CCUS in the USA: Activity, Prospects, and Academic Research - plenary presentation given by Alissa Park at the UKCCSRC Cardiff Biannual Meeting, 10-11 September 2014

1. Ah-Hyung Alissa Park Departments of Earth and Environmental Engineering & Chemical Engineering Lenfest Center for Sustainable Energy Columbia University UKCCSRC meeting, Cardiff, UK September 11th, 2014
CCUS in the USA:
Activity, Prospects, and Academic Research

2. http://www.ipcc.ch/report/ar5/wg1/#.Uk0OXVO8ySo

3. http://www.scientificamerican.com/article.cfm?id=latest-ipcc-climate-report-puts- geoengineering-in-the-spotlight

4. Towards Sustainable Energy and Environment
Gas
Synthesis
Refining
Use domestic energy sources to achieve energy independence with environmental sustainability
Use carbon neutral energy sources
Heat
Electricity
Carbon
Hydrogen
Chemicals
Ethanol
Methanol
DME
Gasoline
Diesel
Jet Fuel
Wind ,
Hydro
Geo
Nuclear
Solar
Fossil
Biomass
Municipal
Solid
Wastes
Integrate carbon capture, utilization and storage (CCUS) technologies into the energy conversion systems
Recycled CO2
Stored CO2
Fossil fuels are fungible…

5. Large-scale CCS projects in key markets by project lifecycle
North America continues to dominate the projects landscape; China increasing in importance; project progress has stalled in Europe
•
(Brad Page, CEO, Wye River Thought Leadership Forum, 24 June 2014)

6. Develop Technology Options for GHG Management

Capture Goals: captured cost of CO2 less than $40/tonne in the 2020- 2025 timeframe with longer commitments to extending R&D support to even more advanced transformational carbon capture technologies beyond 2035.

Carbon Storage: predict geologic storage capacity to within +/- 30% and permanence of geologic storage up to 99%. Increased EOR activities from 32 million tons of CO2 per year

Monitoring, Verification and Accounting (MVA)

CO2 Utilization: enhanced oil/gas recovery, CO2 as feedstock, non- geologic storage of CO2, indirect storage, beneficial use of produced water, breakthrough concepts
US DOE Goals (energy.gov)

7. Office of Coal and Power R&D Total FY 2012 Funding ~ $333 Million

Carbon Capture: $68.9 Million

Carbon Storage: $115.4 Million

Advanced Energy Systems: $99.9 Million

Advanced Combustion Systems: $15.9 Million

Gasification: $39 Million

Turbines: $15 Million

Fuel Cells: $25 Million

Fuels: $5 Million

Cross Cutting Research: $49.1 Million
US DOE Funding
http://www.westcarb.org/pdfs_bakersfield12/Brown.pdf

8. FutureGen 2.0
Artist's rendering of the proposed FutureGen plant (FutureGen Alliance)
FutureGen 2.0 will be the world’s first, near-zero emissions commercial scale coal-fueled power plant that is fully integrated with geologic carbon capture and storage • CO2 capture: Retrofitting an existing coal-fueled power plant in Meredosia, Illinois with cutting edge oxy-combustion clean coal technology • Transport: Construction of a CO2 pipeline from Meredosia to a CO2 storage facility • Storage: northeastern Morgan County, Illinois in Mt. Simon sandstone formation
Total capital cost is ~$1.65 billion ($ 1 billion from DOE and the rest is from the private sector); Construction to start in 2014 and operations to begin in 2017
On Sept 2, 2014, the EPA approved its injection permit

9. Collecting CO2 with Synthetic Trees
Current GRT Development
Mass-Manufactured Air Capture Units
GRT Pre-Prototype Air Capture Modules - 2007
From Technology Validation to Market-Flexible Products to Scalable Global Solutions
Courtesy GRT* *K. S. Lackner is a member of GRT

10. Carbon Capture, Utilization and Storage Technologies (CCUS)
Carbon Capture Technologies
Capture
Utilization
Storage

Required characteristics for CCS

Capacity and economic feasibility

Environmental benign fate

Long term stability

MEA Challenges

Corrosion and solvent degradation

High capital and operating costs

High parasitic energy penalty
(NETL, 2011)
(NETL, 2010)

11. Novel CO2 Capture Materials
Song at Penn State
Giannelis at Cornell and Park at Columbia

12. Solid Sorbents & Chemical Looping Technologies
Water-Gas Shift: CO + H2O  H2 + CO2
Carbonation / Calcination cycle
Oxidation / Reduction cycle
MO + CO2  MCO3 MCO3  MO + CO2
MO + CO  M + CO2 M + H2O  MO + H2
e.g., ZECA process
(Los Alamos National Lab)
e.g., Chemical Looping process for H2 production
(Ohio State Univ.: U.S. Patent No. 11/010,648 (2004))
KIER’s 100kW CLC system (2006-2011)
Micro- vs. Mesopores

13. Energy Frontier Research Center: gas separations
EFRC - Carbon Capture
Capture of CO2 from gas mixtures requires the molecular control offered by nanoscience to tailor-make those materials exhibiting exactly the right adsorption and diffusion selectivity to enable an economic separation process. Characterization methods and computational tools will be developed to guide and support this quest.
MFI
PPN-6
ZIF-78
Mg-MOF-74
HMOF-992
CaA

14. Coal, natural gas , and air

15. Carbon Capture, Utilization and Storage Technologies (CCUS)
Carbon Capture Technologies
Capture
Utilization
Storage

Required characteristics for CCS

Capacity and economic feasibility

Environmental benign fate

Long term stability

MEA Challenges

Corrosion and solvent degradation

High capital and operating costs

High parasitic energy penalty
(NETL, 2011)
(NETL, 2010)

16. Novel CO2 Capture Solvents (2011 & 2012 NETL CO2 Capture Technology Meeting)

Ionic liquids

CO2BOLs

Liquid-like Nanoparticle Organic Hybrid Materials

Carbonic Anhydrase (Enzyme)

Phase changing absorbents

17. Nanoparticle Organic Hybrid Materials (NOHMs)

Solvent-free liquid-like hybrid systems
Solvent tethered to nanoparticle cores
Zero-vapor pressure and improved thermal stability
Tunable chemical and physical properties
Liquid, solid, gel
Solvation in NOHMs driven by both entropic and enthalpic interactions
Straightforward synthesis
Easy to scale up

18. 
Introduction of nanoparticles increases the viscosity of the system
Viscosity

19. Effect of Water

Viscosity decreases in the presence of H2O and with T

Only small amounts of water are required to significantly reduce the viscosity

Water acts as an antisolvent for CO2

No apparent effect on thermal stability
Composition effect
Viscosity vs Capture Capacity
Petit et al., J. Colloid Interf. Sci. 2013, Submitted

20. CO2-to-Chemicals and Fuels

Development of multi-functional nanomaterials as a dual purpose reactive media

Investigation of interfacial reaction mechanisms

Combined CO2 capture and conversion

The use of heat of absorption during the reaction?

21. Now, we have CO2, what do we do?

22. Carbon Storage Schemes
Capture
Utilization
Storage

Mimics natural chemical transformation of CO2 MgO + CO2 → MgCO3

Thermodynamically stable product & Exothermic reaction

Appropriate for long-term environmentally benign and unmonitored storage

Ocean storage

Biological fixation

Geologic storage

Mineral carbonation
CO2 Injection Well
Gas Processing Platforms
1 million tons of CO2 injected every year since 2006
USD 100,000 saved daily on CO2 tax
Graphic courtesy of Statoil
(Geotimes, 2003)
Statoil’s Sleipner West Gas reservoir in the North Sea
600,000 tons of CO2 injected every year since 2004
In Salah Gas Project in Algeria
Graphic courtesy of BP (Geotimes, 2003)

23. Regional Carbon Sequestration Partnerships (DOE NETL)
Launched in 2003 7 partnerships 43 US states 4 Canadian provinces > 400 state agencies, universities, and companies involved
•
Characterization Phase (2003-2005)
•
Validation Phase (2005-2011): Small- scale CO2 injections (< 500,000 metric tons of CO2)
•
Development Phase (2008-2018+): Large-scale field tests at least 1 million metric tons of CO2

24. Overview of Small Scale Field Tests
24
http://www.westcarb.org/pdfs_bakersfield12/Brown.pdf

25. Various Feedstocks for Carbon Mineralization
Source: Kurt Houz
Availability silicate minerals >> industrial wastes Crystallinity industrial wastes < minerals Reactivity industrial wastes > minerals Pre-processing requirements (e.g., mining, crushing etc.,) industrial wastes < minerals
Carbonation of industrial wastes results in reclassification of these materials as non-hazardous hence safe for landfilling and for long-term carbon storage

26. Effect of Mineralogy on CO2 Storage
26
Magnetite Anorthite BasaltTalc Augite Lizardite Antigorite Fayalite ForsteriteWollastonite 020406080100 Extent of Carbonation (%)
Experiments performed at 185oC, PCO2 of 150 atm in 1.0M NaCl+0.64M NaHCO3. 15 wt. % solid Reaction time:
Abundance of less reactive minerals vs. limited availability of highly reactive minerals
1 hr
0.5 hr
4 hr
4 hr dry attrition grinding All others – 1 hour dry attrition grinding
Serpentine
Carbonation efficiency defines
whether mineral is utilized for
ex-situ or in-situ storage
Ex-situ CO2 Storage
In-Situ CO2
Storage
Shorter time scales (~hours)
Longer time scales (~years)
Limited spatial scale
Larger spatial scale with utilization of earth as a reactor (~hundreds of miles)
Relatively homogenous mineralogy
Heterogeneous mineralogy
More flexible tuning in reaction conditions
Possible production of value-added products
No monitoring required
Not limited by reactor size; Use of geothermal gradient
Multiple CO2 trapping mechanisms
Relatively economical at this time
O’Connor et al., AAPG Annual Meeting, 2003

27. Availability of Minerals
Basalt
Labradorite
Magnesium-based Ultramafic Rocks (Serpentine, Olivine)
Mineral Carbonation of Peridotite
Photo by Dr. Jürg Matter at LDEO (2008)
Belvidere Mountain, Vermont
Serpentine Tailings

28. Chemical and Biological Catalytic Enhancement of Weathering of Silicate Minerals as Novel Carbon Capture and Storage Technology
Serpentine
Dissolution reactor Mg3Si2O5(OH)4 + 6H+  3Mg2+ + 2Si(OH)4 + H2O
MgCO3
Mg2+(aq)
Flue gas
un-dissolved minerals
Carbonation reactor
Mg2+ + CO32-  MgCO3
CO32-(aq)
Bubble column reactor with CA CO2(g) + H2O  H2CO3 H2CO3  H+ + HCO3- HCO3-  H+ + CO32-
L/S separator
L/S separator
Recycled process water
silica
Industrial CO2 sources
Mine
Value-added products (e.g., paper fillers, construction materials)
Disposal (mine reclamation)
Bio-catalyst Make-up Carbonic anhydrase (CA)
Chemical catalyst Mg and Si-targeting Chelating agents

29. CO2 conversion and utilization?

30. Publications in CCUS

31. CO2 Utilization
http://www.netl.doe.gov/research/coal/carbon- storage/research-and-development/co2-utilization

32. CO2-EOR: the bridge to storage
Majority of projects in operation, construction or close to FID use or intend to use CO2 for EOR
(Brad Page, CEO, Wye River Thought Leadership Forum, 24 June 2014)

33. CO2 - EOR
33
80% of CO2 is from natural resources
•
12 Mt /yr from anthropogenic sources (e.g., coal gasification, gas processing)
•
50 Mt/yr from naturally occurring underground deposits
Long-term CO2-EOR Market Potential:
•
67 billion barrels of recoverable oil
•
40% of production
•
0.25 GT CO2 per year
EOR is projected to grow to 40% of US oil production
•
123 EOR projects
•
350,000 barrels of oil/day
•
6% of oil production
•
62 million tons of CO2
Source: http://neori.org/Melzer_CO2EOR_CCUS_Feb2012.pdf

35. 
Development of Multifunctional smart CO2 capture media

Integrated systems (e.g., chemical looping technologies, ZECA, and enhanced WGS using mineral carbonation) for process intensification and flexibility (production of heat, electricity, chemicals and fuels in any combination)

Use of industrial wastes (e.g., stainless steel slags, scrap metals)

Diverse portfolio of projects ranging from read to make market to highly innovative efforts

Wide range of injection projects – some more successful than others

Carbon Capture, Utilization and Storage

Need for international collaborations as demonstrated by PCOR project
Summary and Future Direction

36. Path Forward
32.6
3.7
1.6
1.4
0.4
0.3
0
5
10
15
20
25
30
35
Global CO2 emissions as of 2011
Total CO2 emissions avoided
Replacing 10% of building materials with carbonate minerals
Non-conversion use of CO2: EOR and solvents
Replacing 5% of liquid fossil fuel with biomass-based liquid fuel
Chemical and electrochemical conversion of CO2 into value-added
chemical feedstock
CO2 emissions (Gt/year)
[Data from: CO2 Utilization: N. Sridhar and D. Hill, 2011, Electrochemical Conversion of CO2 - Opportunities and Challenges, Research and Innovation - Position Paper 07-2011]

37. NSF RCN-SEES: Multidisciplinary Approaches to Carbon Capture, Utilization and Storage (CCUS) PI: Ah-Hyung Alissa Park (09/2012 – 08/2016, NSF Program Director: Bruce Hamilton)
CO2 Capture & Conversion Thrust Thrust leader: Petit & West Aines (LLNL), Panagiotopoulos & Bocarsly (Princeton), Chen, Coppens (UCL), Lee (SKU), Farrauto, Liu & Heldebrant (PNNL), Li (NCSU), Wang (Zhejiang), Park, Reimer (Berkeley), Snurr (Northwestern), Song (PSU), Wilcox (Stanford), Yegulalp, Zhang & Zhang (CAS-IPE), etc
CO2 Transportation, Storage & EOR Thrust Thrust leader: Matter (USH) & Brady (SNL) Baciocchi (UR-TV), Bonneville (PNNL), Blunt (Imperial), Bryant (UT Austin), Dipple (UBC), Dlugogorski (UNewcastle), Goldberg, Lee (KAIST), Park, Peters & Fritt (Princeton), Sageman & Husson (Northwestern), Wang (Yale), Zhu (Indiana), etc
CO2 MVA & Risk Analysis Thrust Thrust leader: Stute & Venkat Bonneville (PNNL), Goldberg, Lackner, Meinrenken, Park, Peters (Princeton), Romanak (BEG Texas), Zhu (Indiana), etc
Policy, Business & Law Thrust Thrust leader: Barrett & Gerrard Coppens (UCL), Fox (IMECHE), Lackner, Marcotullio, Shindell, Urpelainen, van Ryzin, Weber, Welton, van der Zwaan (ECN), etc
Industrial Thrust Thrust POC: Gupta (RTI) & Schuster (AIChE) B&W (Vargas), GE (Perry), RTI (Gupta), SK Energy (Park), ARAMCO (Katikaneni), ORICA Ltd. (Brent), POSCO (Jung), etc
Educational Thrust Thrust POC: Schuster & Pfirman
•
K-12: K-12 teachers (Buck and Miller)
•
Young Professional (TBA)
•
MCM at Columbia (Lackner)
•
Research Experience in C Science (Tomski)
•
Women in Science and Engineering (Gadikota)
•
Council of Environmental Deans and Directors (CEDD, TBA)
PE Society Thrust
Thrust POC: Keairns & Schuster (AIChE)
AIChE (TBA), AIME (TBA), ASCE (TBA), ASME (TBA), IEEE (TBA), Fox (IMECHE)
Project Management LCSE - Columbia University PI: A.-H. Alissa Park CU PMs: Taylor and Gadikota & AIChE team: Schuster
Steering Committee Thrust POC: Park Members: Park, Lackner, Schlosser, Kelemen & Mutter (Columbia), Aines (LLNL), Fan (OSU), Fitts & Socolow (Princeton), Jones (Georgia Tech), Keairns (AIChE), Mazzotti (ETH-Zurich), Rubin (CMU), Sageman (Northwestern), Smit (Berkeley), Snurr (Northwestern) and Song (Penn State)
* Columbia participants unless noted * International participants are in blue
RCN-SEES on CCUS
Interdisciplinary Research
Academic

39. Overview of Large Scale Field Tests
39
http://www.westcarb.org/pdfs_bakersfield12/Brown.pdf