CO-SYNTHESIS OF HYDROGEN AND HIGH-VALUE CARBON PRODUCTS FROM METHANE PYROLYSIS Matteo Cargnello, Arun Majumdar, Stanford University Raghubir Gupta, Susteon Project Vision We are preparing active, stable and reusable methane pyrolysis catalysts for CO 2 -free production of hydrogen and high-value carbon products by developing catalyst active phases and carbon-catalyst separation technologies Total project cost: ~$1.5M Length 24 mo.
The Concept : we will use the carbon buildup “problem” to our advantage Our Approach 1. Grow carbon nanotubes (CNT) while producing H 2 2. Use metal oxide catalyst supports to “cleave” 15 min deposited CNT’s Deposited 1. Pyrolysis CNT’s Fe Fe 90 min Metal oxide support Weakens Fe-C bond 2. Carbon at interface removal Cargnello Lab Mobile oxygen from metal oxide support J. Zhang, L. Jin, Y. Li, H. Si, B. Qiu, and H. Hu, International Journal of Hydrogen 2 Energy, vol. 38, no. 21, pp. 8732–8740, 2013
The Team : integrating catalyst development, separation, scale-up and reactor design - Arun Majumdar Expert in carbon structures, CNT growth - Matteo Cargnello Expert in catalyst design, synthesis and testing - Raghubir Gupta Expert in catalyst scale-up, reactor design, industrial catalysis 3
Project Objectives: Co-synthesis of H 2 and High-Value Carbon Goal : Scientific understanding and novel !" # ↔ ! + 2" ' technology for GHG-free H 2 production at net cost of $1/kg at scale Δ" ∘ = +75.6 /0/234 Hydrogen generation Graphitic Carbon Fiber Production • Solid carbon. No CO 2 . • Single step reaction • Lower temperature and pressure required • Potentially cost-competitive with SMR at scale https://www.caloric.com/en/product/hydrogen-generation/ Tao Tong, Yang Zhao, Lance Delzeit, Ali Kashani, M. Meyyappan and Arun Majumdar, Nano Letters 2008 8 (2), 511-515.
Project Objectives: timeline 2/2020 8/2020 2/2021 8/2021 2/2022 Develop catalytic M.1 reactor Catalyst M.2 Development Design and initial M.2.1 evaluation M.2.2 Optimize conversion Evaluate and optimize M.2.3 rate and yield effects Demonstration of M.3.1 catalyst regeneration Quality of Carbon M.4 Products Scalability of Reactor M.5 Design Scalability of M.6 Process Design
Project Objectives: final project targets Objective: catalyst/oxide support with methane conversion >75% and >50% CNT content Objective: 25 cycles of catalyst regeneration after carbon separation Objective: stable CNTs production for >25 cycles Objective: hydrogen production at <1.5 $/kg
Preliminary results: catalyst design and separation strategy Ellingham diagram for oxides !" !" # !" # !" Cetinkaya, S., and S. Eroglu. International Journal of Refractory Metals and Hard Materials , vol. 51, 2015, pp. 137–140; Ha, Hyunwoo, et al. Scientific Reports , vol. 7, no. 1, 2017.
Challenges and potential partnerships Catalyst development Active and selective catalysts for CNT growth; mitigation: accelerated catalyst screening Catalyst/carbon separation process Active regeneration in-situ; mitigation: understand the science leading to carbon growth and oxidation of the active phase Scalability of reactor/process design Understand conditions for scale-up/optimization; mitigation: carefully consider process parameters and alternative options Potential partnerships Collaborations: experts in CNT growth, quality evaluation Follow-up funding: companies involved with Stanford Strategic Energy Alliance
T2M Industry Investment Follow-on Funding Current Project Final goal: TRL 7 - 9 TRL 5 - 7 TRL 3 - 5 demonstrate Lab and Catalyst and technology is Technology Bench-scale Process competitive with SMR Demonstration Feasibility Development Current: evaluation of critical parameters on Engineering Favorable TEA 2024-2027 2020-2021 2022-2024 data for a small and FEL-3 which to focus pilot plant Design Package research Needs: Partners Value Proposition • Industrial partnerships • Strong TEA (stress-tested) • Catalyst manufacturers • Strong IP portfolio • Carbon Users • Freedom to operate (FTO) • Engineering companies • Market pull for the carbon products • H 2 suppliers and end users • Committed channel partners • Clear understanding of technology and market risks
Conclusions : novel approach to carbon separation ! " Fe NP MOx support # = %&& ∘ ( - Strong complementarity in the *! + CN T research team - Novel approach to separation challenges # = )&& ∘ ( - Science-focused effort C-Fe bond Oxygen cleavage at migration from - Deep knowledge of interface support to CNT competitive processes ! " ,
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