Future Fossil Fuel Usage &

Carbon Capture Technologies

Dr Paul Fennell

Department of Chemical Engineering and Chemical Technology, ICL

Summary

(1)CCS is not a synonym for clean coal

(2) There is an urgent need for accelerating full-scale

deployment

(3)There are major non-technical barriers

(4)There is a need to reduce the cost of capture

(5) New technologies must use basic engineering / lifecycle analysis to

demonstrate feasibility. This should be done before public money

is spent.

Questions...

What is CCS?

What are the barriers to capture?

What are the barriers to storage?

What are the overall barriers for the technology?

Why CCS?

Today all major economies

are underpinned by the

use of fossil fuels

Figure: CO2 emissions from

the combustion of fossil fuels,

excluding use in cement

industry Boden T, Marland G Andres RJ. Carbon

Dioxide Information Analysis Centre

Oak Ridge National Laboratory, Oak

Ridge, Tennessee

CCS, alongside increased renewable sources, energy efficiency , nuclear

and lifestyle changes, is a critical to mitigate against climate change

Space in the atmosphere is in shorter supply than fossil fuels

Basic data from IPCC 3rd assessment report

CARBON IN

FOSSIL FUELS

CARBON THAT CAN BE EMITTED TO

ATMOSPHERE

1990-2100

‘Unconventional oil’ includes oil sands and oil shales. Unconventional gas’ includes coal bed methane, deep geopressured gas etc.

but not a possible 12,000 GtC from gas hydrates.

Space in the atmosphere is in shorter supply than fossil fuelsCarbon in atmosphere vs. carbon in fossil resources

“ What is

CCS? ”

&

“ Why CCS is

not just a

synonym for

clean coal? ”

pre-combustion

oxy-fuel

post-combustion

coal, gas and/or

biomass

power plant

boiler,

fluidised

bed,

industrial

furnace

electricity, heat

CO2

captureflue

gas

high-pressure/

high-purity

CO2

for

transportation

& storage

N2

CO2

coal and/or

biomass

gasifier

reformer

shift

reactor

CO2

capture

electricity,

heat and/

or H2

CO2

air

air, O2

gas or oil

steam

CH4

H2

airair

separation

unit

O2

coal, gas and/or

biomass

N2

CO2

CO2

CO

CH4

H2

electricity, heat

CO2

CH4

H2

power plant

boiler,

fluidised

bed,

industrial

furnace

Technology options

Pre-combustion

• partially oxidise the fuel to CO(2) and H2, separate them, and burn the H2 in a (modified) gas turbine or fuel cell.

– Integrated Gasification Combined Cycle

– Chemical Looping Combustion

– ZECA process

Post-combustion

• Burn the fuel as usual in a (more-or-less) unmodified power plant.

• Add on a separate separation unit to remove CO2.

– Solvent Scrubbing

– Calcium looping

– Chemical Looping Combustion (alternate schemes)

Oxyfuel

• Burn the fuel in a mixure of pure O2 and recycled flue gas (to moderate the temperature)

CO2 capture technology overview

Post-combustion capture

http://www.bellona.org/imagearchives/

Heat input for

regeneration of

solvent accounts

for decrease in

process /cost

efficiency

‘End of pipe technology’,

can be retrofitted

Post-combustion capture

Closest to market technology:

Amine (MEA) Scrubbing

MEA scrubbing

• CO2 – rich gas is

exposed to MEA (15 –

30 wt. %) in a scrubbing

column, at around 55oC,

at a pressure of 1 bar.

• The loading of CO2 at

the exit of the column is

around 0.4 mol CO2 /

mol MEA.

• The CO2 is then

removed from the MEA

by boiling (at a pressure

of ~ 2 bar and a

temperature of ~120oC).

Loading = 0.15 .

Capturing the CO2 from the

power station has to reduce

its efficiency, relative to a

non- capture power station.

Thus, there are two costs

for CO2. The cost for CO2

captured (CC), and the cost

for CO2 avoided (CA).

The costs are related by the

fractional efficiency penalty

(EP).

CC = CA (1 – EP)

Thus, the capture cost is

always lower than the cost

for avoidance.

MEA scrubbing

Advantages

(i) Industrial experience – although much smaller scale

(ii) Known costs (?)

(iii) Post combustion method requires minimal changes to

the power station and suitable for retrofit (applicable to

other post-combustion methods)

Disadvantages/technical challenges

(i) Corrosion of equipment in the presence of O2 and other

impurities

(ii) High solvent degradation rates due to reaction with

oxygenated impurities

(iii) High energy requirements

(iv) Potential emissions of solvent to the environment

(v) Very large equipment required due to the huge volumes

of flue gas

Post-combustion carbonate looping

E.g. Shimizu et al, 1999

Advantages

(i) sorbent derived from cheap and abundant natural limestone

(ii) relatively low efficiency penalty

(iii) synergy with cement production

(iv) technology proven on medium scale plant

Disadvantages

(i) deactivation, particularly in the presence of sulphur,

(can be reactivated, but increases plant complexity)

strategies exist to reduce deactivation

(ii) produces hot CO2 – wastes energy unless the system is

pressurized

(iii) particle attrition

Post-combustion carbonate looping

EU CaOling project – first of a kind demonstration (2 MW).

Re-use spent sorbent in cement plant

kiln/cooler/grinder

raw meal cement

Cement production using spent sorbent

3 kW spouted bed reactor

•This work used ‘pure’ oxides instead of typical raw materials (e.g. sand/clay) to allows any change in the concentration of trace elements in the sorbent to be measured

Dean et al. Energy and Environmental Science , 2011

CaO+SiO2+Al2O3+Fe2O3

ground, mixed and fired at 1450 °C

Technology readiness level

1.7 MWth pilot taking slip stream from the Hunosa 50 MWe CFB coal power plant,"La Pereda“, Spain

pre-combustion

oxy-fuel

post-combustion

coal, gas and/or

biomass

power plant

boiler,

fluidised

bed,

industrial

furnace

electricity, heat

CO2

captureflue

gas

high-pressure/

high-purity

CO2

for

transportation

& storage

N2

CO2

coal and/or

biomass

gasifier

reformer

shift

reactor

CO2

capture

electricity,

heat and/

or H2

CO2

air

air, O2

gas or oil

steam

CH4

H2

airair

separation

unit

O2

coal, gas and/or

biomass

N2

CO2

CO2

CO

CH4

H2

electricity, heat

CO2

CH4

H2

power plant

boiler,

fluidised

bed,

industrial

furnace

Technology options

Pre-combustion capture

Integrated gasification combined cycle (IGCC)

Key chemical reactions

Gasification

fuel + O2/H2O/CO2 → H2,CO2,CO,CH4 + char + tar

Shift

CO + H2O ↔ CO2 + H2

Exothermic, conducted over a Ni catalyst

(poisoned by sulphur), pressure independent

Reforming

CH4 + 2 H2O ↔ CO + 3 H2

Endothermic, pressure sensitive, i.e. higher

pressure enhances methanation

These reactions lead to a H2-rich fuel gas, CO2can be separated from this gas mixture

H2,

CO2,

CH4,

CO

Reform

H2,

CO,

CO2

CH4 + 2 H2O → CO2 +4 H2

Shift

CO + H2O → CO2 +H2

H2,

CO2

CCS

H2

CO2

H2,

CO2,

CH4,

CO

Shift

H2,

CO2,

CH4

CCS

H2,

CH4

CO2

gasifier

H2,

CO2,

CH4,

CO

CCS

H2

CH4

CO

CO2

CO + H2O → CO2 +H2

Inc

rea

sin

g c

os

t a

nd

de

cre

as

ing

CO

2

Emissions equivalent to natural gas

fired power station

“Clean”

H2

stream

for FC

gasifier

gasifier

H2 rich fuel gas

Pre-combustion capture

Extra steam

(or water quench)

Jon Gibbins, Imperial College London, New Europe, New

Energy. Oxford, 27 Sep 2006; IEA GHG www.ieagreen.co.uk

FutureGen – $ 1.5 billion US clean coal concept

www.fossil.energy.gov/programs/powersystems/futuregen/

FutureGen timeline

Oxyfuel

Oxyfuel

Oxy-fuel

Advantages

(i) Technology suitable for retrofit (burners)

(ii) Comparatively simple

Disadvantages/ technical challenges

(i) Leaks (air inwards reduce purity)

(ii) Pure O2 (pneumatic conveying difficult)

(iii) Burner redesign (high CO2 makes flame properties different)

(iv) Safety concerns

(v) CO2 purity (?)

(vi) O2 produced using air liquefaction is energy intensive and

extremely costly

Schwartze Pumpe

30 MWe test

facility

Chemical Looping

• Chemical Looping Combustion – Richter and

Knoche (1983), Ishida et al (1987)

• Thermal efficiency (Power stations)

• Advantages:

• Efficient and low cost fuel combustion

• Facilitates CO2 Separation (H2O (l)↓)

• Fuel Reactor (Mainly Endothermic)

• (2n+m)MeO + CnH2m ⇒ (2n+m)Me + mH2O +

nCO2 (Complete oxidation)

• (n)MeO + CnH2m ⇒ (n)Me + ((½)m)H2 + nCO

(Partial oxidation)

• Air Reactor (Exothermic)

• Me + ½O2 ⇔MeO

Air Fossil Fuel (H2O)

CO2, H2O N2, Unreacted O2

Air reactor

Fuel reactor

Me

MeO

(CO, H2)

Background

Heat

(H2O)

(H2)

Qo

(Me + H2O ⇔ MeO + H2)

(Re- Generator)

(Reformer)

Chemical Looping Combustion

Thousands of hours running

98 % Fuel Conversion

99.7 % CO2 capture

Low attrition

Controllable, and Scalable

Photograph courtesy of A. Lyngfelt, Chalmers U.

SCALE-UP & DEMONSTRATION

Chalmers University 100 kWth 2011

Darmstadt 1 MW pilot plant (Courtesy TU Darmstadt)

Both technologies have significant future potential for the future – and this is

demonstrated by both technical feasibility, systems and economic analysis

•Both technologies are moving to scale (1 – 2 MWth)

•Both carbonate looping and chemical looping are could be built soon, and would have

significantly higher efficiencies than standard post-combustion CO2 capture.

•Further research is necessary to continue improvements in attrition rates, reactivities,

oxygen capacity and to investigate sulphur resistance, NOx production, etc.

Summary of Chemical and Carbonate Looping

Ionic liquids as solvents

• What is an Ionic liquid?

• Physical Properties

• Chemical Properties

• Industrial Applications

• Current Research

• Challenges and Opportunities

Ionic liquids

• When you heat a salt it will melt (e.g., NaCl,

801°C)

• The melt is composed of mobile ions (ionic

liquid)

Many ion choices

• Ionic liquids are salts that are liquid at or near

room temperature

1-Butyl-3-methylimidazolium [C4C1im]

Tributylmethylphosponium [P4441]

N,N-Butylmethylpyrrolidinium [C4C1py]

Cations

Anions

Triflate Dicyanamide Methylsulfate Dimethylphosphate Acetate

Properties of Ionic Liquids

• Involatility

• High thermal stability

• High polarity

• High density

• High conductivity

• Large liquid range

• Chemically inert

• Variable hydrophilicity

• Synthetic flexibility

• Easily sourced

• Very high viscosity

• Difficult recovery

• Expensive?

• Toxic?

efficiency penalty reduction = cost reduction

Eg, post-combustion using amine- solvent imposes an efficiency penalty of 10–12 points

45 - 12 = 33 %, equivalent to 25 % reduction in power output for amine PC capture

amine-solvents ~ 25 % > solid sorbents ~ 17 % > chemical looping ~ 8 %

Technology readiness levels (TRL)

TRLs Status

Applied and strategic research

1 Basic principles observed and reported

2 Technology concept and/or application formulated

3 Analytical and experimental critical function and/or characteristic proof

of concept

4 Technology / part of technology validation in a laboratory environment

Technology validation

5 Technology / part of technology validation in a working environment

6 Technology model or prototype demonstration in a working

environment

System validation

7 Full-scale technology demonstration in working environment

8 Technology completed and ready for deployment through test and

demonstration

9 Technology deployed

Developed by Nasa and adapted by the

UK Advanced Power Generation

Technology Forum

Technology readiness levels (TRL)… author’s opinion

based on literature survey and publicly available data

Technology TRLs

Post combustion capture with MEA 6

IGCC with physical solvents (e.g. Rectisol process) 6

Oxy-combustion 5

Post-combustion carbonate looping 4–5

Chemical looping combustion 4

Sorbent enhanced reforming 3–4

Post-combustion with algae 3–4

Post-combustion capture with “second generation” sorbents, e.g.:

supported amines, ionic liquids

2–3

Membranes for CO2 capture 2–3

ZECA 1–2

Barriers to Uptake?

Cartoon from

Nature News

Feature, Vol. 454,

August 2008

Public acceptance

is the major barrier

for the deployment

CCS

Efficiency losses

Technology Current state-of-the-art

efficiency / efficiency loss

Target efficiency /efficiency

loss for 2020

Steam Cycle Efficiency (LCV) ~ 45 % ~ 50 – 55 %

CCS-post combustion ~12 % points ~8 % points

CCS-oxy fuel ~10 % points ~8 % points

CCS – pre combustion ~7 - 9 % point ~5 -6 % point

CCS gas – post com ~ 8 % points ~7 % points

CCS gas - oxyfuel ~11 % points ~8 % points

Now Currently would produce around 25% less electricity for

the same amount of coal burned

20 years 14 – 16 % less electricity than equivalent without CCS

40 years Penalty eliminated (intrinsic separation processes)

Demonstration http://www.bellona.org/ccs/ccs/

Demonstration

CO2 sources http://www.bellona.org/ccs/ccs/

Demonstration

CCS projects: possible, speculative,

operational

http://www.bellona.org/ccs/ccs/

Demonstration

CCS projects: operational http://www.bellona.org/ccs/ccs/

CCS in UK

Project Technology Funding Timing

Longannet

(Scottish Power)

300 MWe

Post-combustion

capture, transport

and storage

Awarded

FEED

contracts,

CCS

competition

Planned for

2014

Kingsnorth

(E.On)

300-400 MWe

Post-combustion

capture, transport

and storage

Awarded

FEED

contracts,

CCS

competition

Investment

decision to be

reviewed in

2016

No new

coal

without

CCS

4 full-

scale, full

chain

demos

CCS in the UK (more hopeful) – second competition

Project Technology Funding Timing

Peterhead (SSE

and Shell) 386 MWe

Drax / Alstom 426 MWe Oxyfuel

Killingholme

C.Gen

430 MWe

Precombustion

Don Valley

(Stainforth)

900 MWe

IGCC capture,

transport and storage

180M (EUR)

EC funding

EEPR

Planned for

2015

Hunterston (Ayr) 300 MWe Post

Combustion

Mired in

planning

Tees Valley

(progressive

energy)

800 MWe IGCC

IEA Energy Technology Perspectives 2008

CCS is as big as renewables in 2050 – actually very soon.

How do we get comparable support and activity now?

Fossil fuel is important for grid stability and is the only way to absolutely

prevent future emissions from fossil fuels (lock them underground as CO2!).

Makes power cheaper by increasing flexibility of generation.

Global deployment of CCS , IEA CCS roadmap

100 by

2020

&

3400 by

2050

A lot of

work to

do!

IEA, technology

Roadmap, CCS,

2010

E.ON

Robin Irons

Doosan-Babcock

Gnanam Sekkappan

Imperial

Mathieu Lucquiaud,

Hannah Chalmers

Jon Gibbins

IEA GHG

John Davison

• The aim of building new power plants that are capture ready is

to reduce the risk of stranded assets and ‘carbon lock-in’

• Developers of capture ready plants should take responsibility

for ensuring that all known factors in their control that would prevent

installation and operation of CO2 capture have been identified and

eliminated

• Key issues include: space for capture equipment, access to

geological storage

• Guidance on space requirements: DECC (Florin and Fennell)

IEA GHG Report 2007/4, May 2007.

http://www.iea.org/textbase/papers/2007/CO2_capture_ready_plants.pdf

CO2 capture-ready plants

Bio- energy with CCS (BECCS) Potential to achieve net removal of CO2 from the atmosphere, or –ve emissions

biomass-fired in a power station

CO2 removed from the atmosphere in trees and crops

CO2 captured and stored in geological formation

E.g. biomass burned in power plant (other examples in the pulp and paper industry, ethanol plants, CHP plants which emit of the order of 100 000 tonnes pa ) Is scaleable. Costings are done / being done.

Conclusions

CCS is a new technology, but one which is currently being

demonstrated at increasingly large scale

Storage is safe

Plants in the UK must now be built capture-ready

UK Government + Climate change committee are supportive of the

technolgy

Large number of different technologies proposed (and I’ve just

presented the major ones). No clear winners yet.

Efficiency Penalties being reduced.

Only technology for certain applications (for example, cement).

CO2 capture From the Air

• It is possible to capture CO2 direct from the air

• It is possible for me to generate electricity with a hand crank

• Is it a good idea?

• Is it scalable?

• Should we ask people other than the purveyors of the technology to do

independent analysis?

• How likely is it that a technology which now costs $250,000 per unit will cost

$25,000 with economies of scale?

• Heath and Safety, efficiency, LCA?

• Is it easier to take water from a river or to condense it out from the air?

• Claims of efficiency often rely on minimal stripping of air – 1 ppm removed...

CO2 Re-utilisation

Source Annual CO2

production (MtCO2)

Percentage of Total

Emissions

Power 2530 84.0%

Refineries 154 5.1%

Iron & Steel 82 2.7%

Gas

Processing

77 2.6%

Cement 62 2.1%

Ethylene 61 2.0%

Ethanol 31 1.0%

Ammonia 7.8 0.3%

Hydrogen 6.8 0.2%

Ethylene

Oxide

1.2 0.0%

TOTAL 3013 100%

Process Global Annual

CO2 Usage

Typical source

of CO2 used

Lifetime of

storage

Urea 65-146Mt^ Industrial 6 Months

Methanol 6-8Mt Industrial 6 Months

Inorganic Carbonates 3-45Mt # ? Decades

Organic Carbonates 0.2Mt ? Decades

Polyurethanes 10Mt ? Decades

Technological 10Mt ? Days to Years

Food and drink 8Mt ? Days to Years

TOTAL 102 – 227Mt

Notes:

^, # The demand for CO2 in Urea and Inorganic Carbonate production is

particularly uncertain. Various sources have quoted figures with orders of

magnitude differences.

USA ONLY GLOBAL

Sources outweigh sinks by several orders of magnitude (more than a factor of 100).

The storage of CO2 is frequently short term.

The huge volume of CO2 produced means that any by-product of CO2 at the scale

required to make a difference in climate terms will immediately saturate the market.

The use of CO2 as a novel feedstock is a good idea if it is justified by the economics –

but will not have significant climate benefit, particularly if the storage is short term.

Global ~ 10 x USA emissions

CO2 + 3 H2 = CH3OH + H2O

• Production of liquid fuels from “excess” or “free” renewable energy

• Is there such a thing?

• There is always an opportunity cost – always something else which can be done.

• Is this an efficient way to store the electricity?

Efficiency

H2 from water 50%

H2 + CO2 80%

Use of fuel in ICE 30%

Overall 12%

Efficiency

Pumped hydro 70%

Battery charging1 90%

Electric Vehicle 90%

Overall 57%

Methanol Production and Use Electric Vehicle

Efficiency

Battery1 90%

Electric Vehicle 90%

Overall 81%

1Stevens, J.W. And Corey, G.P. A study of lead-acid battery efficiency near top-of-

charge and the impact on PV systems design. Photovoltaic specialists conference,

1996. 13 – 17 May 1996, Washington DC, USA.

What is the capacity factor for equipment relying on “free” renewable energy? Won’t the

power systems engineers be trying to minimise this?

Mineralisation

• Securely locks away CO2 by reaction with rocks such as serpentine to

produce carbonate rocks

• 3 – 6 times more rock required to be mined than the coal from which it is

capturing the CO2 (basic mass balance)

• Needs to be ground to <100 microns before reaction – electricity use

very significant1

• Reaction slow – approximate sizing for 500MWe equivalent = 4000

tonnes of stone reacting at any moment, with 16,000 tonnes of acid, for a

perfect reactor.

• 100 tonne railway carriage of acid / stone sludge every 8 minutes.

• Scale-up? Contact with CO2? Disposal? LCA (mining CO2 emissions?).

• What else could we do with the resources deployed for this mining?

• Not a viable technology for power stations but does have niche

applications in waste / residue treatment.

1Strubing, MSc, Imperial College, 2007.

Conclusions

• There are more efficient CO2 capture technologies than those

currently planned for deployment.

• Some of these may be easier to scale than solvent scrubbing

towers.

• Future processes must at least demonstrate order-of-magnitude

feasibility before funding

• Once kinetics are available, rough flowsheeting and LCA is critical,

together with consideration of Capex and utilisation factors.

• Some processes can be discarded at this stage.

• Chemical Engineering is not about making interesting but

economically unviable processes.

• There is always an opportunity cost, and this should be considered.

All those who who have been part of the Fennell group at Imperial:

Dr Nick Florin, Dr. Nigel Paterson, Dr. Belen Gonzalez, John Blamey, Dr Mohamad

al-jeboori, Dr Fatima Nyako, Dr. Yatika Somrang, Michaela Nguyen, Charlie Dean,

Kelvin Okpoko, Zhang Zili, Zhou Xin, Tong Danlu, Fola Labiyi

All our collaborators elsewhere:

Prof. Ben Anthony, Dr. Yinghai Wu, Dr. Vasilije Manovic, Dr. Dennis

Lu and Robert Simmons of CanmetENERGY

Prof. Carlos Abanades of INCAR-CSIC

Drs Dennis and Scott at Cambridge

Thanks to John Dennis at Cambridge for his slides on Chemical looping Jason Hallet, Imperial College dept of Chemistry, for slides on ionic liquids Andres Sanchez at Endesa for slides regarding Caoling

Acknowledgements

Acknowledgements

•The research leading to these results has

received funding from:

•Engineering and Physical Sciences Research

Council (EPSRC), UK

•Grantham Institute for Climate Change, IC –European Community's Seventh Framework Programme(FP7/2007-2013)

under GA 241302-CaOling Project

Dr Paul Fennell (p.fennell@imperial.ac.uk)

Department of Chemical Engineering and Chemical Technology, ICL

http://www3.imperial.ac.uk/climatechange/publications

Basic Information

Advanced Information An overview of CO2 capture technologies

Niall MacDowell, Nick Florin, Antoine Buchard, Jason Hallett, Amparo Galindo, George Jackson, Claire S.

Adjiman, Charlotte K. Williams, Nilay Shah and Paul Fennell *

Energy Environ. Sci., 2010, 3, 1645-1669

DOI: 10.1039/C004106H, Review

For Further Information:

• Blamey, J., Anthony, E. J., Wang, J., Fennell, P. S.; The calcium looping cycle for

large-scale CO2 capture; Prog. Energy Combust. Sci. 2010 36, 260-279

• Blamey, J., Paterson, N. P. M., Dugwell, D. R., Fennell, P. S.; Mechanism of Particle

Breakage during Reactivation of CaO-Based Sorbents for CO2 Capture; Energy &

Fuels 2010, 24, 4605-4616

• Blamey, J., Lu, D. Y., Fennell, P. S., Anthony, E. J.; Reactivation of CaO-Based

Sorbents for CO2 Capture: Mechanism for the Carbonation of Ca(OH)2; Industrial &

Engineering Chemistry Research, 2011, 50, 10329-10334

• Gonzalez, B., Blamey, J., McBride-Wright, M., Carter, N., Dugwell, D., Fennell, P.,

Abanades, C.; Calcium Looping for CO2 Capture: Sorbent Enhancement Through

Doping; Energy Procedia, 2011, 4, 402-409

• Fennell, P. S., Al-Jeboori, M.; CaO-based Sorbent Enhancement through Doping;

UK Priority Patent Application number 1114105.8, filed on August 16, 2011 in the

name of Imperial Innovations Ltd

• Donat, F., Florin, N. H., Anthony, E. J., Fennell, P. S.; The influence of high-

temperature steam on the reactivity of CaO sorbent for CO2 capture; Environmental

Science and Technology (submitted)