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

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

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

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…

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)

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)

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

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

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

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)

Novel CO2 Capture Materials

Song at Penn State

Giannelis at Cornell and Park at Columbia

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

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

Coal, nat ural gas , and air

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)

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

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

Introduction of nanoparticles increases the viscosity of the system

Viscosity

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

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?

Now, we have CO2, what do we do?

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)

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

Overview of Small Scale Field Tests

24 http://www.westcarb.org/pdfs_bakersfield12/Brown.pdf

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

Effect of Mineralogy on CO2 Storage

26

Magnetite Anorthite Basalt Talc Augite Lizardite Antigorite Fayalite Forsterite Wollastonite 0

20

40

60

80

100

Ext

ent o

f Car

bona

tion

(%)

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

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

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

CO2 conversion and utilization?

Publications in CCUS

CO2 Utilization

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

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)

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

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

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-addedchemical 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]

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

Overview of Large Scale Field Tests

39 http://www.westcarb.org/pdfs_bakersfield12/Brown.pdf