Catalysis and Reaction Engineering

Research in the areas of catalysis and reaction engineering focus on the conversion of feedstocks, including natural gas, into valuable fuels, chemicals, and products. In particular, research emphasizes modular solutions that can be implemented on a small scale and utilize natural gas resources which are often flared due to transportation challenges.

Two heating approaches are used in these chemical reactions: traditional thermal heating and microwave heating. In thermal reactions, the full reactor and catalyst bed are heated to facilitate chemical bond breaking and formation steps over the catalyst surface. The focus of this research area is on fundamental understanding of catalyst active site structures to enable new reaction pathways and conversion of a wide range of feedstocks.

In microwave reactions, the novelty of the technique is the use of electromagnetic energy to enable activation and transformation of chemical bonds at the interface of catalyst and reactants, overcoming equilibrium limitations, thus achieving higher yields at relatively low overall temperature and pressure. The catalyst and reacting species can interact with a microwave field and provide energy to the reaction through relaxation processes, such as dipolar or Debye processes, which couple microwave radiation with dipoles in the solid catalyst.

Current Research Topics

1. Microwave Catalysis for Natural Gas Conversion (Hu)

Metal-embedded carbon-based catalytic membranes for co-production of ammonia and ethylene (Ball, Hu, co-PIs)

Source of Support: WV HEPC

This work is focused on the discovery of non-conventional microwave-assisted pathways to simultaneously activate two highly stable molecules (CH4 and N2) to produce fundamental value-added chemicals (ethylene and ammonia) using a single task-integrated unit empowered by hydrogen permeable membrane. Catalytic membranes offer the potential for integration of reaction and separations into a single, modular process unit; however, lack of appropriate materials limits the implementation of such processes. To address this grand open challenge, we are investigating an innovative one-step material synthesis strategy which can effectively increase the uniformity and reproducibility of the resulting catalytic membranes and improve scalability of the synthesis.

Core-Shell Oxidative Aromatization Catalysts for Single Step Liquefaction of Distributed Shale Gas (Hu, Co-PI)

Source of Support: DOE/NETL

This technology is a novel, heterogenous, multi-functional catalyst which selectively activates the active metal clusters using microwave energy to reach the 700°C reaction temperature to activate the stable C-H bonds while maintaining lower temperatures at the acid sites to prohibit the polymerization that leads to coke formation.

Renewable Energy to Fuels through Microwave Catalytic Synthesis of Ammonia (Hu, PI)

Source of Support: DOE/ARPA-E

Synthesis of ammonia from renewable electricity (solar or wind power) under low pressure (0-200 psig) and temperature of 250-400 °C. This technology is developed for small scale distributed production of ammonia which can be used as a hydrogen carrier or fertilizer. The technology is specifically developed for energy resources with intermittent production by nature (solar, wind, flaring gas, etc).

Center of Advancement of Science and Engineering for Localized Gas Utilization (Hu, PI)

Source of Support: West Virginia HEPC

A Novel Molten Salt System for CO2 Based Oxidative Dehydrogenation with Integrated Carbon Capture (Hu, Co-PI)

Source of Support: DOE/NETL

Microwave Catalysis for Process Intensified Modular Production of Carbon Nanomaterials from Natural Gas (Hu, PI)

Source of Support: DOE/NETL, NSF

2. Design of Heterogeneous Catalysis for Thermocatalytic Reactions (Ball)

Oxide support effects in Ni-catalyzed CO2 conversion

As mitigation of climate change becomes increasingly urgent, there is a drive to move away from petroleum both for transportation fuels, such as gasoline and jet fuels, but also for commodity and specialty chemicals. The conversion of CO2 into chemicals provides a route for achieving two simultaneous goals: utilizing atmospheric CO2 (in tandem with CO2 capture technologies that are outside the scope of this work) and replacing current fossil fuel-derived chemicals with chemicals from alternative feedstocks. Furthermore, effective conversion of CO2 into valuable products can improve the economics and thus feasibility of processes that remove CO2 from the atmosphere in an effort to mitigate climate change. Catalytic materials play a key role in the development of a sustainable chemical industry, as they are used in over 90% of industrial chemical processes and facilitate reactions at milder conditions (less energy input) and with increased production of the desired product(s). CO2 is the most oxidized form of carbon and is therefore very stable; conversion of CO2 into useful products necessitates effective catalyst materials. This project is focused on the development and study of tunable catalyst structures to readily convert CO2 into products at mild to moderate conditions.

Investigation of CO2-ODH Mechanisms Over Supported Metal Nanoparticle Catalysts (Ball, PI)

Source of support: ACS-PRF

On-purpose olefin production is necessary to meet the growing global demand. In particular, the demand for propylene is expected to reach 165 million tons by 2030 which cannot be reached by conventional production processes. In this context, the increasing production of shale gas in the United States offers an attractive opportunity for olefin production through alkane dehydrogenation. As a possible alternative, “soft oxidants,” such as CO2, offer the potential for reduced COx production and improved olefin selectivity. It is not known, however, how CO2 participates in the overall reaction mechanism for CO2 assisted dehydrogenation (CO2-ODH). The overall objective of this work, which contributes to this goal, is to design improved supported metal and metal oxide catalysts for CO2-ODH.

Affiliated faculty

• Jianli (John) Hu, Statler Chair in Engineering for Natural Gas Utilization, Professor, Chemical and Biomedical Engineering, Director – CIGRU
• Madelyn Ball, Assistant Professor, Chemical and Biomedical Engineering

Recent publications

John Hu

1. Wang, X.; Wang, Y.; Robinson, B.; Wang, Q.; Hu, J. Ethane Oxidative Dehydrogenation by CO2 over Stable CsRu/CeO2 Catalyst. Journal of Catalysis 2022 , 413, 138–149. https://doi.org/10.1016/j.jcat.2022.06.021.
2. Jiang, C.; Wang, I.-W.; Bai, X.; Balyan, S.; Robinson, B.; Hu, J.; Li, W.; Deibel, A.; Liu, X.; Li, F.; Neal, L. M.; Dou, J.; Jiang, Y.; Dagle, R.; Lopez-Ruiz, J. A.; Skoptsov, G. Methane Catalytic Pyrolysis by Microwave and Thermal Heating over Carbon Nanotube-Supported Catalysts: Productivity, Kinetics, and Energy Efficiency. Ind. Eng. Chem. Res. 2022, 61 (15), 5080–5092. https://doi.org/10.1021/acs.iecr.1c05082.
3. Bai, X.; Muley, P. D.; Musho, T.; Abdelsayed, V.; Robinson, B.; Caiola, A.; Shekhawat, D.; Jiang, C.; Hu, J. A Combined Experimental and Modeling Study of Microwave-Assisted Methane Dehydroaromatization Process. Chemical Engineering Journal 2022, 433, 134445. https://doi.org/10.1016/j.cej.2021.134445.
4. Caiola, A.; Robinson, B.; Bai, X.; Shekhawat, D.; Hu, J. Study of the Hydrogen Pretreatment of Gallium and Platinum Promoted ZSM-5 for the Ethane Dehydroaromatization Reaction. Industrial and Engineering Chemistry Research 2021, 60 (30), 11421–11431. https://doi.org/10.1021/acs.iecr.1c01555.
5. Wang, I.-W.; Dagle, R. A.; Khan, T. S.; Lopez-Ruiz, J. A.; Kovarik, L.; Jiang, Y.; Xu, M.; Wang, Y.; Jiang, C.; Davidson, S. D.; Tavadze, P.; Li, L.; Hu, J. Catalytic Decomposition of Methane into Hydrogen and High-Value Carbons: Combined Experimental and DFT Computational Study. Catal. Sci. Technol. 2021, 11 (14), 4911–4921. https://doi.org/10.1039/D1CY00287B.
6. Deng, Y.; Bai, X.; Abdelsayed, V.; Shekhawat, D.; Muley, P. D.; Karpe, S.; Mevawala, C.; Bhattacharyya, D.; Robinson, B.; Caiola, A.; Powell, J. B.; van Bavel, A. P.; Hu, J.; Veser, G. Microwave-Assisted Conversion of Methane over H-(Fe)-ZSM-5: Evidence for Formation of Hot Metal Sites. Chemical Engineering Journal 2021, 420, 129670. https://doi.org/10.1016/j.cej.2021.129670.
7. Mevawala, C.; Bai, X.; Bhattacharyya, D.; Hu, J. Dynamic Data Reconciliation, Parameter Estimation, and Multi-Scale, Multi-Physics Modeling of the Microwave-Assisted Methane Dehydroaromatization Process. Chemical Engineering Science 2021, 239, 116624. https://doi.org/10.1016/j.ces.2021.116624.
8. Mevawala, C.; Bai, X.; Kotamreddy, G.; Bhattacharyya, D.; Hu, J. Multiscale Modeling of a Direct Nonoxidative Methane Dehydroaromatization Reactor with a Validated Model for Catalyst Deactivation. Ind. Eng. Chem. Res. 2021, 60 (13), 4903–4918. https://doi.org/10.1021/acs.iecr.0c05493.
9. Lalsare, A. D.; Khan, T. S.; Leonard, B.; Vukmanovich, R.; Tavazohi, P.; Li, L.; Hu, J. Graphene-Supported Fe/Ni, β-Mo2C Nanoparticles: Experimental and DFT Integrated Approach to Catalyst Development for Synergistic Hydrogen Production through Lignin-Rich Biomass Reforming and Reduced Shale Gas Flaring. ACS Catal. 2021, 11 (1), 364–382. https://doi.org/10.1021/acscatal.0c04242.
10. Xu, M.; Lopez-Ruiz, J. A.; Kovarik, L.; Bowden, M. E.; Davidson, S. D.; Weber, R. S.; Wang, I.-W.; Hu, J.; Dagle, R. A. Structure Sensitivity and Its Effect on Methane Turnover and Carbon Co-Product Selectivity in Thermocatalytic Decomposition of Methane over Supported Ni Catalysts. Applied Catalysis A: General 2021, 611, 117967. https://doi.org/10.1016/j.apcata.2020.117967.
11. Lalsare, A. D.; Leonard, B.; Robinson, B.; Sivri, A. C.; Vukmanovich, R.; Dumitrescu, C.; Rogers, W.; Hu, J. Self-Regenerable Carbon Nanofiber Supported Fe – Mo2C Catalyst for CH4-CO2 Assisted Reforming of Biomass to Hydrogen Rich Syngas. Applied Catalysis B: Environmental 2021, 282, 119537. https://doi.org/10.1016/j.apcatb.2020.119537.
12. Li, Q.; Wang, Y.; Hu, J. Synthesis of C4 Olefins from Acetylene over Supported Copper Catalysts. ChemCatChem 2020, 12 (12), 3321–3331. https://doi.org/10.1002/cctc.202000396.
13. Wang, Y.; Caiola, A.; Robinson, B.; Li, Q.; Hu, J. Hierarchical Galloaluminosilicate MFI Catalysts for Ethane Nonoxidative Dehydroaromatization. Energy Fuels 2020, 34 (3), 3100–3109. https://doi.org/10.1021/acs.energyfuels.9b04457.
14. Robinson, B.; Caiola, A.; Bai, X.; Abdelsayed, V.; Shekhawat, D.; Hu, J. Catalytic Direct Conversion of Ethane to Value-Added Chemicals under Microwave Irradiation. Catalysis Today 2020, 356, 3–10. https://doi.org/10.1016/j.cattod.2020.03.001.
15. Lalsare, A.; Sivri, A.; Egan, R.; Vukmanovich, R. J.; Dumitrescu, C. E.; Hu, J. Biomass – Flare Gas Synergistic Co-Processing in the Presence of Carbon Dioxide for the Controlled Production of Syngas (H2:CO ~ 2 – 2.5). Chemical Engineering Journal 2020, 385, 123783. https://doi.org/10.1016/j.cej.2019.123783.
16. Li, Q.; Wang, Y.; Skoptsov, G.; Hu, J. Selective Hydrogenation of Acetylene to Ethylene over Bimetallic Catalysts. Industrial and Engineering Chemistry Research 2019, 58, 20620–20629. https://doi.org/10.1021/acs.iecr.9b04604.

Madelyn Ball

1. Nezam, I.; Zhou, W.; Shah, D. R.; Bukhovko, M. P.; Ball, M. R.; Gusmão, G. S.; Medford, A. J.; Jones, C. W. Role of Catalyst Domain Size in the Hydrogenation of CO2 to Aromatics over ZnZrOx/ZSM-5 Catalysts. J. Phys. Chem. C 2023. https://doi.org/10.1021/acs.jpcc.3c01306.
2. Ball, M. R.; Proaño, L.; Nezam, I.; Lee, D.-C.; Alamgir, F.; Jones, C. W. Citral Hydrogenation over Dilute Alloy Catalysts. ChemCatChem 2023, 15 (5), e202201396. https://doi.org/10.1002/cctc.202201396.
3. Park, S. J.; Wang, X.; Ball, M. R.; Proano, L.; Wu, Z.; Jones, C. W. CO2 Methanation Reaction Pathways over Unpromoted and NaNO3-Promoted Ru/Al2O3 Catalysts. Catal. Sci. Technol. 2022, 12 (14), 4637–4652. https://doi.org/10.1039/D2CY00515H.
4. Ball, M. R.; Rivera-Dones, K. R.; Gilcher, E. B.; Ausman, S. F.; Hullfish, C. W.; Lebrón, E. A.; Dumesic, J. A. AgPd and CuPd Catalysts for Selective Hydrogenation of Acetylene. ACS Catalysis 2020, 10 (15), 8567–8581. https://doi.org/10.1021/acscatal.0c01536.

Funding agencies/industrial collaborators