CO-SYNTHESIS OF HYDROGEN AND HIGH-VALUE CARBON PRODUCTS FROM METHANE - - PowerPoint PPT Presentation

CO-SYNTHESIS OF HYDROGEN AND HIGH-VALUE CARBON PRODUCTS FROM METHANE PYROLYSIS Matteo Cargnello, Arun Majumdar, Stanford University Raghubir Gupta, Susteon

We are preparing active, stable and reusable methane pyrolysis catalysts for CO2-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.

Project Vision

The Concept: we will use the carbon buildup “problem” to our advantage

15 min 90 min

• J. Zhang, L. Jin, Y. Li, H. Si, B. Qiu, and H.

Hu, International Journal of Hydrogen Energy, vol. 38, no. 21, pp. 8732–8740, 2013

Our Approach

• 1. Grow carbon nanotubes (CNT) while producing H2
• 2. Use metal oxide catalyst supports to “cleave”

deposited CNT’s

Deposited CNT’s

• 1. Pyrolysis
• 2. Carbon

removal

Mobile oxygen from metal oxide support Weakens Fe-C bond at interface

Metal oxide support

Fe Fe

Cargnello Lab

2

The Team: integrating catalyst development, separation, scale-up and reactor design

3

• 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

Project Objectives: Co-synthesis of H2 and High-Value Carbon

!"# ↔ ! + 2"'

Graphitic Carbon Fiber Production

Tao Tong, Yang Zhao, Lance Delzeit, Ali Kashani, M. Meyyappan and Arun Majumdar, Nano Letters 2008 8 (2), 511-515.

Hydrogen generation

https://www.caloric.com/en/product/hydrogen-generation/

• Solid carbon. No CO2.
• Single step reaction
• Lower temperature and pressure required
• Potentially cost-competitive with SMR at scale

Δ"∘ = +75.6 /0/234 Goal: Scientific understanding and novel technology for GHG-free H2 production at net cost of $1/kg at scale

Project Objectives: timeline

M.1 Develop catalytic reactor M.2 Catalyst Development M.2.1 Design and initial evaluation M.2.2 Optimize conversion M.2.3 Evaluate and optimize rate and yield effects M.3.1 Demonstration of catalyst regeneration M.4 Quality of Carbon Products M.5 Scalability of Reactor Design M.6 Scalability of Process Design 2/2020 2/2022 2/2021 8/2020 8/2021

Project Objectives: final project targets

Objective: hydrogen production at <1.5 $/kg Objective: catalyst/oxide support with methane conversion >75% and >50% CNT content Objective: stable CNTs production for >25 cycles Objective: 25 cycles of catalyst regeneration after carbon separation

Preliminary results: catalyst design and separation strategy

!"# !"#

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.

Ellingham diagram for oxides !" !"

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

Current Project TRL 3 - 5

Lab and Bench-scale Feasibility 2020-2021 Catalyst and Process Development Technology Demonstration

Follow-on Funding TRL 5 - 7 Industry Investment TRL 7 - 9

2022-2024 2024-2027

Engineering data for a small pilot plant Favorable TEA and FEL-3 Design Package Partners

• Industrial partnerships
• Catalyst manufacturers
• Carbon Users
• Engineering companies
• H2 suppliers and end users

Value Proposition

• Strong TEA (stress-tested)
• Strong IP portfolio
• Freedom to operate (FTO)
• Market pull for the carbon products
• Committed channel partners
• Clear understanding of technology and

market risks

Final goal: demonstrate technology is competitive with SMR Current: evaluation of critical parameters on which to focus research Needs:

Conclusions: novel approach to carbon separation

MOx support Fe NP !" Oxygen migration from support to CNT

# = %&&∘( # = )&&∘(

CN T *!+ !", C-Fe bond cleavage at interface

• Strong complementarity in the

research team

• Novel approach to separation

challenges

• Science-focused effort
• Deep knowledge of

competitive processes