Clean Coal

Technologies

Robert C. Armstrong

Director, MIT Energy Initiative

Chevron Professor of Chemical Engineering

Carbon Capture, Utilization,

and Storage Opportunities

Global Energy Use As population and incomes

increase, energy needs and

desires will increase – almost

doubling energy use by 2050.

Most energy (~80%) will come

from the same sources currently

utilized: coal, oil and natural

gas.

There is an abundance of fossil

fuel resources:

Coal ~180,000 EJ

Oil ~ 35,000 EJ

Gas ~ 29,000 EJ

By 2050 fossil resources remain

plentiful. Their cumulative use to

2050 is:

Coal ~8,000 EJ

Oil ~ 9,000 EJ

Gas ~ 7,000 EJ 8

http://golbalchange.mit.edu/Outlook2013/

Energy Use by Major Group

• Nuclear and hydropower will increase mostly in developing nations, but not

significantly without mandate or policy changes.

• Energy use overall stabilizes in developed countries, grows substantially in other

G20 nations (to ≈500 EJ), and grows in the rest of the world to about what is

used presently by the developed world.

9

http://golbalchange.mit.edu/Outlook2013/

CO2 Flux Budget Emissions of CO2 are now 40 billion tonnes/yr. Fossil fuel

emissions have been accelerating

~ 45% remains in the atmosphere, ~ 26% ends up in the ocean, ~

29% on-land (plants & soils)

Seasonal variation of CO2 60 Gt (120 Gt/yr)

25% increase in atmospheric CO2 in past 50 years

40 Gt/yr Total CO2 Emissions by ―country‖ and per capita

China & India (mainly coal) growing fast

USA ~ 5 Gt/yr = 1/8 global

Per capita USA and Europe decreasing

USA per capita twice Europe and China

USA 16 t/person/yr ~ 27 m3/person/y at reservoir T & p

Socolow Wedges Burning of fossil fuels has tremendous, and growing, momentum

Unlikely to be stopped for decades

Vast, global problems require multiple solutions

Many candidates – Carbon Capture, Utilization & Storage a crucial

one

eqn.princeton.edu

CCUS – What Problems Must We Solve? Capture is expensive (30 - 60% additional energy penalty)

– Improvements in capture technology are needed

– Utilization provides incentive in the absence of regulations

– Regulations required for capture at necessary scale to be implemented

Meaningful quantities are huge – comparable to hydrocarbon use

5 Gt/yr equivalent to 40 Gbbl/yr

Global oil production: 34 Gbbl/yr

Wastewater injection ~ 100 Gbbl/yr

Transport is required if source is not adjacent to aquifer

Storage is challenging, must be demonstrated at scale:

– Large volumes of permanently isolated pore space required

– Pressure management needed to limit earthquakes

– Monitor for long time

Solutions to these problems can be applied globally

Heat Cool

CO2 Amine Amine/CO2 Complex

CO2

Amine

Electrochemically-Mediated vs Thermal Amine

Regeneration

CO2 Amine Amine/CO2 Complex

Add M++

M2+

CO2

Amine/Met

al

Complex

Remove M++ + -

Metal

Anode

Metal

Cathode M2+

M2+

T < 60⁰C T > 110⁰C

Cath

od

e

An

od

e

Desorber

CO2

Lean Gas

T < 60⁰C T < 60⁰C

T. Alan Hatton

Chemical Engineering

Adsorbents for CO2

Temperature (K）

Capacity (

mm

ol/g)

Temperature (ºC)

MOF,etc.

6

8

100 0 300 200 400 500 600 700

Activated carbon

PEI-impregnated porous silica (MCM41,etc.)

2

4

0

Ca

pa

city (

mm

ol/g

)

10

Aqueous

amine

12

14

C.W.Jones et al., ChemSusChem, 2009, 2, 796

MIT

Nitrate-coated

MgO Adsorbents

Metal-organic Frameworks Zeolites

Metal-Organic Frameworks:

Exquisite Control in the Solid State

10-2 m 10-3 mm 10-9 m 10-9 m (1 atom ~ 10-10 m)

1 g

5000 m2

Mircea Dincă

Department of Chemistry

Nanostructured Catalysts Electro- and Thermocatalytic Conversion of CO2

• Reduction or elimination of platinum group metal (PGM) use

• Improvement of activity by rationally tuning surface electronic properties

• A drastic increase in stability under reaction conditions

Objective: Use a molecular approach to gain a fundamental understanding of and to

engineer novel materials for CO2 activation. Catalyst must meet the design criteria for

sustainable and industrially-viable applications. We aim to achieve:

Nanostructured catalysts activate bonds in CO2

to generate valuable intermediates.

Yuriy Roman

Chemical Engineering

Core-shell Architectures Reduce PGM Loadings and Optimize Reactivity and Stability

Au/TMC NP Pt/TMC NP Pt/bimetallic TMC NP PtAu/TMC NP

> 90% reduction in PGM loadings

Sinter resistance over wide potential and thermal windows

Enable systematic optimization of CO2 conversion catalysts by controlling:

• NP size

• Bimetallic core composition: W, Mo, Ti, Ta, Ni, Cu, Co, etc.

• Bimetallic shell composition: Au, Pt, Ir, Ru, Rh, Pd

• Shell thickness

Impact on CO2 Catalytic Conversion Technologies:

Core-shell transition metal carbide – PGM nanoparticles exhibit remarkable performance during

activation of oxygenates (see. e.g., Hunt et. al. Angew. Chem. Int. Ed. 53 (2014)).

Yogesh (Yogi) Surendranath

Chemistry

Fuels/

Commodity

Chemicals

CO2

conversion

requires

catalysis

Catalysts must be selective to CO2

reduction versus H+ reduction

Can we change the pH at the

surface to improve selectivity?

Materials Design for CO2 Upgrading

Storage must be understood at the scale of

entire geologic basins

• Two constraints

– The footprint of the migrating CO2 plume must fit in the basin

– The pressure induced by injection must not fracture the rock

Ruben Juanes

Capacity estimates from fluid dynamics

• Storage capacity is dynamic

– For small injection times, overpressure is more limiting

– For long injection times, migration is more limiting

Ruben Juanes

Conclusion

• CCUS has the potential to be a key component in a

carbon mitigation portfolio

• Most studies show it can contribute between 15-20%

of the solution

• All components of a CCUS system are in

commercial use today

• However, must address issues related to integration,

cost reduction, and increasing scale of operations

• Biggest hurdle to moving forward is lack of climate

policy

Methane

Water

CO2

Oil

Physics of Multiphase Flow in Porous Media

Apply theoretical, computational and experimental

research to geophysical problems in the area of

energy and the environment

Ruben Juanes

Civil and Environmental

Engineering

Example of Observed Fracture Response: In Salah CO2 Injection

Observations (Onuma & Ohkawa, 2009) Model (Vasco et al., 2010)

Isotropic δv/v ~ 0.5%

Fracture opening ~ 7 cm

Isotropic point

source @ 1.9 km

Fracture point

source @ 1.9 km

Summary

• Strong interest across MIT Campus covering spectrum of issues on carbon capture, utilization and sequestration

• Build consortium around current CCS consortium, current/recent work on CCS, current MITEI member interest

• Three layers – CCS technology update, tracking, assessment. Includes database for

easy access

– Seed funds to stimulate new ideas for CCS

– Sponsored research - from individual sponsor projects to JIPs

• Strong faculty base and interest

• This will be an enabling technology to meet future energy needs in a carbon constrained world.

Pathways to Low-Carbon Fossil

Fuels

• Price signals

• Efficiency

• Fuel switching: coal gas

• Carbon Capture Sequestration, or CCS

• Kemper Plant – Construction started June 2010, Project start-up first half of 2016

– The Kemper County is now projected to cost almost $5.6 billion

– Mississippi Power received a $270 million grant from the

Department of Energy for the project

– Kemper County, one of the US flagship CCS projects has been

beset with delays and cost-increases

Carbon Capture Sequestration

Company Location Size Technology Fate

SaskPower

Boundary

Dam Power

Station

110 MW

retrofit

Amines

Cansolv EOR

Southern Kemper

County, MS

524 MW

3.4 MtCO2/yr IGCC

Transport Reactor EOR

Key Issues in Carbon Capture and

Sequestration

• Carbon capture

– Lower cost

• Sequestration

– Trapping mechanisms

– Long-term fate of CO2

– Monitoring / verification

– Induced seismicity

CCS Technologies: Pre-Combustion • The biggest challenge for pre-combustion capture is to

make an IGCC power plant competitive in cost to a PC power plant. A few years back, vendors like GE thought they could get capital costs for IGCC plants to within 10% of those of a PC plant. Unfortunately, this is not happening. While hard numbers are difficult to obtain, it seems the gap is greater than 30% today.

• Another challenge for IGCC plants is to accept a wider variety of feedstocks, specifically low-ranked coals with high ash and/or water content.

• Capturing of CO2 from IGCC plants is relatively straight-forward. The capital and energy requirements for pre-combustion capture are significantly less than post-combustion capture. However, those advantages cannot overcome the current premium required to build an IGCC plant (versus a PC plant).

CCS Technologies: Post-Combustion

• Most compatible with existing power plant infrastructure.

• There is a significant energy requirement associated with post-combustion capture processes. Thermodynamics places limits on how far we can reduce this energy penalty. By integration with the power plant, we may be able to take advantage of ―waste heat‖.

• Since this is an end-of-the pipe technology, it is capable of being used to retrofit existing plants. However, a major issue is how to supply the significant amount of energy required by the process. This probably means heat integration with the power plant, which complicates implementation for retrofits, and to a smaller degree, new plants.

• Several studies over the past two decades indicate that post-combustion capture is the ―best‖ approach for natural gas-fired power plants.

CCS Technologies: Oxy-Combustion • Because post-combustion capture is already established as a

commercial technology today, oxy-combustion must show clear advantages over post-combustion in order to have significant market penetration.

• Little field experience with oxy-combustion power plants (but there is oxy-combustion experience in other industries).

• There is a major effort to dramatically reduce cost of oxygen. One example is investigating the possibility of integrating ionic transport membranes into power boilers

• Oxy-combustion has been suggested for the following technologies, but not much analysis is found in the literature – CFB (circulating fluidized beds)

– Cement kilns

• Research is continuing in what are usually characterized as advanced oxy-combustion technologies – Chemical looping

– SOFC (Solid Oxide Fuel Cells)

Capture Technologies:

Vattenfall Schwarze Pumpe Plant

Challenges • Large Scale Demos

– Uncertainty

– We have yet to build a large-scale (>1Mt CO2/yr) power plant CCS demonstration

– This implies that 100s of power plants will need to capture and store their CO2

• Policy – global agreements

– accountability methods

– where to store

– carrying carbon dioxide across borders

• Cost – There has been little experience with configuring a price for all of

the components.

– The costs of pipelines depends primarily on the construction costs and operation and maintenance costs

Current Status: Bench-scale proof

of concept

Demonstrated operation for short cycles using off- the-shelve components.

Current efficiency ~ 65 - 70%

Bench-Scale Proof of Concept

Contact Information

Robert C. Armstrong Director, MIT Energy Initiative

Chevron Professor of Chemical Engineering

Email: rca@mit.edu

Phone: (617) 258 - 8891

Website: http://mitei.mit.edu/

Massachusetts Institute of Technology

Cambridge, MA

Global Energy Use -For 2014 Outlook, total

global primary energy use is

nearly identical here

compared to the 2013

Outlook

-In developed countries,

energy use will stabilize and

fall slightly (in part because

of the assumption that these

countries will meet their

Copenhagen-Cancun

pledges and, for Europe,

additional EU ETS

reductions for the post-2020

period)

-Global energy use by fuel

also remains dominated by

fossil fuels.

8

http://globalchange.mit.edu/ - 2014 Outlook

Global Energy Use -In terms of energy and

emissions, the two most

important countries are China

and India.

-By 2050, primary energy use

grows to nearly 300 EJ in China

and 100 EJ in India

-China’s projected 2050

consumption alone is 50% more

than the total consumption of

Developed countries today

-While India’s energy

consumption is only about 1/3

that of China, India remains

almost entirely fossil

energy-based

-In contrast, China has

extensive plans to diversify

energy supply, expanding

nuclear, hydro, renewables and

gas, which leads to coal use

flattening out 8

http://globalchange.mit.edu/ - 2014 Outlook

• Launched in 2006

• Cross-campus Initiative

• Broad … but focused on energy and associated environmental challenges

• energy production, delivery, use, and associated environmental linkages

• Four Components

• Research

• Education

• Campus Energy Management

• Outreach

Linking Science, Innovation, and Policy to Transform the

World’s Energy Systems

About MITei

Changes in Energy and Emissions: expects world energy use to double

by 2050 due to:

– increased energy use in developing countries

– increased access to personal vehicles in wealthier populations

• Global emissions are expected to double by the end of the century

• Globally, clean energy sources will make some progress, but the energy

mix will still be predominantly fossil fuel in 2050

Changes in Climate: predict accelerated changes in global and regional

temperatures, precipitation, land use, sea level rise and ocean

acidification.

Changes in Water Flows: Annual freshwater flow increases globally by

about 15% by 2100. By the end of the century, total water withdrawals are

projected to increase by about 19%. http://globalchange.mit.edu/ - 2014 Outlook

2014 Energy and Climate Outlook

• Expectations for the 2015 UN Climate Agreement: Likely efforts will further

bend the curve of emissions growth, with an estimate of 68 Gt CO2-eq emissions

in 2050—about 9 Gt less than our Outlook estimate for 2050.

Economic Growth:. The IMF’s projection shows slightly slower recovery from the

recession, with the global average annual GDP growth rate from 2010 to 2015

only 0.08% lower compared to the 2013 Outlook, mostly attributed to 1.1% slower

growth in China during that period. After 2015, the most substantial changes are in

China (where the average annual GDP growthrate through 2050 is reduced by

0.5%) and India (where the average annual GDP growth rate through 2050 is

increased by almost 0.15%).

Slower Energy Efficiency Improvement in China: New information suggests

slower efficiency improvement in industry than in our 2013 Outlook, somewhat

counterbalancing the effect of slower GDP growth on energy use.

http://globalchange.mit.edu/ - 2014 Outlook

2014 Energy and Climate Outlook

2013 Energy and Climate Outlook

• Incorporates 2020 emissions reduction targets G20 nations made at the 2009 UN Framework Convention on Climate Change (i.e. Copenhagen pledges) and further specified in Cancun in 2010

• Reports results for 3 broad groups: – Developed countries (USA, Canada, Europe, Japan, Australia

and New Zealand)

– Other G20 nations (China, India, Russia, Brazil, Mexico, and several fast-growing Asian economies)

– The rest of the world

• Work of the MIT Joint Program on the Science and Policy of Global Change

http://golbalchange.mit.edu/Outlook2012/

Carbon Capture Sequestration is not a single

technology, but a collection of technologies. All key

components of a CCS system are in commercial use

The Boston Globe, ―MIT

smokestack scrubber

promises lower costs,‖

Feb. 2, 2015