CEP April 2009 www.aiche.

org/cep 33
DOEs National Energy Technology
Laboratory is spearheading R&D on a
variety of post-combustion and oxy-combustion
technologies to cost-effectively achieve
90% CO
2
capture.
Jared P. Ciferno
Timothy E. Fout
U.S. Dept. of Energy, National
Energy Technology Laboratory
Andrew P. Jones
James T. Murphy
Science Applications
International Corp.
C
oal-red power plants generate about half of the
electricity in the United States today, and will con-
tinue to be a major source of energy for the fore-
seeable future. The U.S. Dept. of Energys (DOE) Energy
Information Administration (EIA) projects that the nations
300+gigawatts (GW) of coal-red electricity-generating
capacity currently in operation will increase to more than
400 GW by 2030 (1).
However, electricity production from fossil-fuel-based
power plants will be challenged by growing concerns that
anthropogenic emissions of greenhouse gases (GHG),
such as carbon dioxide, are contributing to global cli-
mate change. The existing eet of coal-red power plants
emits about 2 billion tons of CO
2
annually, accounting for
roughly two-thirds of the total CO
2
emissions from the
U.S. power sector. Moreover, as shown in Figure 1, more
than 90% of the CO
2
emissions expected to be emitted
from coal-red plants from 2007 through 2030 will origi-
nate from todays existing coal-red power plants, since
less than 4 GW of capacity is likely to be retired during
that period (1).
Carbon dioxide emissions could be regulated in the
near future to address climate change. Recognizing that
current CO
2
-capture technology is not cost-effective
and has not been demonstrated at scale, DOEs National
Energy Technology Laboratory (DOE/NETL) has initiated
a research and development program directed specically
at post- and oxy-combustion CO
2
-capture technologies
that can be retrotted to existing coal-red power plants,
as well designed into new plants. The goal of this effort,
which is being carried out as part of the Existing Plants,
Emissions and Capture (EPEC) Program, is to develop
advanced CO
2
-capture and compression technologies for
both existing and new coal-red power plants that, when
combined, can achieve 90% CO
2
capture while limiting the
increase in cost of electricity (COE) to no more than 35%.
This aggressive R&D plan aims to develop multiple CO
2
-
capture options capable of meeting the cost and perfor-
mance targets at a commercial scale by 2020.
A diverse technological portfolio will be necessary
to stabilize global GHG emissions (2), including carbon
capture and storage (CCS) as an option for directly reduc-
ing CO
2
emissions from coal-red power plants. Under an
integrated CCS concept, CO
2
would be captured, com-
pressed, transported via pipeline, and permanently stored
and monitored in geologic formations, such as depleted
oil and gas elds, saline formations, and unmineable coal
seams (3).
DOE/NETL has been working to advance all aspects
of CCS systems for more than a decade (4). This article
focuses primarily on the CO
2
capture R&D tailored for the
existing eet.
Capturing Carbon
Existing Coal-Fired
Power Plants
from
Reprinted with permission from CEP (Chemical Engineering Progress,
April 2009. Copyright 2009 American Institute of Chemical Engineers.
34 www.aiche.org/cep April 2009 CEP
Energy
CCS basics
The two general approaches to reducing carbon emis-
sions from existing plants are post-combustion capture and
oxy-combustion.
Post-combustion CO
2
capture, or separation of CO
2

produced by conventional coal combustion in air, presents
several technical challenges. The uegas is at atmospheric
pressure and the CO
2
concentration is 1015 vol.%, which
results in a low CO
2
partial pressure and a large volume of
gas to be treated. Despite this difculty, post-combustion
CO
2
capture offers the greatest near-term potential for
reducing GHG emissions, because it can be retrot to
existing units and can also be tuned for various levels of
CO
2
capture, which may accelerate market acceptance.
Chemical processes for separating CO
2
from existing
power-plant uegas streams, such as amine-based scrub-
bing with an aqueous monoethanolamine (MEA) solution
(Figure 2), are capable of achieving high levels of CO
2

capture (90% or more) from uegas due to fast kinetics
and strong chemical reactions. However, off-the-shelf
amine solvents are corrosive and susceptible to degrada-
tion by trace uegas constituents (particularly sulfur oxides
[SO
X
]). They also require signicant amounts of energy, in
the form of low-pressure steam, for sensible heating, heat
of reaction, and stripping to regenerate the liquid solvent

for reuse.
DOE/NETL has estimated that MEA-based CCS will
increase the COE for a new pulverized coal (PC) plant by
about 8085%, and even more for retrots, while reducing
the power plants net efciency by about 30% (5, 6). And
although MEA-based scrubbing has been utilized for more
than 60 years for natural gas purication and food-grade
CO
2
production, it has not been demonstrated at the larger
scale necessary for 90% CO
2
capture at a 500-MW coal-
red power plant where 10,00015,000 tons of CO
2
would
be removed per day.
With the potential of large-scale power plant CO
2

mitigation on the horizon, technology developers, such as
Fluor Corp. (Econamine FG Plus) and Mitsubishi Heavy
Industries (KM-CDR Process), have begun to optimize
chemical scrubbing technology (7, 8). The modications
are focused primarily on extensive thermal integration of
the CO
2
-capture system with the power plant and develop-
ment of improved solvent formulations with lower strip-
ping steam requirements and lower solvent circulation
rates than MEA (9). These process improvements have the
potential to reduce the cost and energy intensity of post-
combustion CO
2
capture, which is estimated to account
for about three-fourths of the total cost of an integrated
CCS system.
PC oxy-combustion power plants are designed to utilize
high-purity oxygen mixed with recycled uegas (primarily
CO
2
) to combust coal and produce a highly concentrated
CO
2
stream (more than 60% by volume). The CO
2
is further
puried by condensing the water vapor through the use of
cooling, desiccant systems, and compression to a dew point
of 40F. Depending on the end-use and pipeline specica-
tion, additional treatment may be necessary to reduce other
gas constituents (O
2
, SO
X
and nitrogen oxides [NO
X
]).
Although PC oxy-combustion is a relatively new
concept and experience with integrated systems is limited,
most key process components, including the cryogenic air
separation unit (ASU) for O
2
production, are proven and
commercially available. PC oxy-combustion is currently
being evaluated at the 30-mega-
watt thermal (MW
th
) scale by
Babcock & Wilcox Co. (B&W)
in Alliance, OH, and Vattenfall
at Schware Pumpe in Germany
(10, 11).
However, the appeal of
oxy-combustion is tempered by
a few key challenges, namely
the capital cost and energy con-
sumption for cryogenic ASU
operation, boiler air inltration
that dilutes the uegas with ni-
trogen, and excess O
2
contained
Year
C
O
2

E
m
i
s
s
i
o
n
s
,

m
i
l
l
i
o
n

m
.
t
.
Existing Units:
79.4% of coal-fired
CO
2
emissions in 2030
91.9% of cumulative
CO
2
emissions from
2008 to 2030
3,000
2,000
2,500
1,500
1,000
500
0
1995 2000 2005 2010 2015 2020 2025 2030
Unscrubbed Steam
Scrubbed Steam
New Steam
IGCC
307 GW
402 GW
Figure 1. Projections of carbon
dioxide emissions from U.S. coal-red
electric power generation. Source: (1).
CEP April 2009 www.aiche.org/cep 35
in the concentrated CO
2
stream. Fluegas recycle (about
7080%) is also necessary to approximate the combustion
characteristics of air, since currently available boiler mate-
rials cannot withstand the high temperatures resulting from
coal combustion in pure O
2
(12).
Consequently, the economic benet of oxy-combustion
compared to amine-based scrubbing systems is limited. In
comparison to a supercritical PC plant without CCS, a new
oxy-red supercritical PC plant would incur an estimated
60% increase in the COE (6).
Given the signicant economic penalties associated
with current CO
2
-capture technologies, step-change
improvements in both cost and energy efciency will be
required to ensure that CCS for existing plants can be done
with economically acceptable costs and impacts.
The EPEC R&D program
The EPEC program is conducting R&D on advanced
post- and oxy-combustion CO
2
-capture technologies, as
well as novel CO
2
compression techniques, for existing
coal-red power plants. In addition to funding external
projects, DOE/NETL, through its Ofce of Research and
Development (ORD), also conducts in-house research to
develop innovative concepts for CO
2
capture that could
lead to dramatic cost and performance improvements rela-
tive to todays technologies. The EPEC program also spon-
sors systems analysis studies of the cost and performance
of CO
2
-capture technologies (5, 6).
In J uly 2008, DOE/NETL awarded 15 new coopera-
tive agreements focused on laboratory- through pilot-
scale post- and oxy-combustion CO
2
-capture R&D
projects. These projects (denoted by an asterisk in
Table 1) build on the current port-
folio of CO
2
-capture research and
focus on ve technology pathways:
membranes, solvents, and sorbents
for post-combustion CO
2
capture,
oxy-combustion (uegas purication
and boiler development), and chemi-
cal looping combustion (CLC).
Membranes
Membrane-based CO
2
capture
uses permeable or semi-permeable
materials that allow for the selective
transport and separation of CO
2
from
uegas. Gas separation is accom-
plished by some physical or chemical interaction between
the membrane and the gas being separated, causing one
component in the gas to permeate through the membrane
faster than another. In general, membrane processes offer
several potential advantages: they operate passively, with
no moving parts; they can be designed to withstand chemi-
cal contaminants (SO
X
, NO
X
); they are energy-efcient,
with low operating costs; and they are modular and have a
small footprint.
Although membranes are best suited for separating
CO
2
in high-pressure applications, such as coal gasication,
the EPEC Program is focused on developing highly selective
and permeable membrane systems designed specically for
CO
2
separation from low-partial-pressure uegas streams.
For instance, gas absorption membranes, where separation
is achieved by a hybrid system that combines a membrane
with an absorption liquid (e.g., amine solvent or enzymes) to
selectively remove CO
2
from the uegas stream (Figure 3),
are a promising retrot technology.
Membrane Technology and Research (MTR) is
investigating thin-lm, composite polymer membranes
and associated process congurations to increase the ux
of CO
2
across the membrane, thereby reducing the required
membrane area. A novel countercurrent design that is being
pursued uses a portion of the incoming combustion air as
a sweep gas to maximize the driving force for membrane
permeation. Preliminary results indicate that 90% CO
2
cap-
ture at a 600-MW coal-red power plant will require about
700,000 m
2
of membrane, or 135 of MTRs nested module
skids with a total footprint of about 0.5 acres (13).
Another membrane process, under development by
Carbozyme, leverages the carbonic anhydrase (CA)
Absorber
Fluegas
Fluegas
from
Plant
Structured
Packing
Lean MEA
Semi-
Lean
MEA
Semi-Lean
Cooler
Lean/Rich
Cross
Exchanger
Rich MEA
To Reclaimer
Low-Pressure
Steam
45 psi
Excess Water
Reflux Pump
Reflux
Drum
Stripper
CO
2
to
Compression
Figure 2. Amine-based chemical scrubbing
can achieve high levels of CO
2
capture.
36 www.aiche.org/cep April 2009 CEP
Energy
Project Focus Participant
Post-Combustion Membranes
Biomimetic Membrane Carbozyme, Inc.
CO
2
Membrane Process* Research Triangle Institute
Membrane Process for CO
2

Capture*
Membrane Technology and
Research
Novel Dual-Functional
Membrane
Univ. of New Mexico
Novel Polymer Membranes Membrane Technology and
Research
Electrochemical Membranes DOE/NETLs ORD
Post-Combustion Solvents
High-Capacity Oligomers* GE Global Research
Integrated Vacuum Carbonate
Absorption Process*
Illinois State Geological Survey
Phase Transitional Absorption Hampton Univ.
Ionic Liquids Univ. of Notre Dame
Reversible Ionic Liquids* Georgia Tech Research Corp.
Post-Combustion Sorbents
Amine-Grafted Zeolites Univ. of Akron
Dry Carbonate Process Research Triangle Institute
Low-Cost CO
2
Sorbent* TDA Research
Metal Organic Frameworks UOP LLC
Carbon Sorbents* SRI International
Solid Sorbents* ADA-ES, Inc.
Reactor Design Studies DOE/NETLs ORD
Carbon-Supported Amine
Sorbents
DOE/NETLs ORD
Supported Amine Sorbent
Modeling
DOE/NETLs ORD
CO
2
Capture Sorbent-Based
Device Simulation
DOE/NETLs ORD
Surface Immobilization
Nanotechnology for Sorbents
DOE/NETLs ORD
CO
2
Sorbent Development DOE/NETLs ORD
O
2
Supply
Oxygen Transport Membrane-
Based Oxy-Combustion
Praxair, inc.
Compression
Novel Concepts for CO


Compression
Southwest Ressearch Institute
Supersonic Shock Wave
Compression Technology
Ramgen Power Systems
Project Focus Participant
Oxy-Combustion
PC Oxy-Combustion
Pilot Testing
Babcock & Wilcox
Oxy-Combustion Impacts in
Existing Coal-Fired Boilers*
Reaction Engineering
International
Oxy-Combustion Boiler Devel-
opment for Tangential Firing*
Alstom Power
Oxy-Combustion Boiler
Material Development*
Foster Wheeler NA Corp.
Oxy-Combustion CO
2
Recycle
Retrot
Southern Research Institute
Pilot-Scale Oxy-Fuel Research Canada Centre for Mineral and
Energy Technology (CANMET)
PC Oxy-Combustion with
Integrated Pollutant Removal
Jupiter Oxygen Corp.
Evaluation of CO
2
Capture/
Utilization/Disposal Options
Argonne National Laboratory
Fluegas Purication using
SOx/NOx Reactions During
CO
2
Compression*
Air Products and Chemicals, Inc.
Near-Zero Emissions
Oxy-Combustion Fluegas
Purication*
Praxair, Inc.
Oxy-Combustion with CO
2

Capture
DOE/NETLs ORD
Oxy-Fired Combustion
Simulation
DOE/NETLs ORD
Materials Performance in
Oxy-Combustion Environ-
ments
DOE/NETLs ORD
Oxy-Fuel Flame Property
Measurement
DOE/NETLs ORD
Wireless Sensing in Oxy-Fuel
Environments
DOE/NETLs ORD
Chemical Looping Combustion (CLC)
CLC Prototype* Alstom Power, Inc.
Coal Direct Chemical Looping* Ohio State Univ.
CLC Oxygen Carrier Studies DOE/NETLs ORD
CLC Model Development DOE/NETLs ORD
Laboratory-Scale CLC
Combustor
DOE/NETLs ORD
Design and Control of CLC
Systems
DOE/NETLs ORD
* New projects announced in 2008.
Table 1. Current CO
2
-capture technology R&D projects.
CEP April 2009 www.aiche.org/cep 37
enzyme to catalyze the conversion of CO
2
to bicarbonate
at the uegas interface, and reverses the process via a pres-
sure swing at the CO
2
product interface. The Carbozyme
permeator consists of two hollow-ber, microporous mem-
branes separated by a thin liquid membrane. CA is attached
to the hollow-ber wall to ensure that the incoming CO
2

contacts the CA at the gas-liquid interface to maximize
conversion efciency. The CA process has been shown
to have a low heat of absorption that reduces the energy
penalty typically associated with absorption processes.
However, several potential technical limitations need to be
better understood, including membrane boundary layers,
pore wetting, surface fouling, loss of enzyme activity,
long-term operation, and scaleup. The Carbozyme system
was validated recently during laboratory-scale testing on a
0.5-m
3
permeator, and 85% removal of CO
2
from a 15.4%
CO
2
feed stream was achieved. Upon fabrication, the next-
scale permeator will be shipped to the Energy and Envi-
ronmental Research Center for testing on coal-combustion
uegas (14).
The article, Capturing CO
2
: Membrane Systems Move
Foward, on pp. 4247 provides more detail on the devel-
opment of membranes for CO
2
separation and purication.
Solvents
Solvent-based CO
2
capture involves the chemical or
physical sorption of CO
2
from uegas into a liquid carrier.
Although solvent-based scrubbing is currently used com-
mercially to remove CO
2
from industrial uegases and
process gases, it has not been applied to removing large
volumes of CO
2
, as would be encountered in the uegas
from a coal-red power plant. Research projects in this
pathway address technical challenges to solvent-based CO
2

capture, such as large uegas volume, relatively low CO
2

concentration, uegas contaminants, and high parasitic-
power demand for solvent recovery.
Chemical solvents. Chemical absorption involves
one or more reversible chemical reaction(s) between
CO
2
and an aqueous solution of an absorbent, such as an
alkanolamine (e.g., MEA), hindered amine, aqueous
ammonia, or a carbonate, to form water-soluble com-
pounds. Chemical solvents are able to capture high levels
of CO
2
from uegas streams with a low CO
2
partial
pressure due to chemical reactivity, but capacity is equilib-
rium-limited. Thus, chemical-solvent-based systems incur
signicant cost and efciency penalties during the regen-
eration step, which involves a temperature swing to break
the absorbent-CO
2
chemical bond.
DOE/NETL is investigating advanced solvents that
have lower regeneration heat duties than MEA as well as
resistance to uegas impurities. Previous research focused
on potassium carbonate promoted with piperazine (15);
future work will evaluate an integrated vacuum carbonate
absorption process (16) and novel oligomeric solvents.
Physical solvents. Also currently in use in smaller-scale
industrial applications, physical absorption is a bulk phe-
nomenon where inorganic or organic liquids preferentially
absorb a gaseous species from the gas mixture. Although
the regeneration of physical solvents is less energy-inten-
sive than chemical-solvent regeneration, this technology is
considered more practical for processing the high-pressure
uegas generated at coal gasication (rather than com-
bustion) plants, since CO
2
solubility in physical solvents
increases with partial pressure (17).
The Univ. of Notre Dame and Georgia Institute of
Technology are investigating a new class of physical sol-
vents designed to capture CO
2
from low-pressure uegas
streams. Ionic liquids (ILs) include a broad category of
salts that typically contain an organic cation and either an
inorganic or organic anion. ILs have essentially no vapor
pressure and are thermally stable at temperatures up to sev-
eral hundred degrees Centigrade, which minimizes solvent
loss during CO
2
separation. Task-specic ILs containing
amine functionality have recently been developed with
CO
2
solubility 40 times greater than that of earlier ILs. A
possible drawback is that the high viscosity of many ILs
could adversely affect the ability to pump them in a power
plant application (18).
CO
2
-Rich Solvent
to Regeneration
Regenerated Solvent
C
O
2
C
O
2
C
O
2
C
O
2
C
O
2
C
O
2
C
O
2
C
O
2
C
O
2
C
O
2
C
O
2
C
O
2
C
O
2
C
O
2
C
O
2
C
O
2
Membrane
Gas Phase Liquid Phase
Exhaust Gas to Stack
Fluegas Containing CO
2

Figure 3. A gas absorption membrane combines a membrane with a
solvent to selectively remove CO
2
from the uegas.
Article continues on next page
38 www.aiche.org/cep April 2009 CEP
Energy
Sorbents
Solid sorbents, including sodium and potassium
oxides, zeolites, carbonates, amine-enriched sorbents,
and metal-organic frameworks, are also being explored
for CO
2
capture at existing plants. A temperature swing
facilitates sorbent regeneration following chemical
and/or physical adsorption, but a key attribute of CO
2

sorbents is that less water is present than in solvent-based
systems, thereby reducing the energy requirements for
sensible heating and stripping. Possible congurations
for contacting the uegas with the sorbents include xed,
moving, and uidized beds.
Research projects in this pathway address key technical
challenges to sorbent-based systems, such as solids circula-
tion, sorbent attrition, low chemical potential, heat transfer,
reactive uegas contaminants, and the parasitic-power and
sweep-gas demand for sorbent regeneration.
Scientists in DOE/NETLs Ofce of Research and
Development (ORD) have developed amine-enriched
sorbents that are prepared by treating high-surface-area
substrates with various amine compounds. The implant-
ing of the amine on a solid substrate increases the surface
contact area of the amine for CO
2
capture, thus reducing
sorbent/amine requirements. This advantage, combined
with the elimination of a water carrier, has the potential
to improve the energy efciency of the process relative to
MEA scrubbing. Concurrently, ORD is evaluating
novel reactor designs for large-scale, sorbent-based
CO
2
-capture systems applicable to new and existing PC
power plants (19).
Research Triangle Institute (RTI) International is
investigating the use of supported sodium carbonate
(Na
2
CO
3
, or soda ash) as an inexpensive and efcient CO
2

sorbent. The Na
2
CO
3
reacts with CO
2
and H
2
O to form
sodium bicarbonate via a reversible reaction that requires
a temperature swing from about 60C to 120C for sorbent
regeneration. RTIs dry carbonate process was successfully
integrated into the U.S. Environmental Protection Agen-
cys (EPA) Multi-Pollutant Control Research Facility
a 4-million Btu/h bench-scale furnace. During 105 h
of testing with coal-derived uegas, the process achieved
90% CO
2

capture. It offers four economic advantages over
MEA scrubbing: reduced capital costs, lower auxiliary
power load, reduced steam-turbine power de-rating, and
lower reactive-material costs (20).
UOP LLC is leading the effort to develop metal organic
frameworks (MOFs) materials that are thermally stable,
have adjustable chemical functionality that can be tailored
for high CO
2
-adsorption capacity, and possess very high
porosity. UOP has developed a virtual high-throughput
screening model to reduce the number of MOF synthesis
experiments to only those that have the highest probability
of success. A wide variety of MOFs have been successfully
synthesized, and preliminary results indicate that MOFs
are hydrothermally stable and capable of separating CO
2

from simulated uegas streams (21).
Oxy-combustion
PC oxy-combustion involves the use of relatively pure
O
2
mixed with recycled uegas (primarily CO
2
) for coal
combustion to produce a concentrated CO
2
stream. Experi-
ence with coal oxy-combustion is limited, so continued
R&D on oxy-combustion ame characteristics, burner and
coal-feed design, and analyses of the interactions between
oxy-combustion products and boiler materials is necessary
to ensure the development of low-cost and efcient oxy-
combustion power plant systems. DOE/NETL is conduct-
ing laboratory- through pilot-scale R&D related to:
advanced oxy-combustion boilers designed with new
materials of construction to handle higher ame tempera-
tures and potentially higher sulfur concentrations for
co-sequestration applications
advanced oxy-burner designs to maintain a stable
combustion ame
novel boiler designs with integrated O
2
separation to
reduce the cost of O
2
production
Taking the Next Step
Researchers in the DOE/NETL Ofce of Research and
Development developed and patented a novel ammonia-
based CO
2
-capture technology that relies on a tempera-
ture swing to cycle between ammonium carbonate and
ammonium bicarbonate. This reaction has a signicantly
lower heat of reaction than amine-based systems,
resulting in energy savings, provided the absorption/
desorption cycle can be limited to this mechanism.
Other advantages of ammonia-based absorption over
amine-based systems include the potential for high CO
2

capacity, the lack of degradation during absorption/
regeneration, a tolerance of O
2
in the uegas, low cost,
and the potential for regeneration at high pressure.
Powerspan Corp. subsequently licensed the aqueous
ammonia process in 2007 and re-branded it as ECO
2
.
Through integration with its ECO

multi-pollutant control
system, Powerspan is currently conducting a 1-MW
pilot test at FirstEnergys R.E. Burger Power Station in
Ohio. Powerspan has also announced plans to conduct
full-scale demonstrations (120 MW) of the ECO
2
process
at NRG Energys W. A. Parish Power Plant in Texas and
Basin Electrics Antelope Valley Station in North Dakota
beginning in 2012 (28).
CEP April 2009 www.aiche.org/cep 39
advanced uegas purication and compression
technologies.
B&W successfully completed oxy-combustion testing
at the 1.5-MW
th
scale and is currently operating a 30-MW
th

oxy-combustion pilot unit at its Clean Environment
Development Facility in Alliance, OH. Preliminary results
indicate that uegas volume is reduced by about 80% while
achieving CO
2
concentrations higher than 80%. Pilot-scale
testing has also demonstrated a smooth transition between
air- and oxy-ring modes, and led to the development of two
near-full-scale oxy-burners the DRB-XCL for eastern
bituminous coal and the DRB-PAX for low-rank coals (10).
In 2004, Alstom Power conducted pilot-scale (3-MW
th
)
testing of an oxygen-red circulating uidized bed (CFB)
combustor with both bituminous coal and petroleum coke
in O
2
/CO
2
mixtures containing up to 50% O
2
by volume.
The testing successfully addressed several technical
issues, such as furnace operability, temperature control,
heat transfer, recarbonization, criteria-pollutant and trace
gaseous emissions, and unburned carbon. The pilot-scale
tests conrmed the operability and technical feasibility of
an oxygen-red CFB system. Alstom completed a concep-
tual design and economic analysis for the conversion of
an existing 90-MW CFB unit to oxy-ring that indicated a
cost of $37 per ton of CO
2
avoided (22).
Oxygen supply
For oxy-combustion to be a cost-effective power
generation option, a low-cost supply of pure O
2
is required.
Although a cryogenic ASU can be used to supply high-pu-
rity O
2
to the boiler, this commercially available technol-
ogy is both capital- and energy-intensive (6). Novel O
2

production technologies currently under development, such
as ion transport membranes, have the potential to reduce
the cost of O
2
production.
Praxair, Inc., is investigating the design and operation
of oxygen transport membranes (OTMs), which utilize
chemical potential for the O
2
separation driving force
instead of pressure. The OTMs are designed to integrate
directly with the boiler such that the combustion reaction
occurs on the fuel side of the membrane, thus creating a
low O
2
partial pressure that serves as the driving force.
This chemical potential gradient drives O
2
through the
membrane without the need for additional air compression.
In preparation for pilot-scale testing, a ceramic membrane
and seal assembly has been developed for thermal inte-
gration between the high-temperature membrane and the
combustion process. Prototype single- and multiple-tube
reactors have been built to demonstrate membrane per-
formance and durability. Praxair estimates that OTMs can
deliver O
2
for oxy-combustion using only 20 to 30% of the
energy required for a cryogenic ASU (23).
(For more on air separation technology developments,
see Shelley, S., Oxygen and Nitrogen: Onward and Up-
ward, Chem. Eng. Progress, 105 (1), pp. 610, J an. 2009.
Editor)
Chemical looping combustion
CLC is an advanced coal oxy-combustion technology
that involves the use of a metal oxide or other compound
as a carrier to transfer O
2
from the combustion air to the
fuel. CLC (Figure 4) splits combustion into separate oxida-
tion and reduction reactions. The metal oxide (e.g., iron,
nickel, copper, or manganese) releases the O
2
in a reducing
atmosphere, and the O
2
reacts with the fuel. The metal is
then recycled back to the oxidation chamber, where the
metal oxide is regenerated by contact with air.
Since direct contact between the fuel and combustion air
is avoided, the products of combustion (CO
2
and H
2
O) are
kept separate from the rest of the uegas (primarily N
2
). The
main advantage of the CLC process is that an ASU is not
required and CO
2
separation takes place during combustion.
R&D projects will advance the development of CLC
systems by addressing key issues such as solids handling
and O
2
carrier capacity, reactivity, and attrition (24, 25).
Alstom Power plans to install and operate a 3-MW
th

CLC prototype at its existing power plant laboratory in
Windsor, CT. The prototype will utilize limestone as the
O
2
carrier and include process loops to transfer solids and
Air
Fuel
Air
Reactor
(Oxidizer)
Fuel
Reactor
(Reducer)
Metal
Metal
Oxide
Steam to
Power Cycle
N
2
+ O
2
CO
2
+ H
2
O
Figure 4. In chemical looping combustion, direct contact between the
fuel and the combustion air is avoided.
40 www.aiche.org/cep April 2009 CEP
Energy
O
2
between the reduction and oxidation reactors. Informa-
tion obtained from operation will be used to develop a
technical plan and cost estimate for a subsequent commer-
cial demonstration project at a full-scale power plant (26).
CO
2
compression
In preparation for pipeline transport and permanent
storage (e.g., in deep geologic formations or used for
enhanced oil recovery), the concentrated CO
2
stream must
be further dehydrated and compressed to a supercritical
liquid (1,070 psi [74 bar]). DOE/NETL estimates that for
a new 667-MW
gross
supercritical PC power plant, multi-
stage, centrifugal CO
2
compression from the stripper
regeneration column (2025 psi) to a pipeline pressure
of 2,200 psi would consume nearly 50 MW of auxiliary
power, or about 0.1 MW per ton of CO
2
(6).
Liquefaction of CO
2
to supercritical conditions can take
place via either of two thermodynamic routes multi-stage
compression with interstage cooling, or a combination of
compression, cooling, and pumping to supercritical pressures.
In pursuit of the latter approach, Southwest Research
Institute is investigating the use of refrigeration to liquefy
the CO
2
so that its pressure can be increased using a pump
rather than a compressor. The primary power requirements
for the hybrid refrigeration approach are for the initial
compression to boost the CO
2
to approximately 250 psi,
and for the refrigeration required to liquefy the gaseous
CO
2
. Once the CO
2
is liqueed, the pumping power to
boost the pressure to pipeline supply pressure is minimal.
Ramgen Power Systems is developing a supersonic
shock-wave compression technology that features a rotat-
ing disk operating at high peripheral speeds to generate
shock waves that compress the CO
2
. The so-called Ram-
pressor is said to have several advantages over conven-
tional multi-stage or hybrid refrigeration. Because shock
compression employs only two stages of compression
(vs. six to ten stages for the multi-stage approach), it
offers potential capital cost savings up to 50%. In addition,
the compressed CO
2
is recovered at higher temperatures
(400600F, depending on the efciency) due to fewer
stages (higher compression ratio), providing an opportunity
for heat recovery through integration into either the power
plants steam cycle or CO
2
-capture process. Recent proto-
type testing has achieved a 7.8:1 compression ratio (27).
In summary
It is anticipated that through federal research, develop-
ment, and demonstration (RD&D) programs such as these,
a broad suite of cost-effective CO
2
-capture technologies
will be available for commercial deployment by 2020 to
respond to any future climate change regulations imposed
upon the nations power generation sector.
Additional information related to DOE/NETLs EPEC
Program is available at www.netl.doe.gov/technologies/
coalpower/ewr/co2/index.html.
JARED P. CIFERNO is the technology manager of the Existing Plants
Emissions and Capture Program at the U.S. Dept. of Energys National
Energy Technology Laboratory (626 Cochrans Mill Road, Pittsburgh
PA 15236; Phone: 412-386-5862; E-mail: [email protected]).
He is responsible for overseeing NETLs $40-million/yr Existing Plants
Program, which consists of more than 40 projects related to power
plant water management and carbon dioxide control for new and
existing pulverized-coal power plants. His experience encompasses a
broad spectrum of technology areas, including electric power genera-
tion, advanced separation processes, coal conversion processes,
and simulation/systems analysis. Ciferno has BS and MS degrees in
chemical engineering from the Univ. of Pittsburgh.
TIMOTHY E. FOUT serves as a project manager in the Existing Plants Div.
of the National Energy Technology Laboratory, where he manages
cooperative agreements that focus on carbon-capture technology
development. He received his BS and MS in chemical engineering
from West Virginia Univ.
JAMES T. MURPHY is a senior environmental engineer with Science
Applications International Corp. (SAIC), which serves as an onsite
support contractor for National Energy Technology Laboratory.
Murphy currently serves as the subtask manager, providing technical
support for DOE/NETLs Existing Plants R&D program. Prior to joining
SAIC, he worked for about 30 years for Allegheny Energy in various
positions relating to coal-red power plant environmental controls.
He holds a BS in mechanical engineering and an MBA from the Univ.
of Pittsburgh.
ANDREW P. JONES is an environmental engineer with SAIC. He provides
general site support for National Energy Technology Laboratory, with
a focus on mercury and carbon dioxide control technologies for new
and existing coal-red power plants. He received a BS in chemical
engineering from the Univ. of Pittsburgh.
Acknowledgement
This article would not have been possible without the efforts of the
DOE/NETL project managers and researchers who provided valuable
technical input. The authors would like to acknowledge the contribu-
tions of Thomas Feeley III, Henry Pennline, Charles Alsup, Heino
Beckert, Jose Figueroa, David Lang, Bruce Lani, William Aljoe, Charles
Miller, Morgan Mosser, Robert Patton, and Andrew OPalko.
Disclaimer
Neither the United States government nor any agency thereof, nor any of
their employees, makes any warranty, express or implied, or assumes
any legal liability or responsibility for the accuracy, completeness,
or usefulness of any information, apparatus, product, or process dis-
closed, or represents that its use would not infringe privately owned
rights. Reference therein to any specic commercial product, process,
or service by trade name, trademark, manufacturer, or otherwise does
not necessarily constitute or imply its endorsement, recommenda-
tion, or favoring by the U.S. government or any agency thereof. The
views and opinions of authors expressed herein do not necessarily
state or reect those of the U.S. government or any agency thereof.
CEP
CEP April 2009 www.aiche.org/cep 41
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