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

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0.20

0.0 10.0 20.0 30.0 40.0 50.0 60.0

S:F

e R

atio

(Part

icle

)

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