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Rational Design for Coke-resistant Dry Reforming Catalyst using Combined Theory and Operando Raman Experiments

Periodic Reporting for period 1 - Biogas2Syngas (Rational Design for Coke-resistant Dry Reforming Catalyst using Combined Theory and Operando Raman Experiments)

Reporting period: 2019-11-01 to 2021-10-31

With dwindling fossil reserves and increased energy and chemical demands, finding an alternate source to fulfil chemical and energy requirement is essential. In this direction, CO2 conversion processes involving syngas production are promising. However, activation of CO2 is a major challenge that requires high temperature, leading deactivation of catalyst due to carbon formation. The MSCA Research Fellow employed theoretical and experimental catalysis with an aim to understand how the activity and stability of dry reforming catalyst reduce due to carbon deposition and howa catalyst can rationally be designed to enhance overall stability with the least impact of coke formation. Biogas2Syngas has an interdisciplinary nature as it lies in the intersection of chemistry and chemical engineering involving theoretical studies and experimental details to understand deactivation mechanisms. The common denominator is the catalyst which we studied through a fundamental multiscale analysis involving both theoretical and experimental results. Despite the COVID-19 pandemic and multiple lockdowns, the project has achieved most of its objectives and milestones for the period, with relatively minor deviations.
The overall goal is to develop high-performance coke resistant catalyst for syngas production and understand mechanism of coke formation using operando Raman experiments integrated with computational studies. The objective of the project can be summarized as follows: 1. Preparation and characterization of coke resistant catalysts; 2. Testing of prepared catalysts for biogas to syngas production; 3. Operando Raman spectroscopic experiments to establish detailed molecular structural information, activity relationships and catalyst deactivation mechanism during syngas production under varying reaction conditions and 4. Interpretation of experimental and DFT data in multiscale analysis.
1.2 Explanation of the work carried out per WP (Work Package)
The MSCA Fellow worked at Polytechnic University of Milan (PoliMi) in the department of Energy under the day-to-day supervision of Prof. Matteo Maestri. The achievements identified in this report reflect the positive learning environment at the host institution.
1.2.1. Work Package (WP) 1: Technical part: Catalyst synthesis and characterization
The study under WP1 was to prepare and characterize supported metal catalysts for syngas production. The purpose was to study stability of the catalyst for enhancing catalytic properties and minimizing deactivation. The idea was presented in I2CM with the following details
M. I. Alam, M. Maestri, Rational design for carbon resistant dry reforming catalyst: combined theory and operando Raman experiments, I2CM Villars-sur-Ollon, Switzerland, February 3-6, 2020.
In addition, I had an opportunity to interact with different researchers of chemistry and chemical engineering backgrounds and learn many tools and techniques related to MSCA project requiring knowledge on Reactor types and their corresponding behavior. Bench scale reactors, intrinsic kinetic verification, kinetic model development during the said periods. The fellow has gained experience to deliver the tasks.
1.2.2. Work Package (WP) 2: Experimental part: Catalyst screening and activity test using operando Raman (Figure 1). The fellow has identified major scientific challenges and their proposed solution in the proposed area which is published recently in the journal, Catalysis Science & Technology. The details are mentioned below:
M. I. Alam, R. Cheula, G. Moroni, L. Nardi, M. Maestri, Mechanistic and multiscale aspects of the thermo-catalytic CO2 conversion to C1 products, Catal. Sci. Technol. 2021, 11, 6601-6629. The above publication is a part of larger effort by the fellow to support researchers of diverse background. Figure 2. Effect of dilution at fixed CH4/CO2 = 0.5 under temperature range 300-650 °C.
1.2.3. Work Package (WP) 3: Interpretation of experimental and DFT data in multiscale analysis
The intention of WP3 was to interpret experimental and theoretical results in a multiscale analysis. This involves two deliverables involving proposed mechanism for the coke formation (D3.1) establishment of structure activity relationship and the reaction rate determination (D3.2). As shown in Figure 3 (Right), experimental catalyst evaluation under different time and length scale were performed using diluted catalyst at 600 °C. From Figure 1-3, it may be concluded that mechanism of coke formation is not dependent on a single parameter. Instead, coke formation may be increased due to variation in feed ratios, temperature and presence of reaction/side reaction species.
1.2.4. Work Package (WP) 4: Training activities dissemination and exploitation of results
The intention of WP4 was to communicate findings and involve public engagements. Following deliverables were planned in the proposal. The fellow delivers following activities. 1) Development of soft skills “The impact game-how to structure impact in Horizon Europe proposal?”, Talent development training program 19th and 24th February 2021. 2) Understand management of intellectual property 3) The host group provided training on kinetic modeling software (ASALI) estimate reaction rate and interpret experimental results.4) The fellow collaborated with Prof. Blaz Likozer and spent a month in his department at National Institute of Chemistry, Ljubljana, Slovenia as a visiting scientist in August 2020. 5) Dissemination and exploitation of the research achievements. 6) Outreach via social media: Published journal article was shared on LinkedIn and ResearchGate.7) Since published article was open access. 8) Researcher Training and Transfer-of-Knowledge
The intention of this activity was to increase the Fellow’s research skills and encourage him to share his own knowledge and skills with other interested researchers.
This MSCA project provided an opportunities to enhance potential of the researcher which is directly related to his future career. Following demonstrable skills have been earned by the fellow: (i) Acquired knowledge and demonstrated skills to operate operando Raman experiments (ii) Learned to perform gas phase reaction and study catalysts for high temperature reactions(iii) gained knowledge to theoretically estimate reaction rate (iv) Become expert in chemical process design for reforming reactions (v) Wrote project for external funding for the host laboratory to reach the advancement in research and improve networking skills. Deactivation of metal catalysts due to carbon deposition is one of the major technical challenges in catalysis for chemical industries. To solve these problems, (i) fundamental understanding of the reaction and (ii) evaluation of chemical species together with catalyst structure and surface states are important. The studied performed by the researcher in an annular reactor, is designed and developed in such a way that it can be integrated with GC and Raman spectrometer to investigate catalyst performance, its activity and structural changes along with the measurement of reaction rates under real working conditions. This could help in minimizing air pollution and protect environment together with supplying sustainable chemicals.
Figure 3. Effect of dilution under varying temperature
Figure 1. Possible reaction path showing dependence of partial pressure of water. Red path involves
Figure 2. Effect of dilution at fixed CH4/CO2 = 0.5 under temperature range 300-650 °C.