the ENERGY lab
Hunaid NulwalaCarbon Capture Group (NETL)Assistant Research Professor
Carne gie Mellon University June 2015
New Materials Development for Carbon Capture Applications
Carbon Capture Technology Meeting, Pittsburgh, PA, June 2015
To boldly go where no one has gone before
• A future with no or little CO2 emission
• Cheap and abundant electricity
• Reliable electricity
We explore new ideas
• In-house NETL-ORD Carbon Capture FWP• Project performance dates: 10/1/2014 – 9/30/2015.• Total cost for transformation program $1.065M
• No cost share• Project objectives: Evaluate new materials and
characterize them to determine the potential forcarbon capture.
• TR 2-3 level
BOLDLY GO WHERE NO ONE HAS GONE BEFORE IN 1- 2 YEARS
Project overview:Transformational technologies
• It’s not:– Basic science– New synthetic methodologies– Pilot-scale testing– Commercialization
• It is:– Examination of novel classes of materials for capture– Exploration of innovative process configurations– Development of advanced screening approaches
What is the NETL-ORD role in transformation technology development?
And what is it not?
Integrated technology development
Process Synthesis & Techno-economic
assessment
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450
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Cost
of E
lect
ricity
[$/M
Wh]
Module Efficiency Factor [fraction]
COE Sensitivity to Module Separation Efficiency
Case 6 …$90/ft2 …
Case 6 1% Efficiency:COE= $291/MWhMembrane ~77% of TPC
Case 6 100% Efficiency:COE= $88.3/MWhMembrane ~3% of TPC
3.5% COEincrease (Case 6)
7% COEincrease (Case 6)
Performance AssessmentIn Real Environments
Material Synthesis & Fabrication
Characterization
Material Processing & DeviceDevelopment
Molecular Design & Optimization
SystemsAnalysis
Materials properties
SystemsFabrication
MaterialsSynthesis
Performance Criteria
Advanced solvents
• Focused on improve the CO2interactions.
• Intramolecular HB causesdecrease in viscosity which isdictated by the spacers.
• Effect of anion and cation onCO2 solubility was evaluated.
Choline-based ILs
H2NO
OHH2N
OO
+O
OH3N
OOH
NH2OHO
HOO
NH
+O
O
H3NO
OH
Simulations were performed by Hyung group in CMU (Fangyong Yan)
HO O NH2
HO ONH2
HOO
NH2
In the process of experimental verification
Advanced solvents
Carbamate Vs. Carbonate
No or little carbonate reaction
CO2 catalyst for amine solvents
H2O + CO2 HCO3- + H+
Zn coordinated water is 10000 more acidic
Carbonic acid formation is 107 faster in carbonic anhydrase
The catalyst is inspired by the function of carbonic anhydrase. (Uky)
• Collaborative work with University of Kentucky, Center for Applied Energy Research have developedcatalysts that boost carbon capture in aqueous amine solutions.
• Developing fundamental understanding of these catalysis.• Currently, Density Functional Theory Nudged Elastic Band calculations on a larger, condensed phase
is being carried out.• Via simulation clear evidence is seen of hydrogen bonded networks as well as a hydrophobic
region inside the catalyst, reminiscent of carbonic anhydrase.
Reaction Profile – Cluster Model
Condensed Phase Model
Lippert et al. Catal. Sci. Technol., 2014, 4, 3620.
CO2 catalyst for amine solvents
Energy efficient regeneration methodologies Redox-driven Regeneration of Amines: Material Development
Combination of innovative process and chemistry; voltage needs to be lower.
Energy efficient regeneration methodologies
• Voltage needs to be lowered
• Current state of the art is 0.5 V (needs to be lowered)
• Proof of concept completed
• Quantitative analysis is currently being performed.
CO2
N2O2
Provisional filed
Processing of materials
Ideal material in a system
ProcessabilityMechanically strong
Chemical and Environmental stability
Gas performance Criteria
6 min after removing from heat
HN
HN C
O
nCH2
6CH2
4CO
increasing concentration of choline chloride
Polyamides (Nylon 6/6)
Nylon film prepared
using acetic acid and choline chloride
Process enables preparation of polymer dope for film casting
20 µm
Nylon films are highly
porous
Innovative processing solutions
Innovative processing solutions
500 µm 500 µm
With choline chloride
Without choline chloride
Chlorine EDX map
Chlorine EDX map
100 µm
100 µm
100 µm
100 µm0.0
5.0
10 20 30 40 50
Inte
nsity
(a.u
.)
2 θ (degrees)
cotton + acetic acid + cholinechloride washed with H2Ocotton + acetic acid + cholinechloridecotton + acetic acid
native cotton
choline chloride
Cellulose Processing and modification
OO O
OHHO
OH
HOOH
O
OH
n
Able to add ionic content in the celluloseTo be evaluated for MMMUsing our insight in ionic liquids
Provisional filed
In-situ MOF growth in polymers
Zirconium MOF: UiO66
Patent pending
New simple, surface-templating approach to fabricate pure MOF membranes that can be transferred to other surfaces
We have developed a novel templating technique to make sheets of MOF materials
Formation of MOF thin films
Acknowledgements
• David Hopkinson (NETL)• Fangyong Yan (CMU)• Prof. Hyung Kim (CMU)• Robert Thompson (NETL)• Anne Marti (NETL/ORISE)• Larry Hill (NETL/ORISE)• John Watkins
(NETL/ORISE)• Jan Steckel (NETL)• Wei Shi (NETL)• David Luebke
