Converting Hydrocarbons to Recyclable Materials for Metal ...
Transcript of Converting Hydrocarbons to Recyclable Materials for Metal ...
Converting Hydrocarbons to Recyclable Materials forMetal Replacement with Positive Hydrogen Output
Matteo Pasquali, Rice UniversityGlen Irvin, Boris Yakobson, Evgeni Penev, Rice UniversityLeonardo Spanu, Carl Mesters*, Joe Powell*, John Lockemeyer, Shaojun Miao, ShellMatteo Maestri, Politecnico di MilanoJeff Blackburn, NREL
Total project cost: $3.45M
Length 36 mo.
Decarbonizing the industrial sector and lightweighting transportation by making lightweight structural materials and conductors via co-production of advanced carbon materials and clean hydrogen
* emeritus
C0 fibersC0 films
3D solids
Properties
Markets:1-10 MT/yr each
Applications
A novel hydrocarbon pathway: materials with structural integrity
© Rice University 2019. All rights reserved.
∆Hr4.7 MJ
Impactful if above 100 MT/yrSteel is 1.6 GT/yr
Carbon Nanotubes
Graphene
1 kg CH4
55.6 MJ
0.75 kg C0
0.25 kg H2
35.5 MJ
Team
Glen Irvin
Jeff Blackburn
Leonardo Spanu
Matteo Pasquali
Joe Powell*
Matteo Maestri
Evgeni Penev
Boris Yakobson
Carl Mesters*
Shaojun Miao
(*retired)
20nm
f
1mm
1mm1mm
100nm
A B C
D E F
Fibers
Solvent
CNT powder
Mixer
Fiber spinning
PROCESSINGCNT SOLUTION
PROPERTIES
CNT + H2
PRODUCTION
Reactor & reaction/catalysis level
Solution level
Materials properties level
Program Flow
Testing
Catalyst
grow process
assess assess
model
scale
external CNT sources
3 GPa
104 L/d
$ $
timeline
efficiency
OUTCOMEValidated Process Model
for Plant ScaleupEconomic CNTF @3,000 T/yr
Rice2021
Taylor et al,Carbon, 2021
Nanoparticle Catalyst: Effect of Sulfur and Generation
Geometric Mean: 1.81 nmGeometric Std: 1.16
Mass Flow : 68.2 mg/hr
*Approx. 0.75 m between plasma
and measurement
Fe nanoparticle sizingsystem (TSI)
Radio Frequency Plasma Nanoparticle Generator
• Stable, controllable production of catalyst nanoparticles below 2 nm diameter
• Particle size stability proven up to 0.75 m from generation point• Direct catalyst injection, simplifies reactions to manage• At 2% Fe utilization will support CNT production rate of 1.35
g/hr with 5% residual catalyst concentration• Available commercial systems provide direct path to scaling
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S:F
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icle
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Particle Size (nm)
S:Fe = 0.134 (SS/IS)
S:Fe = 0.541 (SS)
S:Fe = 2.30 (SS)
S:Fe = 0.313 (IS)
S:Fe = 2.48 (IS)
*
• Sulfur promotes iron nanoparticle formation • Sulfur is found primarily on the surface of nanoparticles (w/ Technion)• The concentration of sulfur fed to the reactor does not influence the
composition of individual nanoparticles• Increasing sulfur content inhibits CNT growth
We are eliminating sulfur in our reactor due to:• detrimental effect on CNT growth• poor scalability options• reduce reaction complexity
~ 0.
2 -
0.7
m
*Yedinak et al., in preparation, Impact of Sulfur on Floating Catalyst Chemical Vapor Deposition Carbon Nanotube Growth via Changes in Catalyst Particle Nucleation Dynamics
Building new, catalyst generator
and injection system
1/r (surface/volume)
movableinjector
Gen-2 Fiber Spinning & Processing lineGen 2 spinning line installed in December 2020
Full operation by Feb 2021 (EHS)
Independent temperature controls
Dope
Coagulation bath
Wash bath
Three stretching points (can be extended)
Post-processing draw capability to broaden system design options
Decoupling “unit ops” for cost and energy efficiency
Proven flow at 10% wt concentration
(old line) Proven spinning at 10%; electrical OK, lower strength
6’ & 10’ coagulation bath
High throughput extruderDraw and wash rollers
High-speed winder
Full motor and temperature control
Temp. control at every process step
All components functional
Post-process drawing unit
Ongoing USANS study to probe fiber microstructure
(w/ Butler @NIST)
Biggest Challenges• Increase catalyst utilization• Minimize amorphous carbon• CNT fiber microstructure from high concentration spinning• “Killer app(s)”
Risk Reductiono Understood catalyst formationo Designed, built, and deploying new catalyst delivery systemo In-line catalyst size measuremento New analytical methods for in-line gas-phase analysiso Gen2 CNT Fiber spinning line expands operating parameters, decouples unit opso Multiple models: CNT nucleation/growth, microkinetic for thermochemistry, nanoparticle
formation, CFD reactor flow; deploying them in redesigns, will integrate modelso Collaborations for application developmento Collaborations for source CNTs
Partnerships and collaboration opportunities• carbonhub.rice.edu• Application development: we can provide material and expertise• CNT material conversion: we can (try to) make fibers, tapes from other’s CNTs• Form sub-team on catalyst generation and delivery? – Common issue across many platforms
Challenges and Potential Technical Partnerships
Dec 2019 Jan 2021 Sep 2022
T2M
• We are building an Integrated Process to Manufacture CNT Fibers with:• Competitive price vs. carbon fiber products at similar tensile strength• Scalable 3 GPa+ CNT Fiber with mass productivity that generates meaningful H2
• Opportunity: electrical & thermal conductivity, flexibility
Overall Programdeliverables
20nm
f
1mm
1mm1mm
100nm
A B C
D E F
Year 2oGen2 fiber spinning line, spin at 3 wt% and 3 GPaoGen1 CNT synthesis reactor + RF plasma catalyst, increase conversion and catalyst utilizationo TEA: refine spinning technoeconomic model to project cost at 3000 T/yr,
o Identify top 3 paths to achieveoWork with Michael Penev on Hydrogen modeling
o iCorps effort in 2nd half 2021 for market opportunities identification, customer engagemento Structural composites (existing focus)—collaboration with Mark Goulthorpeo Electrical Power Cables (new): Carbon Hub project, engagement with leading cable manufacturer
3 GPa, 10 wt % solution
$/kg
Year 3oGen2 spinning line, spin at 10wt% and 3 GPaoGen1 CNT synthesis scaled to 100 g/batch with 3um+ length, and 5 wt% residual catalysto Choose one or more applications to introduce material at next scale up
Spinning @ 10wt%, Gen2 Line, In-line and Post-Stretch Capabilities Deployed Microstructure Development
CNT Synthesis Process Efficiency and Control
Taylor et al,Carbon, 2021