how surface adaptivity and self-organization can be detected, monitored and used for catalyst engineering and processing of complex “waste” feedstock.

The proposed vision includes traditional irreplaceable tools of catalysis research. The research will require advanced catalyst preparation and in situ characterization methods coupled with kinetic and mechanistic studies.

Teaching vision.

My core expertise lies in three cornerstones of chemical engineering: phenomenological and statistical thermodynamics, kinetics and transport phenomena. Outside of traditional scope of disciplines, I am ready to teach spectroscopic (FTIR, Raman, NMR, XPS) and other physico-chemical (TGA, DSC, physisorption) characterization methods relevant to catalysis, material science and organic chemistry.

My own work as TA involved lectures, seminars, and design labs in chemical engineering. Many of the courses that I attended lean heavily on mathematical consistency, general theory, and fundamental physical and quantum chemistry. My teaching philosophy is based on a more balanced approach with the constant connection between fundamentals derived on a chalkboard and real-world application. This will involve the broad application of interactive programming tools available in recent years including MATLAB and Python. Monitoring how changes in the initial parameters or properties of the model will affect the outcome will help to make complex ChemE concepts more understandable and memoizable for students.

Current position.

University of Delaware

Postdoctoral Fellow at Department of Chemical and Biomolecular Engineering, Center for Plastic Innovation (DOE funded EFRC). Nov. 2019- Present

Advisor: Professor Dion Vlachos

Selected publication

1. P.A. Kots, A.V. Zabilska, E.V. Khramov, Y.V. Grigoriev, Y.V. Zubavichus, I.I. Ivanova,. Mechanism of Zr Incorporation in the Course of Hydrothermal Synthesis of Zeolite BEA. Inorganic chemistry, 57 (19), 2018, 11978-11985.
2. P.A. Kots, A.V. Kurkin, V.L. Sushkevich, A.N. Fitch, V.V. Chernyshev, I.I. Ivanova. Synchrotron XRD and NMR evidence of germanium redistribution during silylation of BEC-type germanosilicate. CrystEngComm 19, 2017, 5982-5988.
3. P.A. Kots, V.L. Sushkevich, O.A. Tyablikov, I.I. Ivanova. Synthesis of Zr-containing BEC-type germanosilicate with high Lewis acidity. Micro Meso Mater., 243, 2017, 186-192.
4. P.A. Kots, A.V. Zabilska, I.I. Ivanova. Selective self‐condensation of butanal over Zr‐BEA zeolites. ChemCatChem, 2020, 12(1), 248-258.
5. V.L. Sushkevich, P.A. Kots, Y.G. Kolyagin, A.V. Yakimov, AV. Marikutsa, I.I. Ivanova. Origin of Water-Induced Brønsted Acid Sites in Sn-BEA Zeolites. J. Phys. Chem. C 2019, 123, 9, 5540-5548.
6. P.A. Kots, M.A. Artsiusheuski, Y.V. Grigoriev, I.I. Ivanova. One-Step Butadiene Synthesis via Gas-Phase Prins Condensation of Propylene with Formaldehyde over Heteropolyacid Catalysts. ACS Catalysis, 2020, 10, 15149-15161.
7. R.L. Volkov, V.N. Kukin, P.A. Kots, I.I. Ivanova, N.I. Borgardt. Complex pore structure of mesoporous zeolites: unambiguous TEM imaging using platinum tracking. ChemPhysChem, 21(4), 2020, 275-279.
8. S.V. Konnov, V.S. Pavlov, P.A. Kots, V.B. Zaytsev, I.I. Ivanova. Mechanism of SAPO-34 catalyst deactivation in the course of MTO conversion in slurry reactor. Catalysis Science and Technology, 8, 2018, 1564-1577.
9. S. Liu¹, P.A. Kots¹, B.C. Vance, A. Danielson, D.G. Vlachos. Plastic waste to fuels by hydrocracking at mild conditions. Science Advances, 2021, 7(17), eabf8283. (¹ – equal contribution).
10. B.C. Vance, P.A. Kots, C. Wang, Z.R. Hinton, C.M. Quinn, T.H. Epps, III, L.T.J. Korley, D.G. Vlachos. Single Pot Catalyst Strategy to Branched Products via Adhesive Isomerization and Hydrocracking of Polyethylene over Platinum Tungstated Zirconia. Applied Catalysis B, 2021, 120483.
11. P.A. Kots, S. Liu, B.C. Vance, C. Wang, J.D. Sheehan, D.G. Vlachos. Polypropylene plastic waste conversion to lubricants over Ru/TiO2 catalysts. ACS Catalysis, 2021, 11, 8104-8115.
12. P.A. Kots et al. Nat. Com., under review.

Education.

Lomonosov Moscow State University, Moscow, Russia

Ph.D. in Physical Chemistry, Dec. 2018

Advisor: Professor Irina I. Ivanova

Formal thesis title: Zr-doped BEA zeolites: synthesis, physico-chemical properties and application in catalysis

Funded grants and proposals

Lead investigator of research proposal #307865 on National Synchrotron Light Source II and proposal #308892 on Center for Functional Nanomaterials, both at Brookhaven National Laboratory (2021-2022)

Individual PI of RFBR grant â„– 18-33-01011: In situ FTIR study of ethanol to butanol conversion over Lewis acid zeolites (2018-2019)

Winner of Haldor Topsoe Ph.D. Scholarship Programme (2017)

K.I. Zamaraev Ph.D. Scholarship for students specialized in catalysis research (2015)

Mentorship

At University of Delaware mentored three Ph.D. students and one visiting scholar in plastic upcycling group. Constant guidance and support to other Ph.D. students and postdocs in plastic upcycling group. At MSU mentored two masters students (both now enrolled in Ph.D. program at ETH Zurich).