International Journal of Greenhouse Gas Control 40 (2015) 55–125

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International Journal of Greenhouse Gas Control

journal homepage: www.elsevier.com/locate/ijggc

Oxyfuel combustion for CO2 capture in power plants

Rohan Stanger a , Terry Wall a,∗∗ , Reinhold Spörl b , Manoj Paneru b , Simon Grathwohl b ,
Max Weidmann b , Günter Scheffknecht b,∗∗ , Denny McDonald c,∗∗,1 , Kari Myöhänen d ,
Jouni Ritvanen d , Sirpa Rahiala d , Timo Hyppänen d,∗∗ , Jan Mletzko e , Alfons Kather e,∗∗ ,
Stanley Santos f,∗
a
Chemical Engineering Department, University of Newcastle, Callaghan, NSW 2308, Australia
b
Institute of Combustion and Power Plant Technology, University of Stuttgart, Pfaffenwaldring 23, D-70569 Stuttgart, Germany
c
Babcock & Wilcox Power Generation Group, Inc., Barberton, OH, USA
d
LUT School of Energy Systems, Lappeenranta University of Technology, FIN-53851 Lappeenranta, Finland
e
Institute of Energy Systems, Hamburg University of Technology, Denickestraße 15, D-21073 Hamburg, Germany
f
IEA Greenhouse Gas R&D Programme, Pure Offices – Cheltenham Office Park, Hatherley Lane, Cheltenham GL51 6SH, United Kingdom

a r t i c l e i n f o a b s t r a c t

Article history: Oxyfuel combustion is one of the leading technologies considered for capturing CO2 from power plants
Received 24 March 2015 with CCS. This involves the process of burning the fuel with nearly pure oxygen instead of air. In order to
Received in revised form 11 June 2015 control the flame temperature, some part of the flue gas are recycled back into the furnace/boiler.
Accepted 13 June 2015
Since the publication of the Special Report on CO2 Capture and Storage by the International Panel
Available online 4 August 2015
for Climate Change (IPCC, 2005), the development of oxyfuel combustion technology has progressed
significantly and could be considered at par in terms of technology maturity as compared to other leading
Keywords:
CO2 capture technologies.
CO2 capture and storage
Oxyfuel combustion
This paper presents an overview to the current state-of-the-art technology on the development of
Oxy-PC oxyfuel combustion applied to (a) PC and CFB coal fired power plants and (b) gas turbine based power
Oxy-CFB plant. It should be noted that it is not the intention of this paper to provide a comprehensive review but
Oxy-GT to present what have been achieved in the past 10 years of RD&D efforts.
Pulverized fuel combustion For coal fired power plant using oxyfuel combustion, this paper primarily presents the different devel-
Fluidized bed combustion opment aspects of the burners and boilers (combustion and heat transfer), emissions, operation of the
gas turbine plant (i.e. start-up and turndown) and its integration to the ASU and CPU.
For gas turbine based power plant using oxyfuel combustion, the different GT cycles are described,
looking at the different aspects in combustion, emissions, cycle efficiency and development of the tur-
bomachineries.
Also presented in this paper is a snapshot to what we have learned from the operation of the different
large-scale pilot plants and development of large scale demonstration projects worldwide.
The paper concludes by presenting the potential of this technology and highlighting the importance of
realizing large scale demonstration plant as a necessary step to achieve its ultimate goal of technology
commercialization.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction

Oxyfuel combustion is one of the leading technologies consid-

∗ Corresponding author. Tel.: +44 1242 802957.
∗∗ Corresponding authors.
E-mail addresses: terry.wall@newcastle.edu.au (T. Wall),
guenter.scheffknecht@ifk.uni-stuttgart.de (G. Scheffknecht),
dennykmcdonald@yahoo.com (D. McDonald), timo.hyppanen@lut.fi (T. Hyppänen),
kather@tuhh.de (A. Kather), stanley.santos@ieaghg.org (S. Santos).
1
Retired.
ered for capturing CO2 from power plants with CCS. This involves
the process of burning the fuel with nearly pure oxygen instead of
air. In order to control the flame temperature, some part of the flue
gas are recycled back into the furnace/boiler.
To capture the CO2 from a power plant, the main purpose of
using this technology is to generate a flue gas with high concen-
tration of CO2 and water vapour; and then separate the CO2 from

http://dx.doi.org/10.1016/j.ijggc.2015.06.010
1750-5836/© 2015 Elsevier Ltd. All rights reserved.
56 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
the flue gas by dehydration and low temperature purification pro-
cesses.
Oxyfuel combustion for power generation generally consists of
the following major units:
• Air Separation Unit (ASU) – oxygen production;
• Boiler or Gas Turbine – combustion of fuel & generation of heat;
• Flue Gas Processing Unit – flue gas cleaning or gas quality control
system (GQCS);
• CO2 Processing Unit (CPU) – final purification of the CO2 for trans-
port & storage.
The application of oxyfuel combustion for coal fired power plant
could be broadly classified according to: (a) oxy-PC and (b) oxy-CFB.
On the other hand, the application of oxyfuel combustion for gas
turbine based power plant could be broadly classified according to
its working fluid namely: (a) CO2 based GT cycles and (b) Water
based GT cycles.
This review is focused on the technical progress made in the
development of oxyfuel combustion technology for coal and gas
based power plants with CCS. This paper mainly covers the develop-
ment in the boiler or gas turbine section of the oxyfuel combustion
power plant; and briefly discusses the process line up of the flue gas
processing unit. Developments in the air separation unit and CO2
processing unit for oxyfuel combustion application are presented
in another paper (Santos, 2015).
For coal fired power plant using oxyfuel combustion, this
paper primarily presents the different development aspects of the
burners and boilers (combustion and heat transfer), emissions,
operation of the plant (i.e. plant control, start-up and turndown)
and integration to the ASU and CPU.
For gas turbine based power plant using oxyfuel combustion, the
different GT cycles are described, looking at the different aspects
in combustion, emissions, cycle efficiency and development of the
turbo-machineries.
Also presented in this paper is a snapshot to what we have
learned from the operation of the different large-scale pilot plants
and the large-scale demonstration projects worldwide.
2. Oxy-PC power plant
Pulverized coal (PC) combustion is predominantly used by util-
ities for their electricity generation. Efficiency improvements have
been gained over the years by increasing the steam conditions used
in the Rankine Cycle. Current state of the art PC combustion power
Fig. 1. Simplified schematic flow diagram of oxy-PC coal fired power plant with CO2 capture, including possible locations for flue gas recirculation and O2 addition – adapted
from Davidson and Santos (2010).
plants in operation today have a maximum operating capacity
in the range of ∼1100 MWe (gross) producing steam at ultra-
supercritical (USC) conditions of around 280 bar and 600 ◦ C/620 ◦ C.
Due to the dominance of the PC technology in the power sector,
the development of the oxyfuel combustion technology in the past
decades focussed on PC boilers. The progress of its development
in the past 10 years has been rapid. The technology readiness has
increased due to the successful operation of various integrated
large-scale pilot plants worldwide. The first generation large-scale
demonstration Oxy-PC power plants with CO2 capture to be built
should have capacities in the range of 100–500 MWe (gross).
In a conventional PC boiler, air is used as the comburent. The
CO2 in the flue gas is diluted by the N2 in air, thus resulting to a
lower CO2 concentration (typically 12-16%v dry basis). In an Oxy-PC
boiler, the air is replaced by a nearly pure oxygen (typically between
95% and 97% O2 ) mixed with recycled flue gas (RFG) as comburent,
thus resulting to a flue gas containing a high CO2 concentration
(typically between 65 and 85%v dry basis – mainly influenced by
the level of air ingress and the purity of the oxygen).
This section presents the developments of the oxy-PC high-
lighting the various aspects of operating the boiler in oxyfuel
combustion mode. There are several review papers (Buhre et al.,
2005; Tan et al., 2005; Wall, 2007; Wall et al., 2009; Normann
et al., 2009; Toftegaard et al., 2010; Davidson and Santos, 2010;
Scheffknecht et al., 2011; Stanger and Wall, 2011; Chen et al.,
2012; Lockwood, 2014) and books (Zheng, 2011; Toporov, 2014)
published in the open literature. All of them have provided com-
prehensive information about the different aspects of oxy-PC
combustion. This paper aims not to repeat these discussions but
only to highlight the important recent developments of oxy-PC
combustion.
It is also noteworthy to mention that these literature put
together should present the various progress made since the first
pilot test of the oxy-PC combustion undertaken in the early part
of the 1980s (Payne et al., 1989), until the recent activities in large
scale pilot plants and demonstration projects done by various key
stakeholders as summarized in Section 6.
2.1. Process configuration
The main parameters to control the combustion are dependent
on how the oxygen and the recycled flue gas (RFG) are introduced
into the boiler. Fig. 1 illustrates a number of different oxy-PC con-
figurations depending on where the flue gas is recycled (i.e. points
1–5) and where oxygen is injected (i.e. points A to E).
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125 57

Fig. 2. Simplified schematic flow diagram of oxy-PC fired power plant (developed by B&W) – illustrating the impact of the sulphur content of the coal to the plant’s process
options and configuration (McDonald, 2013). ASU – air separation unit; CDS – Circulating Dry Scrubber; CPU – CO2 processing unit; DCCPS – Direct Contact Cooler Polishing
Scrubber; FD – Forced Draft Fan; PJFF – Pulse Jet Fabric Filter; SDA – Spray Dry Adsorber; WFGD – Wet Flue Gas Desulphurisation.

Factors such as the sulphur and water contents of the fuel,
and the SOx and water content in the flue gas are the main
considerations in determining the location where RFG are taken.
Additionally, the amount of SO2 and SO3 that are recycled back
into boiler will be conservatively limited to a tolerable level to
minimize the problems to the boiler tubes, flue gas ducting and
coal mills (i.e. corrosion issues).
In conventional PC boilers, the main function of the flue gas
desulphurization (FGD) is to reduce SOx emissions to the atmo-
sphere. This is different for oxy-PC systems where an FGD has two
functions. Firstly, it should ensure that the SOx concentration in the
recycled flue gas is not too high to cause excessive corrosion to the
mills and/or furnace, ducting and other associated equipment; and
secondly, it has to guarantee that the amount of SOx in the flue gas
delivered to the CPU meets the CPU specification. Thus, the design
of an oxy-PC process depends also on the question of “when” and
“where” to remove SOx within the process line-up.
The sulphur content of the coal and hence the level of SOx in the
flue gas influence the selection of the configuration for an oxy-PC
power plant. In addition to the location where the RFG is taken,
the choice for the desulphurization technology also plays a role in
the selection of the process configuration. To emphasize the impor-
tance of these parameters, Fig. 2 illustrates an example showing the
different options for the flue gas desulphurization available in the
market – i.e. from dry/semi-dry scrubbers (i.e. CDS, SDA) to wet
scrubbers.
58 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 3. Oxygen distribution schemes employed at Vattenfall Schwarze Pumpe Pilot Plant (Burchhardt et al., 2013).
The most optimum process configuration is not only dependent
on sulphur content of the coal or SOx content of the flue gas; but
also dependent on the power plant performance. It is desirable to
have the highest possible efficiency that could be achieved (i.e. by
using hot or warm flue gas recycle) in designing the power plant.
Other factors such as NOx reduction considerations (i.e. use of
staged burners), and optimizing or minimizing the usage of O2
without affecting the combustion stability and burner/boiler per-
formance (i.e. avoid high concentrations of CO in flue gases and
unburned carbon in the ash) need also to be considered and can
influence the manner on how O2 and RFG are introduced into the
burners/boiler.
An optimized design of the firing system should consider all
the above mentioned points delivering a stable flame with good
combustion efficiency that also minimizes the level of excess O2 in
the flue gas.
2.1.1. Handling of the RFG during oxyfuel combustion
Generally, the oxy-PC process is designed to match the heat
transfer profile of an air fired boiler. To match this, around 65-75%
of the flue gas from the boiler are recycled. Depending on the fuel
properties and the flue gas recirculation ratio, the overall oxygen
content in the furnace is maintained at around 28-32%.
The recycled flue gas is typically split into primary RFG (about
30-35% of the total RFG – depending on the performance of the
mill) and secondary RFG (about 65-70% of the total RFG). Certain
boiler/firing system designs also incorporate tertiary RFG or over-
fire “air” (OFA)/overfire oxygen (OFO).
The primary RFG that is supplied to the mill and used in fuel
transport is generally cooled and washed in the flue gas condenser
(FGC) to reduce its water content and to remove most of the halides
(i.e. HCl, HF, HBr) and SO3 . When alkaline solution (i.e. NaOH,
NaCO3 , NaHCO3 , etc.) are added to the wash water of the flue gas
condenser (FGC) or direct contact cooler with polishing scrubber
(DCCPS), some of the SO2 can also be removed. The removal of
most of the water and acid components can prevent problems to
the operation of the mill.
Most proposed oxy-PC designs are rather conservative and pre-
fer a flue gas recycle with low dust loading (i.e. flue gas taken from
points 1, 2 or 3 as shown in Fig. 1). However, the option to use
RFG with high dust loading is also possible – i.e. flue gas taken at
points 4 (warm recycle) or 5 (hot recycle) as shown in Fig. 1. The
application of this option depends on the level of SOx in the flue
gas; and the selection of the type of RFG fans is critical (i.e. radial
flow fans could withstand up to ∼75-80 g/m3 dust [@ STP] and tem-
peratures in the range of ∼250-300 ◦ C, but radial fan’s efficiencies
are generally lower compared to axial fans). Limits for the high
dust recirculation are set by issues such as corrosion, erosion and
clogging/fouling.
2.1.2. Handling of the O2 from the ASU during oxyfuel combustion
As mentioned earlier, one of the objectives in designing the
burners and boiler for oxy-PC combustion is to reduce O2 con-
sumption and at the same time to maintain flame stability, without
increasing the CO and unburnt carbon in the ash. This can be man-
aged by how oxygen and RFG is introduced into the burners/boiler.
O2 from the ASU can be introduced into the boiler in several
ways:
• O2 can be pre-mixed with the RFG.
• O2 can be pre-mixed with the RFG via the individual registry of
the primary, secondary, and/or tertiary RFG.
• O2 can be pre-mixed with RFG and introduced into boiler via the
OFA/OFO port.
• O2 can be introduced directly into the burner via direct O2
lance(s).
• O2 can be introduced directly via OFO port.
Different permutations on how O2 can be introduced into the
burners were demonstrated at Vattenfall’s Schwarze Pumpe oxy-
fuel pilot plant (as shown in Fig. 3). The addition of O2 to the RFG
can be done before (pre-heated) or after (not preheated) the gas-gas
heater. Pre-heating of O2 can also be done separately using steam
coil gas heaters (SCGH).
The impact on how oxygen was introduced should provide a
good insight to the operating envelope of the burners. For example,
in pre-mixed mode, combustion stability could not be maintained
at the lower range of oxygen content in the flue gas; whilst in expert
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125 59

equipment manufacturers (OEM) in several pilot scale test cam-

paigns. The references listed in Table 2 should provide a wealth
of information about the different burner characteristics – such
as flame shape, length, luminosity and others. The information
about the flames including the flame pictures taken from these tests
should be useful in specifying the inputs to the different furnace or
combustion models.
The development of oxyfuel burner and boiler designs includes
the following main areas:

• Fundamentals of devolatilization and char burnout;

• Flame stability and burner aerodynamics;
• Heat transfer – Radiation and Convection;
• Ash Deposition, Slagging and Fouling; and
• Corrosion.

This paper presents a short overview on several of these com-

bustion properties in the following subsections.

Fig. 4. Operating envelope of the Hitachi DST Burner operated at Vattenfall

2.2.1. Devolatilization and char burnout
Schwarze Pumpe Pilot Plant in Premixed and Hybrid mode (Rehfeldt et al., 2011).
There is great interest in understanding the effect of CO2 -rich
environments (i.e. oxyfuel conditions) on coal devolatilization and
Table 1
Different desirable features of the burners for oxyfuel combustion operation adapted
char burnout. This knowledge is important to understand pilot scale
from (Burchhardt et al., 2013). test results and improve modelling of such phenomena. In the past
years, investigations have been performed in laboratory scale facil-
Burner characteristics Requirements
ities using coals of different rank for experiments with both, single
Fast start ability with stable • Capable of achieving ignition within 5 s and clouds of particles. In the following, main findings of vari-
ignition and stable flame • Capable of hot-, warm- and cold start ability
ous research studies regarding coal pyrolysis and char combustion
• Capable of smooth transition between air
blown combustion to oxyfuel combustion under oxyfuel conditions are presented.
mode and vice versa With respect to devolatilization, results point out a higher
High combustion quality: • Excess O2 in the flue gas (downstream of
volatiles’ release in a CO2 -rich environment compared to a N2 -
• Low excess O2 the boiler) should be <4% rich environment. Al-Makhadmeh et al. (2009) performed pyrolysis
• Emissions • Should be able to comply with emission investigations in a drop tube furnace under CO2 and N2 envi-
• Low UBC in the ash limits covering CO, NOx , and PM ronments using a medium volatile bituminous coal and lignite at
• Unburned combustibles in ash should
temperatures ranging from 700 to 1100 ◦ C. The results showed that
be < 2%
above 850 ◦ C a CO2 -rich environment enhances mass release by
Transport gas and comburent • Expected to handle comburent using air or approximately 10% and by 11-14% with the medium volatile coal
(oxidant/combustion gas) O2 -mixed with flue gas (21%-39%)
and the lignite, respectively. The results can be explained by the
• Expected to handle fuel transport gas using
air or O2 depleted CO2 -rich flue gas Boudouard reaction. Rathnam et al. (2006) measured the volatile
• Should be able to operate smoothly with yield of four Australian pulverized coals in a drop tube furnace at
fuel loading of up to 5 kg/kg transport gas 1400 ◦ C in simulated air (O2 /N2 ) and oxyfuel (O2 /CO2 ) combustion
Possibility to swirl the • Should have optimal intermixing of coal environments. Higher volatile yields in the oxyfuel environment
secondary air/RFG stream by swirling the secondary air/RFG were found for all tested coals. Also, the high temperature volatile
• Should be able to manage the flame yields of all coals were higher than their respective volatile yield
characteristics, shape and length with regard
obtained by proximate analysis. Zeng et al. (2008) used an entrained
to the heat transfer behavior
flow reactor to study the devolatilization behaviour of different
Operation flexibility • Capable of handling wide range of particle coals (lignite, subbituminous and eastern high-volatile bituminous
• with variable fuel quality size distribution
• with variable load demand • Should respond well with variation to LHV
coals) at different temperatures under N2 and CO2 entrained flow
• Capable of operating the burners between conditions. The reported results show a higher mass release in the
40-100% of the load with stable flame and CO2 environment than in the N2 environment for temperatures
good ramp rate. below 1400 ◦ C.
Another finding regarding devolatilization is the alteration of
the speciation of pyrolysis products under oxyfuel conditions. Fig. 5
or hybrid mode, the burner could extend their operating envelope shows H2 , CO and CH4 gas concentrations as a function of temper-
even at low oxygen content in the flue gas. An example of this ature from experiments under N2 (left) and CO2 (right) conditions
principle is shown in Fig. 4. performed by Al-Makhadmeh et al. (2009). According to the fig-
ure, H2 is the main non-condensable gas during pyrolysis under
2.2. Burners and boiler development N2 -rich conditions, while CO at a much higher level than in 100%
N2 is evidently the major species during pyrolysis in the CO2 envi-
Key to the development of the oxy-PC process is the develop- ronment. This effect on the gas species can be again explained by
ment of suitable burner and boiler designs. The design of the boiler the Boudouard reaction beyond 850 ◦ C and by the homogeneous
is dependent on the operation of the burners. Table 1 summarized water-gas-shift reaction.
some of the key desirable features required in the operation of the Regarding the effects of oxyfuel conditions on char burnout,
burners (Burchhardt and Griebe, 2013). Rathnam et al. (2006) compared the char burnout of three Aus-
Several different large-scale burners (i.e. >15 MWth ) – as sum- tralian coals in a drop tube furnace at 1400 ◦ C in O2 /N2 (air) and
marized in Table 2 – have been evaluated to date by various original O2 /CO2 (oxyfuel) environments. The oxygen concentration was
60 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125

Table 2
Different large scale burners evaluated for oxyfuel combustion operation.

Burner schematics or picture Key Information References

OEM: International Combustion Ltd. International

Rating: 35MWth Combustion (1995)
Type: Standard low NOx swirl burner
Fuel: Bituminous coal
Tested: 1993-1994
Project: EC Joule II Programme

OEM: Babcock and Wilcox (B&W) Farzan et al. (2008)

Rating: 30MWth Farzan et al. (2009)
Type: B&W DRB XCLTM (low NOx swirl) Burner
Fuel: Bituminous & sub-bituminous coal
Tested: 2007-2009
Project: CEDF Oxy-Combustion Campaigns

OEM: Babcock and Wilcox (B&W) Farzan et al. (2009)

Rating: 30MWth
Type: B&W PAX-XCL (low NOx swirl) Burners
Fuel: PRB and lignite
Tested: 2007-2009
Project: CEDF Oxy-Combustion Campaigns

OEM: Babcock and Wilcox (B&W) Farzan et al. (2009)

Rating: 30MWth
Type: B&W EI (low NOx swirl) Burners
Fuel: PRB
Tested: 2007-2009
Project: CEDF Oxy-Combustion Campaigns

OEM: Air Liquide Marcano et al. (2011)

Rating: 8 MWth (per burner) x4
Type: low NOx swirl burners
Fuel: NG
Tested: 2009-2013
Project: Total Lacq Project

OEM: Alstom Power Burchhardt et al. (2013)

Rating: 30MWth Kluger et al. (2011)
Type: Low NOx jet/swirl burner (Type A) Marion et al. (2011)
Fuel: Lignite
Tested: 2008-2009
Project: Vattenfall Schwarze Pumpe Project

OEM: Alstom Power Burchhardt et al. (2013)

Rating: 30MWth Kluger et al. (2011)
Type: Low NOx pure swirl burner (Type B) Marion et al. (2011)
Fuel: Lignite
Tested: 2008-2009
Project: Vattenfall Schwarze Pumpe Project
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125 61

Table 2 (Continued)

Burner schematics or picture Key Information References

OEM: Hitachi Power Europe Burchhardt et al. (2013)

Rating: 30MWth Rehfeldt et al. (2011)
Type: DST Low NOx pure swirl burner
Fuel: Lignite
Tested: 2010-2011
Project: Vattenfall Schwarze Pumpe Project

OEM: Doosan Babcock Energy Ltd. Sturgeon (2011)

Rating:40MWth Cameron et al. (2011)
Type: OxyCoalTM Low NOx swirl (Mk3) burner Sturgeon et al. (2013)
Fuel: Bituminous coal
Tested: 2008-2010
Project: Oxy-Coal UK Phase 2 Project

OEM: Doosan Babcock Energy Ltd. Burchhardt et al. (2013)

Rating: 30MWth Sturgeon (2011)
Type: Low NOx pure swirl pre-mixed burner Sturgeon et al. (2013)
Fuel: Lignite
Tested: 2001-2012
Project: Vattenfall Schwarze Pumpe Project

OEM: Riley Dodd (original); IHI Corp. (new) Yamada (2009)

Rating: ∼25MWth (per burner) x4 old & x2 new Spero (2011)
Type: - Spero et al. (2013a)
Fuel: Bituminous coal
Tested: 2012-2014
Project: Callide Oxyfuel Projects

OEM: Alstom Power Ltd. Levasseur et al. (2011)

Rating: 15MWth Marion et al. (2013)
Type: Low NOx Tangential Firing Burners
Fuel: High & Low S Bit. Coal, PRB, Lignite
Tested: 2009-2014
Project: US DOE Project

OEM: BBS Bilfinger Burchhardt et al. (2013)

Rating: 30MWth
Type: Low NOx Swirl Burner (Plasma Ignition)
Fuel: Lignite
Tested: 2012-2013
Project: Vattenfall Schwarze Pumpe Project

also varied in a range from 3 to 21 vol% in O2 /N2 and from 5 to
30 vol% in O2 /CO2 . In this study, the volatile yield obtained in O2 /N2
at 1400 ◦ C was subtracted from the measured total coal burnout
to calculate char burnout. Rathnam et al. (2006) investigated the
resulting char burnout by increasing oxygen concentration in both
air and oxyfuel environments. An enhanced char burnout in O2 /CO2
environments is observed for almost the whole range of oxy-
gen concentrations studied. This enhancement is attributed to
the char gasification reaction with the CO2 present. However, Al-
Makhadmeh et al. (2009) found that O2 diffusivity is lower under
O2 /CO2 conditions thereby causing a lower reaction rate and a delay
effect on char burnout, even though after long enough residence
times the maximum burnout was comparable to the one obtained
under O2 /N2 conditions. Shaddix et al.’s (2009) findings support
that char reactivity is lower under oxyfuel combustion conditions
due to diffusion effects. However, analysis of the single-particle
data showed that the surface-specific kinetic rate of oxidation of
the chars is nominally the same in the presence of CO2 or N2 .
This suggests that the decrease in the overall char burning rate
in the presence of CO2 is due to the approximately 20% lower
rate of oxygen diffusion through the CO2 -rich boundary layer.
Computational analysis showed that the effect of CO2 on oxygen
62 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125

12 12
Pyrolysis using 100% N 2 Pyrolysis using 100% CO 2 CO

Gas concentrations [vol%]

Gas concentrations [vol%]

10 10

8 8
H2 H2
H2
6 6
CO CO
CH4 CO
4 4 CH4 H2

2 2
CH4 CH4
0 0
650 750 850 950 1050 1150 650 750 850 950 1050 1150

Pyrolysis temperature, °C Pyrolysis temperature, °C

Fig. 5. Gas concentrations at the end of an entrained flow pyrolysis reactor for Lusatian lignite: pyrolysis in 100% N2 and 100% CO2 environments (Al-Makhadmeh et al.,
2009).

diffusivity reduces char particle temperatures by approximately
50 K at enriched CO2 levels and decreases the burning rate by
approximately 10%.
Shaddix et al. (2010) and Hecht et al. (2010) investigated the
influence of the gasification reactions on char burnout during
coal oxyfuel combustion. Their findings indicate that gasification
reactions slightly increase the overall char conversion rate for
combustion at all investigated O2 concentrations and for wet and
dry recycle conditions. Char characteristics have also been studied
and it was found that the effect of the CO2 environment is coal
rank dependent (Wall et al., 2009). In this area, further research is
needed.
In summary, the oxyfuel combustion environment affects both
coal pyrolysis and char combustion, but some of the effects still
need to be clarified. The Boudouard and the homogenous water
gas shift reactions have a significant effect on both coal pyrolysis
and char combustion.
2.2.2. Flame stability and burner aerodynamics
To evaluate the impact of oxyfuel combustion conditions in
comparison to air-firing, careful attention is needed on the near
burner aerodynamics. The swirl number is one parameter that
should be considered when evaluating other parameters, such as
ignition behaviour, flame shape, heat release, temperature pro-
files, pollutant formation, and particle burnout. Differences in the
design between oxyfuel and conventional air-fired furnaces relate
to altered plant configurations, together with differences in the
net gas flows and in the flue gas composition. Information on the
effect of elevated levels of CO2 on the ignition of coal particles is
important both for understanding how to switch existing burners
from air operation to operating with O2 /CO2 mixtures, and for CFD
modelling of the performance of PC burners in oxyfuel combustion
environments.
Maintaining flame stability under oxyfuel combustion condition
is important and posed a significant challenge to burner controls.
The challenge stems from the lower adiabatic flame temperature,
lower flame propagation speed and the delayed ignition of coal
particles in a CO2 diluted environment.
To date, most studies have found that coal ignition is retarded in
CO2 -rich environments, even at comparable gas temperature pro-
files. Liu et al. (2005) reported an increased coal ignition delay in
20 kW scale tests on O2 /CO2 coal combustion. Kiga et al. (1997)
performed microgravity measurements of the combustion of coal
clouds in 40 vol% O2 with N2 , CO2 and Ar as balance gas and found
that the flame speed decreased in the order: Ar, N2 and CO2 . Molina
and Shaddix (2007a,b) showed via single particle experiments that
the presence of CO2 and a lower O2 concentration increase the igni-
tion delay time but have no measurable effect on the time required
to complete volatile combustion, once it is initiated. In addition,
it was found that particle ignition and devolatilization properties
in a mixture of 30 vol% O2 in CO2 are very similar to those in air.
At this oxygen concentration also a comparable adiabatic flame
temperature as in air combustion is obtained.
Pilot-scale tests showed that the ignition and flame stability is
on the one hand dependent on the oxygen concentration in the
oxidant and on the other hand sensitive to the changed volume
flow in oxyfuel operation.
This is clearly indicated from the results presented by Zhang
et al. (2010, 2011a,b) – where the relationship between flame
shapes and to the probability density functions (PDFs) used to
quantify the fluctuating flame standoff distance in a 40 kW test
rig evaluating a well established turbulent co-axial jet flame were
presented. The later parameter provides key information on the
characteristic of the near field aerodynamics of the oxyfuel flames.
They have concluded that the partial pressure of primary oxygen,
secondary oxygen, preheat temperature of secondary oxygen and
furnace wall temperature have important and quantifiable first-
order effects on flame stability.
A key aspect in the design of oxyfuel systems, therefore, is to
introduce sufficient oxygen into the pulverized coal flame in order
to ensure satisfactory ignition, and to ensure a proper aerodynamic
stabilization, e.g. by keeping the swirl number comparable. After all,
it is also important that flue gas recycling is in a range to allow a
satisfactory balance of the heat transfer in radiative and convective
sections.
Measures that are being tested by plant manufacturers to opti-
mize oxyfuel burners include the direct injection of oxygen through
the burner (i.e. without premixing). This can be realized by using
oxygen lances or modifications to the burner geometry itself like
an additional annular gap to ensure good oxygen migration and
mixing with the coal particles to achieve good ignition and flame
stability characteristics. Grathwohl et al. (2011) have developed,
built and tested a highly variable burner that allows a partial or
even a complete direct injection of the oxygen through the burner
into the combustion zone. Fig. 6 shows the measured tempera-
ture profiles of one air and three different oxyfuel flames that
were obtained with this burner. The experiment with direct oxygen
injection through the burner (right), revealed a stable and com-
pact flame even at a very high flue gas recirculation rate (i.e. low
concentration of oxygen).
Grathwohl et al. (2011) also reported that CO2 can affect coal
ignition when the aerodynamics of the burner and the proportion
of CO2 in the oxidant are not optimized. Fig. 6 shows that the aero-
dynamic stabilization by the burner and its geometry/swirl is at
least as much important than the availability of oxygen. Ignition
and flame stability were in these test cases not dominated by the
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125 63

Fig. 6. Measured temperature profiles for air, oxy-fuel with 33 vol% O2 (mixed with RFG) oxy-fuel with 21 vol% O2 (mixed with RFG) and oxy-fuel with 21 vol% O2 (directly
injected) combustion (Grathwohl et al., 2011).

available oxygen concentration. It was much more influenced by

the total mass flow passed through the swirled burner compart-
ment and the directly related swirl number.
Meanwhile, different combustion- and burner configurations
have been tested in various pilot scale test facilities (as sum-
marized in Table 2). At Vattenfall’s 30 MWth oxyfuel pilot plant
(Schwarze Pumpe, Germany), five different burners from Alstom,
Hitachi, Doosan, and BBS were tested in single burner cell operation
(Burchhardt et al., 2013). At CIUDEN’s 20 MWth pilot plant in Spain,
four 5 MWth burners are installed in an opposed wall fired arrange-
ment, while in the Callide oxyfuel 30 MWe demo plant in Australia,
four burners from Riley Dodd and two burners from IHI are applied
in a 3 × 2 front wall burner arrangements operating with 4 burners
at a given time (Spero et al., 2013a; Spero, 2011; Yamada, 2009).
With the exception of the first burner tested at the 30 MWth
Schwarze Pumpe oxyfuel pilot plant, all the other burners can be Fig. 7. O2 and CO2 concentrations and flue gas recycle flap/damper position
classified as swirl burners. These burners are equipped with at least recorded during a switch from air to oxy-fuel operation at a 500 kWth combustion
one, but some also with two swirl registers and some of them are test rig (Mönckert et al., 2007).
able to inject oxygen directly via lances or a complete separate
annular gap through the burner to the furnace. From the opera- 30 MWth Schwarze Pumpe oxyfuel pilot test facility. These results
tional point of view, it might be more convenient, or even more show that the switching behaviour seems to be practically inde-
practical to use the direct oxygen injection method especially for pendent of the scale, burner configuration and oxygen injection
a direct start-up in oxy-mode, skipping the switching procedure mode.
from air to oxyfuel. Direct injection of O2 offers further possibilities for the utiliza-
In Fig. 7, O2 and CO2 concentrations and flue gas recycle tion of low-volatile or anthracite coals by improving ignition and
flap/damper position recorded during such a switch from air to oxy- stability problems that are often related to those fuels. An advan-
fuel operation at the 500 kWth test facility of University of Stuttgart tage besides the combustion behaviour that may be enhanced by
are exemplary shown. direct oxygen injection is the reduced requirement for an accu-
The main part of the switching procedure took less than 15 min, rate control of the oxygen concentration in and for the materials of
while it took less than 30 min until about 90 vol%(dry) of CO2 were the recirculation lines, burners etc. that are in contact with O2 -
reached. This system behaviour was also proofed in pilot scale by rich oxidant gases in a premixed oxyfuel process configuration.
Anheden et al. (2011). They reported that a changeover sequence These advantages may be particularly important when retrofitting
from air- to oxyfuel-firing can be managed within 20 min at the existing power plants for oxyfuel operation.
64 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 8. Comparison of gas properties of CO2 to N2 at 1200 K (Molina and Shaddix, 2007a,b).
2.2.3. Radiation and convection in oxyfuel combustion –
fundamentals
Heat transfer in coal fired boilers is dominated by radiation and
convection. Both modes depend on the properties of the atmo-
sphere present in the furnace and the convective section. Moreover,
radiative heat transfer is highly determined by the radiation of par-
ticulate matter. In comparison to air-firing, oxyfuel combustion is
characterized by a high share of CO2 and H2 O instead of N2 while
the H2 O concentration depends on the type of recycle applied, i.e.
wet or dry. This alteration of the flue gas composition impacts the
radiative and convective heat transfer behaviour due to different
gas properties of CO2 and N2 . Fig. 8 gives a good overview on the
altered properties.
The convective heat transfer in combustion applications is
determined by the convective heat transfer coefficient h and the
driving temperature difference T between bulk gas and surface.
The convective heat transfer coefficient is a function of thermal con-
ductivity, the characteristic length and the Nusselt number which
depends on the Prandtl and Reynolds number.
The latter is calculated from the bulk gas velocity, the character-
istic length and reciprocal on the kinematic viscosity. The kinematic
viscosity ratio of CO2 and N2 is about 0.64 and thermal conductiv-
ity ratio is about 1.11, thus convective heat transfer increases when
shifting from air to oxyfuel combustion if velocity and bulk gas tem-
perature are kept constant. Both bulk gas velocity and temperature
depend on the recycle ratio, the latter reciprocal. In real oxyfuel
applications, the velocity will decrease due to generally lower vol-
umetric flow rates affecting the convective heat transfer negatively.
To moderate the temperature raise the flue gas recycle will be used
thus increasing bulk gas velocity while decreasing its temperature.
These complex interactions between gas properties, bulk gas veloc-
ity and temperature influencing the convective heat transfer were
investigated by Woycenko et al. (2005). He showed that the ratio
of hoxy to hair increases with increasing recycle ratio indicating that
the increase in velocity over-compensates the decrease in the driv-
ing temperature difference. However, this ratio is close to one in
realistic recycle ratio ranges of between 0.55 and 0.70. In general,
the recycle ratio is an appropriate tuning parameter to achieve sim-
ilar boiler performance for air and oxyfuel combustion as found by
Payne et al. (1989) and Andersson et al. (2008a). This would be the
goal especially if existing boilers are to be retrofitted from air to
oxyfuel operation.
In coal fired boilers, the heat transfer in the furnace is domi-
nated by radiation. In radiative heat transfer mainly the combustion
products CO2 , H2 O and particulate matter (i.e. char, soot and
fly ash particles) are involved. Due to the high concentrations
of the triatomic gases CO2 and H2 O in oxy-fired combustion,
emissivity can be considerably altered since these gases are not
transparent to radiation as N2 is (Chen et al., 2012). Several stud-
ies (Andersson et al., 2008a; Viskanta, 2005) also highlighted the
importance of particulate matters on the radiative heat transfer in
coal combustion and thus, assuming similar particle properties and
concentrations, the impact of oxy-firing on radiative heat transfer
may be limited.
Andersson et al. (2008a) compared the radiative heat transfer
in air- and oxyfuel combustion of lignite in a 100 kW combustion
test rig. They found an enhancement of the gas radiation inten-
sity for oxyfuel compared to air combustion by a factor of 5 due to
the higher CO2 concentration in the oxyfuel case. Andersson et al.
(2008b) in another study showed that the radiation intensity emit-
ted by a propane flame in the oxy case with 21 vol% oxygen is close
to that of the flame in the air case, despite lower temperatures and
less soot present in the flame. That is, the level of the radiation
intensity is partially recovered by the high CO2 concentration in
the OF21 flame. So CO2 recycling influences the intensity of flame
radiation by changing the temperature and the emissivity in the
oxy case. A study conducted by Johansson et al. (2013) at the same
Chalmers reactor emphasizes the importance of particle radiation
and identifies temperature, soot formation, particle load and scat-
tering as main influences on radiation in furnaces. The importance
of particle radiation in air and oxyfuel combustion is also illustrated
in Fig. 9.
In summary, increased radiation is proven for oxyfuel combus-
tion with gaseous fuels. However, with coal due to the large fraction
of particle radiation the impact of gas radiation is reduced by the
gas-particle overlap which can be seen from Fig. 9. A change in
flame temperature caused by changes in the recycle ratio, on the
other hand, can significantly influence the radiation intensity.
From Vattenfall’s 30 MW Schwarze Pumpe pilot oxyfuel test rig
(Burchhardt and Griebe, 2013), it is reported that the heat absorbed
by the evaporator has decreased from 65% during air firing to 62.5%
in Oxy25; and to 64% in Oxy35 when operating at 93% of the load.
This difference is smaller at lower loads.
Experience from Callide’s oxyfuel power plant (Yamada et al.,
2013) has also indicated that the heat to the evaporator is slightly
lower by around 3% when operating in Oxy27 mode as compared
to air firing. This is attributed to the effects of the additional heat
recovery at the flue gas low pressure heater (FGLPH).
Regarding the convective heat exchangers, higher heat transfer
is observed in the heat exchangers closest to the furnace and lower
heat transfer occurs in the heat exchanger further downstream
when switching from air to oxyfuel combustion (Burchhardt,
2014). However, these results can only be an indication of boiler
heat transfer performance and its relation to the RFG ratio and
total oxygen concentration in the oxidant would require further
research.
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 9. Radiative intensity for air (left hand side) and oxy-fired OF25 (right hand side) 100 kW test furnace. Gas radiation is modeled by a statistical narrow band model
(Anderson et al., 2011).
2.2.4. Slagging and fouling
The altered flue gas composition and changes in the tempera-
ture profile of an oxyfuel fired process can impact transformation
of minerals and the formation of ashes and deposits. Previous
studies by Wigley et al. (2009) dedicated to understand coal min-
eral transformations under oxyfuel conditions indicated that the
changes in firing mode do not necessarily alter the transformation
behaviour but can influence the extent of ash transformations. One
doubt that was raised initially was regarding the impact of higher
CO2 partial pressures on carbonate mineral transformations. Avail-
able literature on transformation of carbonate minerals (e.g. CaCO3
and FeCO3 ) suggests that oxyfuel combustion atmospheres influ-
ence the extent of carbonate decomposition and especially increase
the carbonate decomposition temperatures (Wigley et al., 2009).
However, pulverized fuel combustion temperatures are generally
significantly higher than individual decomposition temperature of
relevant carbonate minerals. Wigley et al. (2009) further suggested
that uncertainties about ash and deposition behaviour during
oxy-coal combustion arise mainly from unknown combustion con-
ditions and once the time-temperature history for oxy-firing are
clarified, ash and deposition behaviour will be largely predictable
from current understanding.
Sheng et al. (2010), Zhang et al. (2011a,b) and Yu et al. (2012)
studied the impact of oxyfuel combustion atmospheres especially
on the transformation of iron bearing minerals (e.g. pyrite), both
included and excluded. Based on their experimental studies they
concluded that in general, more iron would melt into glassy sili-
cates in O2 /CO2 atmospheres. The reason for this is the lower char
combustion temperature and higher CO concentrations within the
burning char particles that favour the transformation to iron glass.
This may be particularly the case for included pyrite minerals that
are finely dispersed in the coal matrix, while for excluded pyrite
no specific differences were observed. This can have a significant
impact on viscosities of ash particles and can change the ‘sticki-
ness’ of coal ash particles and the rate of sintering of deposits. Thus,
besides changes in the gas composition and time-temperature pro-
file, other changes in the process, e.g. a different char burning
behaviour under oxyfuel conditions may impact mineral transfor-
mation.
In addition to mineral transformations, also other variables such
as particle trajectory and ash viscosity will affect the deposition
of ashes in boilers. Those depend on particle aerodynamics at the
burner exit and through the boiler, on the burning coal/char and
ash particle sizes, compositions and temperatures, as well as on
the local gas composition (particularly the partial pressure of CO2 ,
O2 and SO2 ). Again there are counterbalancing factors within the
65
boiler, which based on modelling and pilot scale studies to date,
tend to indicate no significant effect of oxyfuel combustion.
A trend that was found in comparative air and oxyfuel experi-
ments with Lusatian lignite and US bituminous coal (Spörl et al.,
2014c) is that ashes and deposits collected during oxyfuel fir-
ing contain more sulphur than corresponding samples from air
combustion, which is basically related to the higher SO2 concentra-
tion in the flue gas. Moreover, higher SO2 concentrations not only
increased sulphur retention in ash and deposits but also pushed
the sulphur stability towards higher temperatures (Paneru et al.,
2013a; Spörl et al., 2014c). Increased sulphur retention in ash and
deposits coupled with increased stability of sulphates intuitively
will have a negative impact on ash deposition (both slagging and
fouling) (Spörl et al., 2014c), e.g. by increased sulphide and sulphate
formation. Such an effect was validated in a small-scale combus-
tion experiment in CO2 /O2 (Spörl et al., 2014c). Deposits have been
collected under four different experimental conditions, all during
combustion of Lusatian lignite in CO2 /O2 gas (temperatures of 1100
and 1200 ◦ C, with an SO2 -concentration of 850 and 6250 ppm (dry),
respectively). SEM BSEs and WDX sulphur maps of the deposits are
shown in Fig. 10: Hardly any sulphur can be found in the deposit
at 1200 ◦ C and 850 ppm (dry) SO2 , while at 1200 ◦ C and 6250 ppm
(dry) in the flue gas the retention of sulphur in the deposit is obvi-
ous. In contrast, at 1100 ◦ C sulphur retention was found with both
temperatures. The tested lignite’s ash contains a significant amount
of Ca and Fe in the ash and shows a characteristic morphology
and composition of the Lusatian lignite deposit particles with an
abundance of spherical Ca/Fe-rich ash particles with a calcium sul-
phate rim that may form linkages between individual ash particles
(see, Fig. 10). Taking into account this mechanism, agglomeration of
particles over time may be more pronounced during oxyfuel com-
bustion. Nevertheless, such behaviour is highly fuel specific and
will be different for coals with other ash-mineral composition (e.g.
low alkali/earth-alkali content).
The impact of oxyfuel atmospheres on deposition (on a cooled
probe surface) has been comparatively studied (i.e. oxy vs. air) by
Li et al. (2013) and Fryda et al. (2012). Li et al. (2013) reported
lower deposition, while Fryda et al. (2012) reported higher depo-
sition rates during oxyfuel, in comparison to air-firing. A similar
study by Yu et al. (2011) also reported higher deposition on an
uncooled probe surface during combustion with air. The investi-
gated coals were different among the individual studies. Despite
different results, all investigators (Fryda et al., 2012; Li et al., 2013;
Yu et al., 2011) speculated the change in deposition behaviour to
be related to changes in factors such as velocity, particle trajectory,
particle size, and particle viscosity. The analysis of the ashes did
66 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 10. SEM BSE images and WDX sulphur maps of uncooled deposits sampled at 1100 ◦ C [(a), (c)] and 1200 ◦ C [(b), (d)] at SO2 concentration of 850 ppm (dry) [(a), (b)] and
6250 ppm (dry) [(c), (d)] (Spörl et al., 2014c).
not indicate a strong variation in the crystallographic phases and
the oxide composition that could explain the differences in depo-
sition behaviour. Since particle viscosity is closely related to the
composition of particles, it was speculated that the changes are
mostly related to aerodynamic changes rather than other phys-
ical or chemical differences in ash. Between air- and oxy-fired
conditions, also some differences with respect to ash particle size
distribution were observed. The ash/deposit chemical composi-
tion and crystalline phases of bulk ashes that were assessed might
not represent the individual deposit particle’s composition. This
composition can significantly vary among particles as does their
‘stickiness’. The stickiness of deposit particles depends on coal min-
eral type and its transformation together with its time-temperature
history during combustion.
Sulphate and carbonate compounds are of specific interest
regarding fouling deposits owing to their impact on fire-side
corrosion as well as agglomeration of deposits. Equilibrium ther-
modynamic calculations suggest that the elements Na, K, Ca,
Mg, and Fe will tend to form sulphates rather than carbonates,
when cooling in flue gas atmospheres. However, kinetics and
inhomogeneity equally dominate the transformation of coal miner-
als during combustion. Kull et al. (2008) reported that carbonates in
deposited ash do not necessarily derive due to reduction in extent
of decomposition of calcite minerals but can also be formed due to
long-time interaction between CaSO4 and CO2 from flue gas. The
laboratory exposure of CaSO4 in CO2 -rich atmosphere without SO2
shows a distinct tendency of formation of carbonates (Kull et al.,
2009). However, higher SO2 concentrations expected in practical
oxyfuel (but also air-fired) boilers and therefore increased stability
of sulphates apparently favours sulphate deposits over carbonates.
Kull et al. (2008), Stanger and Wall (2011) and Spörl et al. (2014c)
reported higher sulphur concentrations in oxyfuel derived ash and
deposits. In the above mentioned tests the sulphur content in ash
and deposits increased by a factor of 1.5–3. Most of the critical
issues in respect to deposition, fouling and also corrosion under
oxyfuel conditions have been raised, due to the increased SO2 con-
centrations in oxy-fired processes. In this context, the impact of the
flue gas recycle mode (wet or dry) and the implemented flue gas
cleaning technique (e.g. WFGD, SDA, DSI) need to be evaluated and
optimized to minimize a negative impact on fouling and corrosion
by high concentrations of critical components such as sulphur (and
chlorine) within the recycle loop. For high sulphur coals and for
certain ash mineral systems higher deposition tendencies may be
found and additional measures may be required for reliable plant
operation.
Changes in decomposition behaviour of carbonate minerals
and transformation behaviour of included iron bearing miner-
als, increased stability of sulphates towards higher temperatures,
increased sulphur retention in fly ash and deposits and increased
agglomeration tendencies are major concerns regarding ash depo-
sition, slagging and fouling in oxyfuel-fired boilers. However,
reduced flame temperatures and increased emissivity of the gas and
particles combined with reduced particle velocities might result in
reduced slagging and fouling tendencies. In general, some changes
in slagging and fouling tendencies between air- and oxy-firing
can be expected. However, their importance and impact of those
changes is varying and may be either positive or negative for com-
bustion systems. The attributed changes probably lay within the
boundary of current understanding of slagging and fouling mecha-
nisms in pulverized fuel combustion. Ash deposition, slagging and
fouling are more dependent to coal specific properties (i.e. coal and
mineral characteristics and composition) and process line-up (i.e.
cleaned vs. un-cleaned recycle) than changes in firing mode (i.e. air
vs. oxy).
2.2.5. Corrosion
Corrosion is a combined influence of deposit and flue gas atmo-
sphere on materials. Many researchers expected elevated corrosion
risks in oxyfuel combustion. The reasons for this are increased con-
centrations of corrosive gases such as SO2 /SO3 , HCl, H2 O and higher
partial pressures of CO2 . Moreover, increased formation of sulphate
deposits in oxyfuel combustion is relevant to fireside corrosion.
Results from Kull et al. (2009) and Kranzmann et al. (2009)
lead to the conclusion that high CO2 partial pressures cause carbon
enrichment of the alloys (i.e. carburization) and resulted in a locally
incomplete oxide scale. Abellán et al. (2010) investigated the oxi-
dation behaviour of number of martensitic 9-12% chromium steels
in a model gas mixture containing CO2 and H2 O. They observed
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
substantial carburization and concluded that the iron or chromium
based oxide scales of low chromium content steels appeared to be
permeable for CO2 molecules. A possible time dependent degrada-
tion of the material can thus be an issue especially for low-alloyed
steels. Similar observations were reported by Otsuka (2013) who
commented that the carburization was increasing with increas-
ing temperature. In earlier corrosion studies performed by Kull
et al. (2008), carburization has been reported also for austenitic
steels where it is associated with increased micro-hardness while
many other oxyfuel studies fail to show similar results. It has been
suggested that the presence of water vapour suppresses the carbur-
ization since water vapour is more strongly adsorbed on the metal
surfaces in comparison to CO2 . In a wet recycle oxyfuel combus-
tion atmosphere a significant amount of water vapour is present so
carburization may efficiently be suppressed. Nevertheless, carbur-
ization is likely to be a problematic issue under reducing conditions,
e.g. in water wall areas under certain operating conditions (e.g.
staged oxyfuel combustion).
High water vapour concentrations under wet recycle oxyfuel
conditions may also cause a loss of chromium scale. Such an effect
was reported in a fundamental study by Mu et al. (2013). Inter-
action of water vapour and chromium oxide are likely to form
volatile chromium species and consequently a loss of the protec-
tive chromium oxide scale. The loss of the protective oxide scale
accelerates oxidation rates. A comparative corrosion study simu-
lating wet and dry recycling oxyfuel conditions suggested higher
corrosion rates for wet recycle conditions (Holcomb et al., 2013).
Stein-Brzozowska et al. (2014) and Huczkowski et al. (2013) sug-
gested that the high level of water vapour to be more influential
even in comparison to increased SO2 concentration.
The influence of increased SO2 in oxyfuel combustion and its
consequences regarding corrosion have been extensively studied.
However, there is still a lack of clear evidence to show the detrimen-
tal effects of increased SO2 and the extent of material sulphidation is
likely to be more influenced by temperature and/or alloy composi-
tion. Stein-Brzozowska et al. (2014) showed in oxyfuel experiments
with different alloys that increasing Cr content decreases corrosion
rates. This was attributed to the better chromium oxide scale which
is expected to be protective against SO2 attack. Chromium and mag-
nesium sulphides in the base metal along the grain boundaries were
a common observation in the presence of SO2 (Stein-Brzozowska
et al., 2014; Huczkowski et al., 2013). However, internal oxidation
beneath the oxide scale seems to be reduced in the presence of SO2
which is a beneficial influence (Huczkowski et al., 2013). The rela-
tive rate of adsorption (on metal surface) of studied gaseous species
are in the following order SO2 > H2 O > O2 > CO2 . Formation of sulp-
hides is likely to suppress internal oxidation since sulphides are
forming ahead of the internal oxidation front. Moreover, formation
of sulphides is also likely to reduce chromium oxide evaporation
that may be caused by water vapour (Huczkowski et al., 2013).
Stein-Brzozowska et al. (2014) reported increasing sulphur
contents of deposits over time when exposed to SO2 -rich oxyfuel
atmospheres. An increase of calcium and magnesium sulphates
over time confirmed a continuing capture of sulphur from gas
phase after ash deposition. A CO2 -induced SO2 release that could
accelerate corrosion processes (previously suggested by Kull et al.
(2009) was not observed, since the presence of SO2 stabilizes
sulphates thermodynamically, even in high CO2 atmospheres
(Stein-Brzozowska et al., 2014). Stein-Brzozowska et al. (2014)
and Huczkowski et al. (2013) speculated that the sulphur-binding
capacity of deposit particles partly plays a protective role. The
amount of sulphur capturing species, and hence the protective-
ness of the respective ashes/deposits varies among coal ashes. The
extent of the impact of various sulphate/sulphide deposits on cor-
rosion varies and is likely dependent flue gas atmospheres, stability
of deposit minerals and their interactions with alloy materials.
67
Catastrophic corrosion was observed in lab exposure tests in a
synthetic oxyfuel atmosphere with pyrite (FeS2 ) as a synthetic
deposit on 310 austenitic steel. With CaSO4 as synthetic deposit, no
clear evidence of sulphur induced corrosion was observed (Stein-
Brzozowska et al., 2013). Hot corrosion is critical under molten
deposits. It is not expected in the absence of molten deposit which
was the case in the experiments by Stein-Brzozowska et al. (2013).
In conditions where molten deposits are not expected, the partial
pressure of SO3 (in a range of 10−4 -10−3 bar) is the primary parame-
ter expected to be critical for corrosion phenomena (Holcomb et al.,
2012). Oakey et al. (2013) studied the effect of temperature varia-
tions on air and oxyfuel corrosion under various synthetic deposits.
He observed that for air-firing conditions the highest metal loss was
observed at 650 ◦ C while for in oxyfuel atmospheres it was shifted
to 700 ◦ C. This shift is possibly caused by higher SOx during oxy-
combustion (Oakey et al., 2013). Higher SOx concentrations likely
increase the stability of sulphates which will consequently shift the
corrosion peak towards higher temperatures.
Chlorine induced corrosion may be reduced in oxyfuel atmo-
spheres, since the increased SO2 partial pressure suppresses the
formation of highly corrosive chloride deposits by converting chlo-
rides into relatively less corrosive sulphates (Paneru et al., 2013b).
A comparative study (air vs. oxyfuel combustion) of corrosion
rates (Fry et al., 2011) using an online corrosion probe showed
higher super heater corrosion rates during oxy-firing. Three differ-
ent US coals were combusted during this trial and 3 different super
heater materials were tested. Lower corrosion rates were reported
for materials exposed under water-wall conditions during these
tests (Fry et al., 2011). In contradiction to most other studies, Kung
(2013) reported significantly lower corrosion rates under oxyfuel
conditions and explained this by effects like reduced diffusivity,
formation of carbonates, lower availability of sulphates and base
neutralizing effect of the acid gases like CO2 (Kung, 2013).
To sum up, most of the comparative studies suggested corrosion
may be a critical issue under oxyfuel combustion conditions which
likely demands dedicated consideration in the oxyfuel boiler design
to choose suitable alloys for the different heat exchangers (Anheden
et al., 2011).
2.2.6. CFD modelling for full scale utility boiler
CFD simulations have been used to promote the understanding
of oxyfuel combustion systems and have been used as one of the
tools for full-scale boiler design. An excellent example is presented
by Smith et al. (2014), who have used extreme computing power to
model the combustion process using LES and develop a validation
and uncertainty quantification (V/UQ) tool in order to simulate the
design of a real boiler operating in oxyfuel combustion mode. Their
main objective is to simulate the fireside performance of an ultra-
supercritical boiler – predicting the heat flux and residual carbon
in ash. To validate their results, they have modelled the operation
of Alstom’s 15 MWth boiler simulation facility (BSF). In their work,
they have applied a mesh of 130 million cells corresponding to a
fineness of 1–2 cm edge length and achieving a temporal resolution
of ∼10−6 s. They use the V/UQ methods for verification and vali-
dation; and demonstrated a good agreement between measured
and simulated results.
In general, less detailed simulations of full scale boilers were
performed by numerous researchers using RANS based simula-
tion codes. In these studies, the changing heat transfer caused
by the increased concentrations of CO2 and H2 O in the flue gas
were the primary focus of the modelling work. Lignite fired boil-
ers in the range of 330 MWe to 550 MWe have been studied, e.g. by
Nikolopoulos et al. (2011) and Al-Abbas et al. (2012). Bituminous
fired boilers in the range of 500 MWe to 600 MWe have been inves-
tigated by Leiser (2011) and Black et al. (2013). However, they are all
of predicting manner without validation by measurements, which
68 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 11. Influence of  on SO2 -concentrations in coal combustion, for various O2 -contents in CO2 - (left) and N2 -based (right) oxidants at 1000 ◦ C.
(Adapted from Hu et al., 2000).
can be seen disadvantageous compared to the LES study described
above.
2.3. Formation and reduction of SOx , NOx , and Hg species
Knowing the fate of the other non-CO2 components such as SO2 ,
SO3 , NOx and trace elements (i.e. Hg) during oxyfuel combustion
is important since these components impact the power plant pro-
cess design including flue gas cleaning equipment, construction and
operation in various aspects.
Due to the lack of flue gas dilution by the airborne N2 , the
concentration (reported as %v, ppmv or mg/Nm3 ) of the flue gas
constituents such as CO2 , SOx , H2 O, and others, would generally
increase by a factor of ∼4 during oxyfuel combustion.
If some of these non-CO2 components that are removed within
the recycle loop, their concentrations can be controlled to a level
similar to the concentration reported in air firing. Such behaviour
typically is observed for dust concentrations in oxyfuel combustion
that is controlled within the recycle loop by a particulate control
unit (i.e. ESP or FF). This could also be observed if SOx is removed
in the FGD within the recycle loop.
The impact of oxyfuel combustion on concentrations of other
flue gas constituents that are determined to a large extent by the
combustion process, such as CO and NOx , is less pronounced. These
compounds can be destroyed when passing through the flame zone
after being recycled, which limits their levels in the recycle loop.
The following sections will cover an updated discussion on the
formation and reduction of SOx , NOx and Hg in an oxyfuel PC coal
fired process.
2.3.1. Formation and capture of SO2
Sulphur oxides, SO2 and SO3 , are known for their corrosive-
ness at high and low temperatures. This can impact the boiler,
downstream equipment, flue gas ducting and other associated
equipment. These species also play a key role in furnace slagging
and the fouling of the convective heat exchangers, SCR catalysts and
regenerative gas preheaters. Additionally, SOx (together with NO2 )
contributes to the acid formation during the flue gas compression.
In combustion processes, the sulphur contained in the fuel is
oxidized mainly to SO2 and a small percentage is also converted to
SO3 .
As mentioned above, the exclusion of N2 in oxyfuel combustion
causes a significant increase of SO2 concentrations. As a conse-
quence, in oxy-combustion extremely high SO2 levels can occur:
SO2 concentrations up to above 20,000 ppm were measured during
oxyfuel combustion of a sulphur rich coal (Ahn et al., 2011).
In air as well as in oxyfuel combustion, the most important
parameters influencing the concentration of SO2 in the flue gas are
the sulphur content of the fuel, the availability of oxygen (i.e. stoi-
chiometric ratio/oxygen partial pressure), the capacity of the fuel’s
ash to capture the sulphur, and the temperature-residence time
profile of the combustion process.
The influence of oxygen (i.e. stoichiometric ratio) on the SO2
formation was demonstrated comparatively for CO2 and N2 rich
atmospheres by Hu et al. (2000). They have concluded that the stoi-
chiometric ratio () has a significant influence to the SO2 formation
in both atmospheres (see Fig. 11), while the impact of the changed
combustion atmosphere was limited.
From Fig. 11, it can be noted that the formation of SO2 reaches
its peak at  = ∼0.85 for both conditions. As the stoichiometric ratio
reduces to less than 0.85, the SO2 emissions also decrease. The
reducing trend of the SO2 observed at this regime could only be
attributed to the low O2 content in the environment thus favouring
the conversion of sulphur to other species such as H2 S (Dhungel
et al., 2007; Dhungel, 2010).
Fig. 11 shows that at  > 1, the SO2 also decreases as stoichiomet-
ric ratio increases. In N2 as well as CO2 atmospheres the reduction
of SO2 at higher stoichiometric ratios is more evident at a higher
oxidant oxygen concentration (i.e. >50% O2 ) which may have impli-
cation on oxyfuel combustion processes due to their higher O2
concentrations.
It is well established that the alkaline and alkaline-earth com-
pounds can take up SOx from the flue gas to form sulphates. Liu et al.
(2000, 2001b) investigated the desulphurization by Ca species and
the CaSO4 decomposition reactions at high temperature under air
and oxy-fuel combustion conditions in a fixed bed experiment and
modelling and simulation study.
Fig. 12 presents simulated desulphurization efficiencies of lime-
stone in air and oxy-fuel environments.
It can be observed that the flue gas desulphurization efficiency in
O2 /CO2 (i.e. oxyfuel) atmosphere compared to air-firing is increased
by a factor of about 4. According to Liu et al. (2001b) the desul-
phurization is promoted by: (a) the longer residence time due
to the recycling of the flue gas, (b) the higher SO2 concentra-
tion in flue gas, and (c) the inhibition of the decomposition of
CaSO4 at higher temperature by the high SO2 concentration in
the flue gas. Also, the elevated CO2 partial pressure may have
a positive impact on ash particle porosity and therefore the
desulphurization efficiency (Chen and Zhao, 2006; Chen et al.,
2007).
The increased retention of sulphur in the ash in oxyfuel
combustion was also observed in various experiments made by
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125 69

100 System desulphurisation 100 System desulphurisation

efficiency, [%] efficiency, [%]
80 O2/CO2, S = 2 wt.-% 80

O2/CO2, S = 2 wt.-%
60 60

40 O2/CO2, S = 1 wt.-% 40
Air, S = 2 wt.-%

20 20
Air, S = 2 wt.-%
Air, S = 1 wt.-%
0 0
1.300 1.400 1.500 2 4 6 8
Temperature[K] Residence time of particles [s]

Fig. 12. Left: Calculated temperature dependency of the desulphurization efficiency at  = 1.2, 8s residence time (once-through), Ca/S-ratio = 5 and 10 ␮m particle diameter for
coal combustion in O2 /CO2 atmosphere with a recirculation rate of 0.84 and for air combustion; right: Calculated dependency of the desulphurization efficiency on residence
time at 1400 K,  = 1.2, Ca/S-ratio = 5 and 10 ␮m particle diameter for coal combustion in O2 /CO2 atmosphere with a recirculation rate of 0.84 and for air combustion.
(Adapted with permission from Liu et al., 2001b).

Fleig et al. (2011a) and Spörl et al. (2013). Fleig et al. (2011a) found
in their experiments in a 100 kWth rig firing low sulphur lignite
that in air firing around 67% of the fuel-sulphur is converted to
SO2 , while in oxyfuel firing this was between 41% and 46%. Spörl
et al. (2013) reported conversion rates of 93% and 79%, respectively
for air and oxy-fuel combustion experiments with a high sulphur
lignite. These observations support the results by Liu et al. (2000,
2001b) that SO2 capture by ash is enhanced in oxyfuel combustion.
This is the reason why the SO2 emissions reported as ratio of mass
flow of SO2 to energy input (i.e. mg SO2 /MJ) in oxyfuel operation
are lower than in air-firing (Scheffknecht et al., 2011; Wall et al.,
2009).
To sum up, the retention of sulphur in the ash in oxyfuel fired
systems is enhanced compared to air-fired processes. But this also
depends on a variety of individual factors, which differ between
fuels, plant and combustion settings.
2.3.2. Formation and capture of SO3
SO3 together with moisture forms sulphuric acid (H2 SO4 ) during
cooling of the flue gases. The formed H2 SO4 is known to initiate low
temperature corrosion and SCR and air-heater fouling problems
which highlights the importance of SO3 for combustion processes.
During combustion and along the flue gas path, SO3 is formed from
SO2 in homogeneous (bi- or tri-molecular) gas phase reaction (Eq.
(1)) or in heterogeneous, solids catalyzed reaction for example on
iron oxides.
SO2 + O(+M) → SO3 (+M) (1)
The extent of the formation of SO3 in both air or oxyfuel com-
bustion is significantly influenced by the SO2 partial pressure in
flue gas (and hence by the sulphur content of the fuel).
The importance of the SO2 concentration on the formation of
SO3 is illustrated in Fig. 13 that presents the results of experiments

Fig. 13. SO2 vs. SO3 concentrations in experiments performed at Stuttgart university by Spörl et al. (2014d) and Spörl and Maier (2011), at IHI’s combustion test facility in
Japan (Wall et al., 2009) (combustion of similar coals A, B and C at Stuttgart university and IHI), at Alstom’s 15 MW combustion test rig, by Kenney et al. (2011) and by Tan
et al. (2006) (Canmet); Dotted lines represent SO2 to SO3 conversion percentages.
70 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 14. Catalytic/heterogeneous SO2 /SO3 conversion on coal fly ash and homogeneous SO2 /SO3 conversion at different temperatures under simulated air and oxy-fuel flue
gas conditions (air: 1000 ppm SO2 , 5 vol% O2 , 3 vol% H2 O, and balance N2 ; oxy: 1000 ppm SO2 , 5 vol% O2 , 3 vol% H2 O, 85 vol% CO2 , balance N2 ). Also shown is the SO2 /SO3
conversion according to Marier and Dibbs (Marier and Dibbs, 1974) for 1.8 s residence time, 185 cm3 /min flow rate, and gas composition of 18.9 vol % H2 O, 32.4 vol% O2 ,
8.4 vol% SO2 , and 40.4 vol % N2 (figure from Belo et al., 2014).
undertaken during air and oxyfuel combustion experiments from
a number of different combustion test facilities (different locations
and scales) using different fuels. It is obvious that higher sulphur
contents in coal that lead to high SO2 levels normally result in
higher SO3 concentrations (Fleig et al., 2011b; Spörl et al., 2014d).
Another important parameter is the content of alkaline and
alkaline-earth compounds in the ash that can capture SO3 in form
of sulphates directly (Ellison and Weiler, 2005a,b), but also reduce
it indirectly by capturing SO2 , the precursor of SO3 . Since under
oxy-fired conditions, the capture of SO2 in the ash is enhanced, this
also affects the generation of SO3 in positive way by reducing the
available SO2 . Additionally, SO3 /H2 SO4 can also be separated from
gas phase effectively by condensation on fly ash particles at tem-
peratures near or below the sulphuric acid dew point temperature
(Cao et al., 2010b). Such temperatures can for example be found in
filters. In comparative combustion experiments under air and sim-
ulated oxyfuel recycle conditions (recycling of CO2 , SO2 , NO, Hg0 )
the fabric filter of a combustion test rig that was operated between
195 and 225 ◦ C captured up to 80% of the SO3 measured before the
filter under air fired conditions and up to 66% in oxy-firing (Spörl
et al., 2014b,d). One possible reason for the lower SO3 capture rates
found under oxy-fired conditions may be due to the much higher
SO3 concentration levels in the flue gas as compared to the air
fired case. In oxyfuel tests at semi-industrial scale, a SO3 reduction
of 62% was observed at the ESP when firing high sulphur lignite
(Spörl et al., 2013), whilst at Vattenfall’s 30 MW oxyfuel pilot plant,
a reduction of 40.6% was achieved – also firing lignite (Burchhardt
et al., 2012). Additionally, test undertaken by Alstom (Levasseur and
Botha, 2010) at their BSF indicated more SO3 species collected in the
fly ash from the baghouse during oxyfuel combustion as compared
to air firing of Illinois Bituminous coal.
The SO3 formation in the boiler at temperature down to approx.
500 ◦ C (i.e. convective section of the boiler) is also influenced by
the presence and amount of catalytically active compounds in the
ash (e.g. Fe2 O3 ), with higher contents leading to higher SO3 forma-
tion (Belo et al., 2014; Walsh et al., 2006). Catalytic SO3 formation is
highly dependent on temperature, with a maximum of the SO2 /SO3
conversion at about 700 ◦ C (see Fig. 14) (Belo et al., 2014; Marier
and Dibbs, 1974). The difference between air and oxyfuel gas atmo-
spheres was reported to be low in lab scale testing on the catalytic
SO3 formation on coal fly ashes (Belo et al., 2014). Ellison and Weiler
(2005a,b) reported that SO3 could also be entrained in the fly ash
particles, as well as on ash deposits.
The homogeneous SO3 formation, like its catalytic counterpart,
clearly shows a temperature-dependent behaviour (Belo et al.,
2014; Fleig et al., 2011b). Both reaction mechanisms are relatively
slow (Belo et al., 2014; Walsh et al., 2006), which is the reason
why in a practical firing systems, no equilibrium concentrations of
SO3 can be observed. Therefore, the temperature-residence-time-
profile of the flue gas in the boiler and associated ducting is another
key parameter influencing the formation of SO3 (Belo et al., 2014;
Fleig et al., 2011b; Srivastava et al., 2004).
Also, the O2 concentration in the flue gas has a direct effect on
the SO3 formation rate, which increases with increasing oxygen
content (Belo et al., 2014; Fleig et al., 2011b; Zheng and Furimsky,
2003). Besides the above mentioned fuel properties and operating
parameters, installed flue gas cleaning equipment has a consider-
able impact on SO3 concentrations. For example, 0.5-2% of the SO2
can be catalytically oxidized to SO3 in SCR DeNOx systems, lead-
ing to increased SO3 concentrations (Cao et al., 2010b; Walsh et al.,
2006).
In practice, SO2 /SO3 conversion rates between 1% and 5% (Tan
et al., 2006) with SO3 concentrations up to about 40 ppm in coal
fired air- and over 180 ppm in oxyfuel-facilities were reported
(Ahn et al., 2011; Kenney et al., 2011). This considerable increase
is mainly a result of the increased SO2 concentrations under oxy-
fuel fired conditions. In a studies by Fleig et al. (2011b) and Spörl
et al. (2014d), no clear trends were observed on changes in the
SO2 /SO3 conversion ratios between air and oxy-firing (see also
Fig. 13).
At temperatures below about 400 ◦ C gaseous sulphuric acid
starts to form from the reaction of SO3 and H2 O and reaches
complete transformation at approx. 200 ◦ C (Hardman et al., 1998;
Perujo, 2004). The dew point of the formed H2 SO4 depends on the
concentrations of H2 O and SO3 /H2 SO4 in the flue gas. It can be calcu-
lated based on those species’ partial pressures according to Verhoff
and Banchero (1974), Okkes (1987) or by a more recent correla-
tion by ZareNezhad (2009). In power plants, H2 SO4 dew points
typically range between 95 and 160 ◦ C. With increased H2 O and
SO3 /H2 SO4 concentrations, considerably higher dew point temper-
atures can be found in oxy-fired processes compared to air-fired
ones. When temperature falls below the H2 SO4 dew point, gaseous
H2 SO4 starts to condense. In power plants, relevant temperatures
are found in the region of filters/precipitators and air pre-heaters,
where substantial problems due to low temperature corrosion can
occur (ZareNezhad, 2009). In oxyfuel plants also the recycle lines
are critical in respect to low temperature H2 SO4 corrosion. Gen-
erally, the air/oxidant pre-heater outlet temperature is limited to
temperatures above the acid dew point, which limits the utiliza-
tion of the flue gases’ sensible heat and thereby lowers a plant’s
efficiency. In cold parts of power plants, also fouling by sulphate
deposits can be a severe problem triggered by SO3 /H2 SO4 .
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 15. Percentage reduction of recycled NO during unstaged, simulated wet and dry flue gas recycle experiments for El Cerrejon hard coal & pre-dried Lusatian lignite
( = 1.15).
(Adapted from Ndibe et al., 2013).
2.3.3. Formation and reduction of NOx
In an oxyfuel combustion power plant, understanding the fate
of NOx is essential as it contributes to the HNO3 formation during
the flue gas compression situated in the CO2 processing unit.
Three major pathways of nitric oxides (NOx ) formation are
known: thermal and prompt NOx formation and conversion of fuel
nitrogen to NOx . In oxyfuel combustion, due to the absence of air-
borne N2 and therefore very low N2 concentrations, the thermal and
prompt NOx formation pathways could be negligible. Therefore, the
NOx formation from fuel-N is the most important pathway in oxy-
fuel, as in air-firing. Approximately 95% of the total NOx consists
of nitric oxide (NO), the remainder consisting of nitrogen dioxide
(NO2 ) and small amounts of nitrous oxide (N2 O) and other nitrogen
oxides (Scheffknecht et al., 2011).
NOx formation during coal combustion is a complex phe-
nomenon with simultaneous NOx formation and reduction in the
flame zone. It is partly dependent on the chemical characteristics
of the coal, but more importantly, on the firing conditions in the
furnace. The most important conditions during combustion influ-
encing NOx formation are O2 distribution in the flame and flame
temperature.
Coal properties such as coal rank, nitrogen and volatile matter
content affect the nitrogen evolution during pyrolysis in conjunc-
tion with combustion conditions like temperature, residence time
and heating rate. During pyrolysis, fuel-N is split into volatile-N fur-
ther released as HCN or NH3 , and char-N. Gas phase species are then
transformed either to NO or N2 . NO already formed can in fuel rich
zones be reduced by hydrocarbons to volatile-N and depending on
local conditions, be further transformed into N2 in a process called
re-burning. Char-N undergoes a series of heterogeneous reactions
during the oxidation of char. Char itself can also serve to enhance
the reduction of NO either directly or indirectly by reactions with
CO or H2 formed during char combustion.
Oxygen distribution can be influenced by application of oxi-
dant staging which is a well-established primary measure known
from air-firing. The successful application of oxidant staging for NOx
reduction that was originally developed for air-firing was demon-
strated under oxyfuel combustion conditions by Dhungel (2010).
However, due to the risk of corrosion in reducing high SOx and H2 O
oxyfuel atmospheres and due to the fact that the oxyfuel combus-
tion process may allow an efficient NOx removal in the CPU, oxidant
staging is likely to be practiced only rarely in industrial oxyfuel
power boilers.
Experiments showed that NOx emissions in oxyfuel combustion
(i.e. mg NOx /MJ) are significantly lowered compared to air-fired
conditions (Buhre et al., 2005). The lower NOx values in oxyfuel
combustion can be partly explained by the suppressed thermal NOx
formation. In addition, NOx in the flue gas recycled to the burner is
decomposed and re-burned to large extent when it passes the fuel-
rich flame zone (Ndibe et al., 2013). The effect is illustrated in Fig. 15
71
where the reduction of recycled NO is plotted for different fuels and
oxidant O2 concentrations under wet and dry recycle conditions. In
this figure it can also be observed, that re-burning of recirculated
NO is less efficient at high oxidant O2 concentrations.
Measurements in the near-flame zone showed that NOx precur-
sor components, well-known from air-firing such as HCN and, and
in the case of lignite, NH3 can also be found in a CO2 -rich (simu-
lated) oxyfuel atmosphere at concentrations similar as in air firing
(Dhungel, 2010). Other investigations showed an increase of HCN
and NH3 concentrations in the near-flame zone under oxy-fired
conditions that may be due to the recirculation of NOx to the fur-
nace and its subsequent reduction to NH3 and HCN during an early
stage of the combustion (Tan et al., 2005).
The role of char in NO reduction can be diminished if those
chars have low reactivity. Chars from low rank coals are gener-
ally known to be more reactive than chars from higher rank coals.
However, increasing char reactivity can counteract NO reduction
as reported by Liu and co-workers (Liu et al., 2001a, 2003). They
observed a decrease in the NO reduction efficiency with increasing
coal reactivity especially for combustion involving a 30 vol% O2 /CO2
oxidant. They concluded that highly reactive char is consumed at
a faster rate under high O2 combustion conditions, thus reducing
the possibility of NO reduction on its surface.
During oxyfuel combustion, high CO2 concentrations cause
increased CO concentrations in the near flame region by the
Boudouard reaction, the water gas shift reaction, the gasifica-
tion reactions and the dissociation of CO2 (Al-Makhadmeh et al.,
2009; Toftegaard et al., 2010; Toporov et al., 2008). The increased
CO level can enhance the reduction of NO and therefore con-
tribute to the decrease in NO emissions observed during oxyfuel
combustion (Álvarez et al., 2011; Toftegaard et al., 2010). Also
the increased H2 O concentrations in oxyfuel combustion without
water removal from the recycled gas affect the formation of NOx .
Cao et al. (2010a), by means of CFD modelling, showed high concen-
trations of nitrogen intermediates in the presence of steam which
ultimately favour NO reduction in oxyfuel combustion. Based on
numerical simulations, Stadler et al. (2011) agree to this observa-
tion that wet recycle oxyfuel combustion conditions lead to lower
NOx emissions compared to oxyfuel combustion with a dried flue
gas recycle. Katoh et al. (2006) concluded that steam addition in
flames enhances the production of radical species, such as OH,
H, O and HO2 , which play an important role in NO formation
and reduction mechanisms. On the other hand, increased levels of
radicals such as OH and HO2 may also promote the NO-NO2 oxi-
dation. For wet recycle conditions, Ndibe et al. (2013) observed
a fuel specific increase in the formation of NO2 during combus-
tion experiments simulating wet and dry recycle conditions. In a
practical boiler application, an increase of NO2 was also observed
during various tests at Callide oxyfuel power station (Spero et al.,
2013a).
72 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
It can be summarized that NOx formation and reduction is a
strong function of combustion conditions and the behaviour cannot
always be generalized. However, a general observation in experi-
ments by numerous researchers is that energy based NOx emissions
(i.e. in mg NOx /MJ) are considerably lower in oxyfuel combustion
than in air-firing, which is a clear benefit for the oxyfuel technology.
In addition, it can be concluded that NOx formation and destruction
mechanisms during oxyfuel combustion are fundamentally similar
to conventional air combustion but high water concentrations in
the flue gas can lower the NOx formation in oxyfuel conditions.
2.3.4. Formation, oxidation and capture of Hg
Mercury emissions in conventional coal fired power plants are
an environmental concern. However, in an oxyfuel combustion
power plant, mercury is an operational issue to the CO2 Processing
Unit (CPU) situated downstream of the boiler due to its corrosivity
on any aluminium heat exchangers (Santos, 2008, 2010).
Mercury occurs in coals mostly associated with sulphur com-
pounds (e.g. FeS2 ) or organic fractions (Galbreath and Zygarlicke,
2000; Kolker et al., 2006; Pavlish et al., 2003). During combustion,
Hg is completely evaporated and converted to its elemental form
Hg0 (Wilcox et al., 2012) reaching Hg concentrations in a range of
1-20 ␮g/m3 in air-fired systems (Senior et al., 2000). During cool-
ing of the flue gases and via the interactions with other flue gas
compounds (most importantly Br and Cl containing species) Hg0
becomes oxidized to Hg2+ (e.g. in form of HgCl2 ) and can also be
captured with the fly ash in filters and precipitators (Senior et al.,
2000; Pavlish, 2009; Sliger et al., 2000; Wilcox et al., 2012). In
the past years considerable efforts have been dedicated to clar-
ify how Hg is released, oxidized and captured in air-fired power
plants and how this can be influenced to reduce Hg emissions and
results have been summarized in a number of reviews and arti-
cles (Pavlish et al., 2003, 2010; Pavlish, 2009; Wilcox et al., 2012;
Scheffknecht et al., 2012; Kolker et al., 2006; Spörl et al., 2014a).
The most important factors influencing the concentration levels,
speciation and removal of Hg from flue gas in air fired combustion
are the content of Hg and Cl (and Br) of the coal, the combustion
conditions, the SOx concentrations and speciation, the properties of
the generated fly ash (i.e. unburned carbon (UBC), Ca, catalytically
active compounds), the temperature-residence time profile of the
flue gas in a plant and the application of gas cleaning equipment
(SCR, FGD, filters, sorbent injection). It is expected that the majority
of the listed correlations known from air-fired systems can also be
transferred oxyfuel combustion. However, until now the published
information on Hg behaviour in oxyfuel combustion is limited.
The impact of the change from an N2 to a CO2 atmosphere and
also the higher H2 O concentrations in oxy-firing were shown to
have no considerable impact on equilibrium behaviour of Hg and
other trace elements (Jano-Ito et al., 2014; Zheng and Furimsky,
2003; Edwards et al., 2001). Thermodynamic equilibrium simula-
tions showed however, that the speciation and volatility of trace
elements in oxyfuel combustion may be altered mainly due to
higher concentrations of S and Cl gases (Jano-Ito et al., 2014).
According to Pavlish et al. (2010) and Zhuang et al. (2011), the Hg
speciation and capture in oxyfuel systems can be impacted by the
increase of the H2 O, HCl, SOx and Hg concentrations in the flue
gas and by a change in NOx concentrations. Changes in the HCl,
SOx and Hg concentrations can potentially improve Hg oxidation,
but may also decrease Hg capture. Both however depends onthe
kind and extent of cleaning of the recycled flue gas in an oxyfuel
system. Altered ash loadings and changes in the temperature pro-
file in an oxyfuel combustion process can also affect Hg oxidation
and capture. Moreover, the increased residence time of flue gases
that are partially recycled and therefore passing flue gas cleaning
equipment several times can improve the Hg emission behaviour
(McDonald, 2013).
Oxyfuel combustion in pilot scale showed a doubling (Li et al.,
2012) or tripling (Mitsui et al., 2011) of the Hg concentration in
the flue gas as compared to air-firing. In combustion experiments
under simulated oxyfuel recycle conditions (recycling of CO2 , SO2 ,
NO, Hg0 ) an increase of the Hg oxidation was observed, compared
to air-fired combustion, while Hg capture efficiencies on a fabric
filter were lower in oxy-firing, but at a much higher Hg concen-
tration level at the filter inlet (Spörl et al., 2014a,b). Improved Hg
oxidation under oxyfuel conditions was also observed by other
researchers (Van Otten et al., 2013). Van Otten et al. (2013) also
tested Hg reduction techniques such as activated carbon injection
and CaBr2 additions for Hg oxidation. However, under oxy-fired
operation those techniques had only limited impact on Hg removal
and oxidation for the fuels tested.
To sum up, different researchers measured higher Hg oxida-
tion and Hg concentration levels in oxy-firing compared to air-fired
combustion, while Hg capture efficiency on fly ash may be reduced
under oxyfuel fired conditions. It should however be noted that
published experimental results on Hg behaviour in oxyfuel com-
bustion are limited and that Hg oxidation and fly ash capture are
known to be complex and highly fuel and plant dependent.
2.4. Air ingress and its management
In a conventional coal-fired boiler, the system downstream of
the furnace is typically operated at a negative pressure, air may
leak into the system through cracks in the equipment or areas that
are opened during operation. These air ingress could be as high as
10-15% over the lifetime of the boiler. However, the impact of the
air ingress to the conventional air fired coal power plant is generally
negligible.
The primary objective of oxyfuel combustion is to maximize the
concentration of CO2 by burning the fuel with O2 . This should ben-
efit the whole power plant – as higher %CO2 in the feed gas of the
CPU could help achieve better efficiency and higher CO2 recovery.
Thus, for oxyfuel combustion, air ingress into the boiler is not
desirable, but cannot be completely avoided. Air ingress could con-
tribute to the increase of non-CO2 components such as N2 , Ar and
O2 . This also increases the flue gas flow to the downstream pro-
cesses. Thus could increase cost and power consumption.
Fig. 16 illustrates an indication on how CO2 composition (%dry
basis) of the flue gas from the oxy-PC boiler could be affected
Fig. 16. CO2 composition of the flue gas from the boiler (in % dry basis) and the
impact of O2 purity from the ASU, excess O2 and air ingress (as % of total flue gas
from boiler – wet basis) (Kather, 2007).
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 17. CO2 recovery rate vs feed composition of the CPU cold box – at −55 ◦ C and
30 Bar (White, 2007).
by the purity of the oxygen, level of excess O2 and level of air
ingress.
This graph is estimated based on combustion of hard coal
(Kather, 2007). It should be emphasized that the numbers pre-
sented in the graph are specific to the coal properties (i.e. ultimate
analysis), and operating parameters such as composition of the
recycled flue gas and measures taken to reduce criteria pollutants
(i.e. NOx and SOx ).
The importance of managing the air ingress could be demon-
strated in Fig. 17. This figure illustrates how an increasing air
ingress could impact the performance of the CPU. As the air ingress
increases, the CO2 feed composition to the CPU also decreases and
consequently would reduce the CO2 recovery rate of the plant.
For a new build boiler, the air ingress is about 2-4% (Kather and
Scheffknecht, 2009). As the boiler ages, air ingress is expected to
increase. Thus considerations to avoid air ingress should be made
in the design and the maintenance regime of the boiler and the
downstream equipment.
One way to minimize the air-ingress into the boiler is to adjust
the point of the zero pressure or balance pressure from the top
of the furnace (typical for balanced drought furnace) down to the
lower level (i.e. inlet of the secondary RFG or exit of the FG from
the boiler). This should create a slight positive pressure relative to
atmosphere (McDonald et al., 2013). Due to this adjustment, safety
considerations are important with regard to the ventilation of the
boiler house.
Additionally, the use of CO2 for gas sealing could also be
deployed thus reducing air ingress into the boiler and associated
downstream equipment.
In commercial oxyfuel systems, the application of advanced sys-
tems for the detection and localization of air ingress should be
necessary. This is to take full advantage of the existing plant instru-
mentation, so that leak detection is quick and countermeasures can
be initiated immediately (Preusche et al., 2011a,b; Preusche, 2013).
If the air ingress has increased above the design point considered
as it ages, it could be noticed in the performance of the ID fans, var-
ious flue gas processing units and CPU. An increased in air ingress
could generally lead to an increase in energy consumption of the
CPU due to increase in the flow of the CPU vent and reduced recov-
ery rate. Additionally, this could also be manifested in the reduce
demand of oxygen from the ASU (since oxygen in the air ingress
could increase oxygen content of the RFG).
73
2.5. Power plant operations and flexibility
2.5.1. Plant control and overall operation
Control of an oxy-combustion plant, such as the configura-
tion shown in Fig. 18, though very similar to a conventional
air-fired plant, requires some significant additional considerations
(McDonald and Zadiraka, 2007). The location of the secondary recy-
cle extraction, whether before or after the sulphur removal system
or when there is no sulphur removal system, and equipment selec-
tion which is driven by the sulphur content in the coal, will result
in variations not only in the process configuration as described
previously in Section 2.1, but also in the operation of the plant.
In addition, the steam cycle and balance of plant operation will
vary between subcritical and supercritical cycle but are essentially
the same as with air firing. Oxy-combustion also requires addi-
tional systems such as the ASU, CPU, moisture removal (FGC or
DCCPS) and flue gas reheaters (Gas Htr) which are not present in
conventional coal plants.
Oxy-combustion affords some benefits in boiler operation,
which result in minor differences in the boiler operation. For exam-
ple, to avoid air infiltration the boiler may be operated slightly
pressurized on the gas side and secondary recycle flow can be varied
to control heat transfer.
The oxy-combustion boiler is followed by a flue gas processing
units or GQCS that prepares the flue gas for the boiler and CPU
rather than controlling air emissions as in an AQCS used with air
firing. The GQCS and AQCS have much the same equipment; a dry or
wet scrubber and particulate removal, either a pulse jet fabric filter
(PJFF) or an electrostatic precipitator (ESP). These perform the same
functions of removing particulate, SOx , acid gases, and heavy metals
like Hg, As, and Se. The extent of sulphur removal required depends
on three constraints: (1) the corrosion limits in the boiler, since
recycling flue gas will increase the SO2 concentrations there, (2) the
SO2 concentration allowed by permit limits when air firing to the
stack, and (3) the concentration permitted by the CPU design. Some
CPU designs require low levels of SO2 while others employ a ‘sour-
gas’ process permitting much higher levels. In oxy-combustion the
GQCS also includes moisture removal.
Due to the higher water content entering the GQCS, the adiabatic
saturation temperature in oxy-combustion is slightly higher than
with air firing so the water content and temperature of the flue
gas leaving the scrubber will be slightly higher. This also means
the sulphuric acid dew point will be slightly elevated compared to
air firing. To reduce flow and power consumption in the CPU and
PR fan and provide a drier primary recycle flow to the pulverizers,
moisture reduction is likely be provided. The gas leaving thermal
condensation devices is saturated and must be reheated to avoid
condensation in the downstream flues. In configurations for high
sulphur coals, some reagent can be added to the cooling water to
further reduce the SO2 level entering the CPU if required.
In addition to significant differences in flue gas composition,
the flue gas flow leaving the process at full load is also much
lower in quantity than with air firing (about one-third as much
mass flow) due to the elimination of nitrogen from the combus-
tion process. Since the oxidant can be controlled separately from
the recycled flue gas, where with air firing the oxygen content in
air is fixed, more flexibility in controlling where and how much
oxygen is added in the process can be used to optimize combus-
tion. Independent control of the secondary recycle flue gas flow
(the primary recycle gas flow is dictated by the pulverizer demand)
also allows freedom to adjust the mass flow to the boiler to control
reheater outlet temperature to avoid spray attemperation which is
an efficiency loss.
Since the unit starts up air firing and transitions to recycled flue
gas and oxidant, and the boiler demands a mass flow for steam gen-
eration, the volumetric flows must be measured, converted to mass
74 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 18. Operation schematic for an oxy-pc combustion power plant – illustrating the different dampers position.
flows, and summed to compare to the mass flow set point. Air flow
is measured at the fan air intakes, recycle gas flows are measured
upstream of the PR and SR fans, and oxidant is measured at the
outlet of the ASU. These measured volumetric flows are converted
to mass flows using their known mole weights and temperatures
to compare with the boiler mass flow set point, a complication not
necessary with air firing.
The process is integrated at two basic levels: (1) integration with
the steam cycle and (2) gas side integration. Integration with the
steam cycle consists of utilizing the heat rejected from the ASU
and CPU and providing their process steam needs. These can be
integrated into the steam cycle in various ways to either maintain
net plant efficiency or improve it. The heat rejection can replace
feedwater heating requirements and improve efficiency while the
process steam requirements will extract steam from the cycle
reducing efficiency. Integration of the ASU is relatively straight for-
ward but use of the rejected heat from the CPU is more complex
since it is at the end of the process making it last to start up and first
to shut down and because a CPU trip could have an unrecoverable
impact on the steam cycle if deeply integrated. However, integra-
tion of the CPU heat should be possible with today’s control systems
and some experience. Flue gas reheaters also utilize condensate or
steam from the steam cycle similar to the way a conventional steam
coil airheater might.
Integration within the flue gas process consists of utilizing flue
gas from hotter areas to provide heat for warming cooler gas, such
as the recycle heater or a flue gas reheater, or providing medium for
backpulsing a PJFF, sealing equipment such as the space between
double sealing dampers, conveying material etc. in order to elimi-
nate the use of air which would leak into the process reducing CO2
concentration and increasing mass flow to the CPU, both of which
are detrimental to CPU performance.
2.5.2. Start-up, transition, load changing, and shutdown
(a) Start-up process
Plant startup begins with the ASU followed by the boiler which
is coordinated with the availability of oxidant at sufficient quantity
and purity to allow the boiler to transition to oxy-combustion and
then send flue gas to the CPU. The time required to start the plant
depends primarily on the state of the ASU and CPU and the fea-
tures provided to minimize cool down. If the plant has been idle for
more than 48 h the boiler will be cold and the cold box for the ASU
and CPU will be warm. A boiler can typically reach full load from a
cold start in 8–10 h but the ASU and CPU take much longer if their
coldboxes have reached ambient temperature.
To start a plant from idle (cold boiler, warm coldboxes), suffi-
cient BOP equipment must be started to permit operation of the
ASU including cooling water, power, and wastewater treatment.
These utilities are usually provided by an auxiliary boiler and the
grid. The transition from air to oxy firing can be accomplished at a
lower (minimum) purity depending on the system but the oxidant
and flue gas flows will be increased due to impurities in the oxidant.
If the ASU is being started after an extended outage, with no liq-
uid oxygen level in the coldbox and no LOX storage, it can take 3–4
days for the ASU to reach full oxidant purity depending on when
oxidant flow begins. With LOX and CO2 storage and other enhance-
ments, ASU and CPU startup times from an extended idle period
(warm cold box, cold boiler) can be drastically reduced compared
to that required with conventional auto-refrigeration. Under these
ideal conditions assuming mature technology with enhancements
to minimize ASU and CPU startup times. It is expected that the total
duration to full load would be on the order of 30 h. Fig. 19 shows
the entire process in a Gantt format.
If the ASU has been shut down for a short period of time (plant
restart), it will still be at cryogenic temperatures and maintaining
liquid levels. In this case the ASU can be restarted fairly quickly by
starting the main air compressor, establishing clean dry air flow to
the cold box through the adsorbers, and pressurizing the cold box.
Once the cold box is pressurized, the expander can be started to
produce the temperature drop required for cryogenic separation,
product purity and subsequent production. The cryogenic pumps
are then started and the facility placed on line. Starting up the ASU
after a derime is essentially the same as a cold start-up with the
exception of the plant being warm and requiring a longer period of
time for cool down of the cold box.
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125 75

Fig. 19. Sample start-up from extended idle period.

Fig. 18 and Table 3 show the damper positions for initial startup
with air firing. With the ASU started, the boiler would be started
to coordinate achieving boiler transition load (one pulverize at
minimum pulverizer load) when the ASU is able to produce the
minimum oxidant purity required for transition. At a sufficient time
prior to starting the boiler, the remainder of the BOP including feed-
water treatment and preheating, fuel supply to the lighters and coal
handling are started. Once the necessary BOP systems are operat-
ing and the permissives are met, boiler startup is the same as for
conventional air fired units. Firing of the lighters is initiated in the
boiler and steam pressure is raised to the required pressure for the
steam turbine to be rolled. Once rolled, the turbine is operated for a
few hours until it has ‘soaked’ up to temperature and is ready to be
loaded. At that point the steam turbine-generator is synchronized
with the grid and the plant produces minimum power. The GQCS
system (particulate removal and FGD) is started prior to coal firing
but the steps vary depending on whether it is a dry or wet scrub-
ber, which is determined by the coal sulphur content and boiler SO2
corrosion limits.
When all permissives for coal firing have been met, the first
pulverizer is brought into service, reducing lighter input as needed
to maintain a reasonably constant heat input to the boiler. Once
the oxidant has reached minimum purity and the boiler is in stable
operation with one pulverizer in service at minimum pulverizer
load (usually about 30% of full pulverizer input), the process is
ready for transition to oxy-combustion. The transition load (% of
full load firing rate) depends on the number of pulverizers and
the minimum stable pulverizer load and the type of boiler (sub
or super critical). To minimize emissions to the air (especially
if here is no NOx control), the boiler should be transitioned to
oxy-combustion at as low a coal firing rate as practical. If the
boiler is supercritical, selection of the transition load should be
after dry-out and weaning from the steam-side startup system
to avoid complications and unnecessary disruptions. Typically
supercritical boilers can be once-through at around 35% firing
rate. The transition from air to oxy firing and allowing the gas
composition to stabilize should take about 30 min (or less) in
automatic control.
(b) Transition to oxy-combustion – see Fig. 18 for damper numbering
With the ASU ready to supply oxidant at acceptable oxidant
quantity and purity and with the boiler in stable coal firing opera-
tion at minimum load on one pulverizer at the transition load, the
transition from air firing to oxy-combustion can commence.
Lower purity oxidant can be used during transition to reduce
startup time but may extend the time required to reach full load if
the time required for the ASU to reach full purity is greater than the
time required to ramp the boiler and steam turbine to full load. The
actual quality and availability of oxidant flow depends on the ASU
design. It is expected that the ASU will achieve full purity before the
transition of the flue gases to the CPU. The transition from the stack
to the CPU also depends upon the readiness of the CPU to accept
the flue gas and produce CO2 to the required pipeline purity. Both
the ASU and CPU use a cryogenic process so the startup time is
governed by the time required to achieve the necessary cold box
conditions for oxygen separation in the ASU and CO2 separation in
the CPU as previously explained by example. Overlapping the ASU,
boiler, and CPU startups not only reduces the overall startup time
but minimizes air emissions.
Prior to the initiation of the transition, the SR and PR fan air
intake control and isolation dampers are fully open and the SR
and PR flue gas flow control dampers are fully closed. The stack
damper and stack gas tight dampers are both open and the CPU
inlet is closed (air firing positions in Table 3). The transition to
oxy-combustion begins by first adding a specific amount of oxidant
to the operating burners in order to maintain stable and attached
flames throughout the process. In addition, oxidant control valves
are released to control based on oxidant demand.
Next the SR Recycle damper (5) is gradually opened allowing flue
gas to be drawn into the SR fan inlet. The secondary stream is tran-
sitioned first to avoid upsets to the combustion process since it is a

Table 3
Damper position during start-up, transition and shut down operation of the oxyfuel combustion power plant.

Damper number Damper description Air firing AR transition PR transition Stack-CPU transition

1 SA Intake – controllable Open Closeda Closeda Closeda

2 SA Intake – isolation Open Closed Closed Closed
3 Stack – controllable Open Open Open Closeda
4 Stack – isolation Open Open Open Closed
5 SR – controllable Closed Open Open Open
6 PA Intake – controllable Open Open Closeda Closeda
7 PA Intake – isolation Open Open Closed Closed
8 CPU Inlet – controllable Closed Closed Closed Open
9 CPU Inlet – isolation Closed Closed Closed Open
10 PR – controllable Closed Closed Open Open
a
Damper is reset to idle position when isolation damper is closed.
76 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
larger flow than the PR flow. Once the SR recycle damper (5) is fully
open, the SR fan inlet air damper (1) is gradually closed, increas-
ing the recycled flue gas flow into the SR fan inlet flue. Oxidant is
added to the secondary recycle to maintain the excess oxygen mea-
sured at the boiler outlet at the control set point at the given load
throughout the process to compensate for the oxygen lost as the
air intakes are closed.
Once the secondary stream has been fully transitioned, the
moisture removal system and flue gas reheater must be started
before admitting flue gas into the PR stream. Once these are in
service, the transition of the primary stream can commence using
the same procedure as the secondary stream; gradually opening
the PR recycle damper (10). As the primary stream composition
to the pulverizer transitions from air to recycled flue gas, the
oxygen in the primary stream to the pulverizers is maintained
at a prescribed set point which provides some oxidant with the
fuel to the burner without risking pulverizer fires. When the PR
recycle damper is fully open, the PR fan air intake damper (6) is
gradually closed. Once both the PR (6) and SR (1) fan air intake
dampers are fully closed the boiler process is in full oxy-combustion
mode and the PR and SR fan air intake TSO dampers (2 and 7)
can be closed and the intake dampers (1 and 6) set to their idle
positions.
If the desired recycle flue gas flow is not achieved when the SR
and PR fan air intake dampers (1 and 6) are fully closed and the
flue gas recycle dampers (5 and 10) are fully open, the stack inlet
damper (3) can be closed enough to increase backpressure and force
additional flue gas to the SR and PR fan inlets. Flue gas flow to the
stack must be maintained until the CPU is in service and ready to
accept the flue gas.
Unit load demand controls the PR flue gas demand to satisfy
the needs of in-service pulverizers and SR flow is controlled to sat-
isfy total mass flow to the boiler for combustion and heat transfer.
SR gas flow is also used to control reheat outlet steam tempera-
ture by varying furnace and convection pass absorption. The SR
and PR flows are measured and temperature and density (air or
oxygen/recycle gas) compensated to determine mass flows. This
density compensation accounts for the changing constituents of
the SR and PR streams with air, oxygenated flue gas and a mixture
of the two.
Oxidant (a function of oxygen purity) is demanded from the ASU
as burner, PR and SR oxidant flows. The total demand is the quantity
of oxidant required to deliver the difference between the theoret-
ical stoichiometric oxygen requirement corresponding to the total
Btu input and the oxygen available from any air coming into the
PR or SR fans (measured). The SR oxidant demand is then trimmed
(increased or decreased) to maintain the target excess oxygen at
the boiler outlet (measured). The PR oxidant controls automatically
maintain a minimum oxygen concentration in the PR streams and
the remainder of the oxidant is sent to the SR stream.
The oxidant flow is controlled to maintain volumetric oxy-
gen concentration in the SR and PR streams with their minimum
and maximum limits. The total oxidant to the in-service burn-
ers is a proportional function of the total oxidant demand on the
unit. The oxidant flow to the individual burners associated with
a pulverizer is a function of that individual pulverizer demand
compared to the total firing rate demand. Distribution between
burners is preset during commissioning using valves on each
burner to optimize combustion across the width of the boiler. The
demand for total oxidant is coordinated between the boiler and
the ASU. Once the plant is in full oxy-combustion mode, a sec-
ond pulverizer can be brought into service and so on until BMCR is
achieved.
During the transition of the boiler and GQCS to oxy-mode, the
exhaust flue gas is sent to the stack. Once the boiler/GQCS is in oxy-
mode with the flue gasses sent to the stack and the CPU ready to
receive flue gas, the exhaust flue gas is transitioned from the stack
to the CPU. This transition process should also take about 30 min
in automatic control. The CPU can be started as soon as flue gas is
available from the boiler/GQCS at a CO2 concentration that can be
accepted by the cold. Once pipeline quality CO2 purity is achieved,
CO2 is sent to the pipeline and the only emissions are from the CPU
vent and any leakages from the system.
The CPU startup begins by allowing flue gas to enter the CPU by
opening the CPU TSO damper (9) and then gradually opening CPU
inlet damper (8). Usually a booster fan in the CPU is then started
to control the pressure at the flue gas extraction point in the
boiler-GQCS process and provide sufficient pressure at the inlet to
the CPU main compressor to allow normal compressor function
while preventing significant pressure fluctuations at the flue gas
extraction point which would upset the combustion process. As
the CPU fan is ramped up, flue gas is drawn away from the stack.
When the pressure at the CPU inlet is stable and controlled by the
booster fan at its set point, the stack damper (3) can be gradually
closed to force the remainder of the flue gas flow to the CPU.
Once the stack damper (3) is fully closed, the stack TSO damper
(4) can be closed and the stack damper reset to its idle position. This
idle position is selected to mirror the resistance to the CPU at full
load so a rapid flow shift from the CPU back to the stack can occur in
the event of a CPU trip without creating a significant pressure upset
in the combustion process which would trip the plant. During this
process the CPU receives flue gases and progressively sends them
through its internal processes returning it to the stack at each step
until the entire system has fully started at which point the pure CO2
is sent into the pipeline. The pipeline transports the nearly pure CO2
to the utilization facility or storage site.
When operating in steady-state, the flue gas flow to the CPU (or
stack) is equal to the sum of the oxidant (air and/or oxygen plus
impurities) added, air infiltration from systems operating below
atmospheric pressure, any gases used for conveying or sealing
that are taken after the CPU inlet that enter the flue gas stream,
and the products of combustion less the constituents removed by
the GQCS and leakage or losses from the systems operating above
atmospheric pressure.
(c) Load changing
Starting an additional pulverizer under oxy-combustion condi-
tions is similar to starting a pulverizer under normal air firing. The
total oxidant demand is increased incrementally ahead of fuel input
and the burner oxidant demand is temporarily increased to the load
change set point to maintain flame stability of the in-service burn-
ers during the transient. The burner registers associated with the
pulverizer to be placed in service are confirmed to be at light-off
position. Load is raised using the in-service pulverizer(s) and the
lighters to provide about the same additional heat input as the
pulverizer being brought into service at its minimum load. As fuel
flow increases, SR and PR flow increase as does burner, SR and PR
gas oxidant demand. As load is increased, the increased PR and SR
demand will temporarily decrease the flow to the CPU and the CPU
booster fan will maintain backpressure on the system to avoid any
significant pressure upsets.
Excess oxygen set point is increased beyond the normal set point
as load is changed to ensure safe combustion. To start the pul-
verizer, PR flow is established when its burner line shutoff valves
are opened and increased to the required value. As the PR flow is
increased, the SR flow will correspondingly decrease to maintain
total mass flow to the boiler at the load. The oxygen concentration
in the PR stream is maintained at its prescribed set point which will
correspondingly reduce the oxidant flow to the SR stream.
When oxidant injection to the burners coming into service
has been established, the feeder is started, and coal is fed to the
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
pulverizer and burners. Heat input is automatically controlled as
coal is fed to the pulverizer by rapidly reducing lighter input and
backing down the other in-service feeder(s) and pulverizer(s) to
maintain heat input. Once stable conditions are achieved at the new
total heat input, burner oxidant demand is returned to its normal
set point and excess oxygen is released to trim back to the normal
set point at the associated load which will adjust the PR and SR
oxidant demand.
Recycled flue gas and oxidant flow demands will follow changes
in boiler heat release demands similar to normal air-fired systems.
Oxidant flow to the burners is temporarily increased during tran-
sient conditions until steady state load conditions are achieved.
Since the PR stream is maintained at a specific oxygen concentra-
tion, changes in oxidant demand are realized primarily in the SR
recycle stream.
Recycle flue gas flow leads oxidant flow which leads fuel flow
on load increases. The process is opposite for a load decrease with
fuel flow decrease leading oxidant flow decrease which leads
recycle flue gas flow decreases. The individual load change rate
capabilities for the boiler, GQCS, ASU, and CPU must be designed
to be sufficient to support the overall plant load change rate
requirement.
(d) Shut down
To shut the plant down from oxy-mode, load is reduced to the
transition load with one pulverizer in service at minimum pulver-
izer load. Oxidant flow to the in-service burners is increased to the
transition set point and the lighters for the in-service burners are
brought into service. With the plant load reduced to the transition
load, the CO2 flow to the pipeline is diverted to the stack and halted.
The CPU process is then shut down by opening the stack isolation
damper (4) and then opening the stack damper (3) gradually from
its idle position allowing flue gas to flow to the stack while back-
ing down the CPU booster fan accordingly to control pressure at
the CPU inlet. Once the stack damper (3) is fully open the booster
fan outlet is diverted to the stack and the main compressor is shut
down. The booster fan is then reduced to minimum flow, the CPU
inlet damper (8) closed and the fan shut down. Once the CPU is
shut down the CPU inlet TSO damper (9) is closed and all flue gas is
flowing to the stack with the unit in oxy-mode at transition load.
With the CPU out of service, the boiler and GQCS can be tran-
sitioned to air firing and shut down. The boiler is firing coal at
the transition load with one pulverizer in service at minimum
pulverizer load. Oxidant flow to the in-service burners is at the
transition set point and the lighters for the in-service burners are in
service.
The transition from oxy-combustion back to air firing is the
reverse of the transition procedure previously described. The
boiler/GQCS is transitioned from oxy to air firing by transitioning
the PR stream first, followed by the SR stream. The PR and SR tran-
sitions are accomplished as follows with the burner oxidant to the
in-service burners remain at the transient set point and the lighters
to the in-service burners remain ignited. First the controllable PR
fan air intake damper (6) is closed from its idle position and the PR
TSO damper (7) is opened. The controllable PR air intake damper
(6) is then gradually opened from its idle position allowing air into
the fan inlet flue. As air mixes with the recycled flue gas, oxidant
demand to the PR stream will decrease to zero. As air is introduced,
the oxidant demand to SR stream will also decrease (burner oxidant
demand is held until the transition is completed). Once the control-
lable air intake damper (6) is fully open, the PR recycle damper (10)
is gradually closed until the PR fan is supplying only air to the pro-
cess and PR recycle flow has been stopped. The moisture removal
system and flue gas reheater can be taken out of service at this
point.
77
The SR is transitioned to air in the same manner. As the SR is
transitioned the SR oxidant demand will decrease to zero. Once
the SR oxidant demand reaches zero the control valves are closed
and locked out of service. During this process, the burner oxidant
demand has been maintained at the transition set point. Once the
PR and SR streams have been fully transitioned, the burner oxidant
demand can be reduced to zero and the oxidant system shut down.
Once both the primary and secondary streams have reverted to
air, no oxidant is being added to the flue gas, the oxidant flow to
the in-service burners has been stopped and the boiler and GQCS
are operating in the air-fired mode with all flue gas exiting to the
stack. From this state the pulverizer load is decreased to minimum
and then shut down followed by the PR fan in the conventional
manner. During this process the GQCS remains in service to control
particulate and SO2 to the stack. Load is further decreased to turbine
trip load using the lighters and SR and ID fans and the turbine is
shut down. The lighters are then shut off and the furnace is purged
using the SR and ID fans. Once the purge is complete the GQCS can
be shut down. The SR and ID fans are also shut down, unless they
are needed to increase the boiler cool down rate.
Once the total oxidant demand has been reduced to zero and
the oxidant control valves taken out of service, oxidant produced
by the ASU will be vented to the atmosphere briefly as the ASU is
shut down in the conventional manner.
2.5.3. Major plant trips
Though any component can experience a failure or trip, redun-
dant equipment should be selectively provided to allow continued
operation of essential remaining systems as determined by the
reliability-availability requirements. However, certain trips will
result in cessation of plant operation including an MFT (Master
Fuel Trip), an ASU trip when in oxy firing mode, a steam turbine
trip, or a fan trip. Other trips such as a CPU trip, pulverizer trip, CDS
trip, DCCPS trip, or a pipeline trip may not lead to an MFT and plant
trip. The plant can usually run through these trips to allow the
operator the option to shut down the plant normally, or if the trip
can be resolved quickly to continue to operate until the equipment
is back on-line. Descriptions of the causes and consequences of an
MFT, ASU, Steam Turbine CPU, pipeline and CPU compressor trip
are provided in later sections. A brief overview of the ASU, steam
turbine, pulverizer, and GQCS trips are provided here.
(a) Master fuel trip
The MFT system is a combination of control system logic and a
hardwired relay circuit. When activated, the MFT stops the flow of
all fuel to the boiler within a period of time that does not allow a
dangerous accumulation of combustibles in the furnace. The MFT
relay circuit is de-energize to trip fail-safe system, requiring opera-
tor action to reset only after a boiler purge is completed. The input
signals indicating an MFT condition must be hardwired directly
from the sensing elements and through two or more digital input
modules for redundancy.
Conditions that would initiate an MFT include loss of ignition,
loss of fuel flow, loss of SR, PR, or ID fan, low excess oxygen at
the boiler outlet (when in transition or oxy firing mode), less than
minimum air flow (air firing mode), loss of oxidant flow or ASU trip
(oxy firing mode), high or low vertical separator or boiler steam
drum level, high or low furnace pressure, high calculated pressure
difference across the particulate control device, equipment maxi-
mum temperature limits, high oxygen concentration in the SR or
PR recycle stream, or steam turbine trip. The operator may also
initiate a master fuel trip. In either case, all fuel flow and sources
of ignition are stopped immediately, the CPU is tripped, the stack
dampers opened, and the furnace is purged.
78 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
When an MFT is initiated, all lighters are stopped, all pulverizers
are stopped and isolation (swing) valves are closed, the PR fan(s) is
stopped, the oxidant flow to the primary stream is stopped, the SR
and PR air intakes are opened and the recycle dampers are closed,
the CPU isolation damper is closed, the stack isolation damper is
opened, and the steam turbine is tripped. Oxidant to the secondary
stream and the burners are continued to maintain an O2 concen-
tration of at least 21% by volume while the SR fan air intake control
damper is opened and the SR recycle damper is closed. Once the
SR stream has reverted to air, the oxidant flow to the secondary
can be stopped. The ID and SR fans continue to operate for furnace
post-purge. The controllable air intake and stack dampers are at
always parked at a set an idle position so that air will immediately
enter the SR fan and flue gas will exit the stack when the isolation
dampers open.
If the air flow is above the purge rate, it will be allowed to
decrease gradually to the purge rate for a post-firing purge in
accordance with applicable fire protection standards. Usually the
unsafe condition can be corrected and the fuel reignited with little
delay following a furnace purge.
(b) ASU trip
Should the ASU experience difficulty during startup or air firing
before the transition to oxy firing, the plant will continue to run
in air fired mode to allow the operator the option of continuing
to run if the ASU trip can be quickly remedied or shut down if it
cannot (NOx emissions are the main consideration in continuing
to operate). Should the ASU trip during the transition or when oxy
firing, an MFT is automatically initiated.
(c) Steam turbine trip
Prior to synchronization, a steam turbine trip will not initiate
a shutdown of the boiler. However, once synchronized, a steam
turbine trip will automatically initiate an MFT.
(d) Pulverizer trip
When a pulverizer trips, there will be a load runback on the
turbine due to the rapid loss of heat input to the boiler. Though
this can be a severe transient, the control system is usually able
to compensate (depending on the steam turbine response) and
avoid a unit trip. In the event of a pulverizer trip, the total oxidant
demand is maintained until combustion is stabilized to ensure safe
conditions. If the event is too rapid it will initiate an MFT.
(e) GQCS trip
Several potential trips can occur within the GQCS depending
on the type of equipment employed. However, these trips are
well known from conventional experience and would follow the
same procedures. It may be possible for the boiler to run through
a scrubber trip for a brief period (some hours) depending on the
level of SO2 concentration in the boiler and duration (corrosion)
and the stack permit requirements if the scrubber trip also trips
the CPU. Depending upon the CPU process provided the significant
increase in SO2 and gas temperature is likely to trip the CPU
reverting gas flow to the stack. If the scrubber trip can be recovered
without shutting down the boiler due to corrosion, violating stack
permit requirements, or leaving oxy-mode, the CPU can be quickly
restarted. If the scrubber causes too great a pressure excursion, an
MFT might also be initiated by the boiler draft control. Loss of the
particulate removal device (PJFF or ESP) will always result in an
MFT to protect the ID fan and other downstream equipment from
erosion.
(f) Moisture removal trip
If the moisture removal device trips, it is probable that the CPU
will also trip due to high temperature and moisture. The remainder
of the process may be operable if the coal is such that the higher
moisture in the primary stream can be tolerated. It is advantageous
to remain in the oxy-mode if possible, because of the much lower
NOx emissions. The limiting factor on the time available to recover
is likely the stack emissions of NOx and SO2 in the absence of the
CPU. If operation can be recovered quickly the CPU can be quickly
restarted. Otherwise the plant will be shut down.
(g) Forced shutdown
Forced shutdown procedures are used to remove the unit from
service as quickly as possible, but in a more controlled manner
than a MFT. This process is identical to a normal load reduction and
shutdown but accomplished as rapidly as practical. The procedure
requires that the turbine control valves be used to control the load
down to the transition load. Once at transition load, the CPU flow
is reverted to the stack and the CPU is shut down. Once the flow to
the stack has been reestablished, the unit is reverted to air firing
and the turbine load is further reduced to the turbine trip load.
After the turbine is removed from service, all fuel is stopped and
the unit is purged.
(h) CPU trips
A CPU trip will automatically and rapidly open the stack isola-
tion damper and then close the CPU inlet isolation damper. Since
the controllable stack damper is set at an idle position, flow will
immediately be established to the stack at a rate that minimizes
the pressure upset to the boiler/GQCS system as the flow that was
going to the CPU rapidly shifts to the stack. A DCS initiated CPU
trip could occur for several reasons including an MFT or a problem
within the boiler or GQCS that requires reverting to the stack due
to potentially unacceptable changes in composition, temperature
or pressure at the CPU inlet.
In the event of a CPU trip, the Operator must decide the appro-
priate action which would typically be reduction to transition load,
remaining in oxy firing, while the cause of the CPU trip is investi-
gated. Once the cause has been determined the operator then must
decide whether correction and restarting of the CPU can be accom-
plished in a short enough time to continue operating the plant
(emission limits must be considered) or the plant must be shut
down normally to make repairs.
Within the CPU there are several sub-system trip scenarios that
could allow continued CPU operation such as pipeline shutdown,
which would result in blowing off production to the stack through
pressure reduction while determining which sub-systems should
be shutdown or if a global CPU Trip is needed. In case of main com-
pressor trip, the inlet booster fan outlet flow will be redirected to
the stack while determining if a CPU trip is needed. Since the flue
gas is still flowing into the CPU inlet, this will shorten the start-up
time considerable once the compressor is ready to restart. How-
ever, loss of the booster fan or determination that a sub-system
trip cannot be remedied rapidly enough will result in a full CPU
Trip. Means for pressure relief to prevent under or over pressure
conditions in the CPU inlet flue work must also be provided.
2.5.4. Turndown and load change rate
(a) Turndown
Turndown and load change rate are determined by the ‘weakest
link’ in the process. Boiler, GQCS, and steam cycle turndown and
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125 79

load change rates are the same as for conventional air fired plants.
Minimum plant electrical production is determined by minimum
load on the steam turbine which is usually achieved on lighters
prior to coal firing. In oxy-combustion this occurs in air firing mode
where emissions to the atmosphere are a concern and air firing
is minimized. Once in oxy-mode, plant turndown is dictated by
the transition load which is based on one pulverizer firing at its
minimum rate plus any lighter heat input. Larger units with more
pulverizers and burner levels have much greater turndown in oxy-
mode than smaller units with fewer pulverizers and fewer burner
levels.
The turndown of ASU’s and CPU’s employing large compres-
sors is driven by the number of parallel compressors employed
(modules). Since a compressor can only turn down to about 70%
of its full capacity, multiple parallel compressors allow greater
turndown. For example an ASU with one main compressor can
turn down to 70% load without venting oxidant. Oxidant flow
to the boiler can be reduced further but the vented oxidant will
adversely affect operational economics. However, if two 50% ASU
modules were used, the system could turn down to 70% of 50% or
35% of full load oxidant output efficiently (without venting).
Since the flue gas composition does not change significantly
throughout the oxy-mode operating range, the boiler and GQCS do
not limit the CPU turndown. However, the CPU has the same main
compressor limitations requiring recirculation of gas around the
main compressor when the inlet flue gas flow falls below about
70%. In addition there are minimum flow rate requirements to
maintain proper conditions in the cold box which may further limit
CPU turndown. The CPU minimum load condition will therefore
define the plants lowest oxy-mode operating load.
(b) Load change rate
The maximum rate at which an oxy-combustion plant can
change load has yet to be determined by experience. Experience
to date has only been in small demonstration facilities such as the
30 MWth Vattenfall oxy-combustion plant at Schwarze Pumpe in
Germany. However, expectations can be suggested based on what
is known about current power plant and ASU technologies at large
scale.
Modern conventional power plants with once-through boilers,
AQCS, and full steam cycle are currently designed to be capable of
changing load as fast as about 5% of full load per minute, though
they typically operate at about 2% per minute. Current ASU pro-
cesses for oxy-combustion are designed for about 2% load change
rate but some have reported test results as high as 8% per minute.
CPU’s are expected to have similar load change rates but no oper-
ating experience currently exists.
Higher load change rates increase thermal stresses within all
components and reduce their cyclic life. Due to the much higher
costs of operating carbon capture plants it is unlikely that fast ramp-
ing will be practical in the foreseeable future. It is anticipated that
most carbon capture plants will run at base load at first due to their
higher cost of electricity though load following capability will be
needed as the basis for dispatch evolves. This is similar to experi-
ence in the conventional power market except dispatching will be
much different. In the conventional market the lowest cost plants
are dispatched first but in a carbon constrained world the penalty
for emitting CO2 must be factored in meaning it may not be the
lowest production cost that governs in dispatch. Only stable and
well defined carbon policies will allow an understanding of how
dispatch will be driven.
3. Oxy-CFB power plant
Circulating fluidized bed (CFB) boilers were introduced in the
end of 1970s after first experiences of bubbling fluidized bed boil-
ers earlier in that decade. With its capability to burn multiple types
of fuels and features for low emissions of SO2 and NO2 , it started to
emerge in the boiler markets. First it appeared in smaller industrial
scale and gradually it has been scaled into its current commer-
cial capacity. Largest units in operation are now in the scale of
550-600 MWe and supercritical CFB units of 800 MWe are now
commercially offered by vendors in competition with PF boilers
for utility scale power production.
In the IPCC Special Report on CO2 Capture and Storage pub-
lished in 2005 (IPCC, 2005), Oxy-PF boiler was the only option
referred for oxyfuel combustion. However, since 2005 there have
been significant efforts in the development of oxyfuel combustion

Table 4
Test facilities for oxygen-fired combustion in circulating fluidized beds.

Operator and locationa Sizeb FGRc Fuelsd Referencee

CIUDEN, Ponferrada, ESP 30 MWth Both Anthr, Petcoke Lupion et al. (2013)
Valmet, Tampere, FIN 4 MWth Both Bit Varonen (2011)
Alstom, Windsor, CT, USA 3 MWth No Bit, Petcoke Nsakala et al. (2004)
IET-CAS, Beijing, CHN 1 MWth Dry Bit Li et al. (2014)
IET-CAS, Beijing, CHN 100 kWth Dry Bit, Lig Li (2012)
IET-CAS, Beijing, CHN 30 kWth No Lig Lu (2012)
CanmetENERGY, Ottawa, CAN 800 kWth Dry Anthr, Bit, Subbit, Lig, Petcoke, Wood Jia et al. (2012a)
CanmetENERGY, Ottawa, CAN 100 kWth Dry Bit, Subbit Jia et al. (2010)
University of Utah, UT, USA 330 kWth Wet Bit Eddings et al. (2009)
Cranfield University, GBR 300 kWth Both Coals, Biomasses (planned) Anthony (2013)
University of Stuttgart, DEU 150 kWth Wet Bit Hofbauer et al. (2014)
VTT, Jyväskylä, FIN 140 kWth Wet Anthr, Bit, Lig, Petcoke, Wood, Straw Eriksson et al. (2007)
Czestochowa Univ. of Tech., POL 100 kWth No Bit Czakiert et al. (2009)
Czestochowa Univ. of Tech., POL Batch/single part. No Bit Luckos et al. (2011)
Czestochowa Univ. of Tech., POL Batch No Lig Czakiert et al. (2005)
Vienna Univ. of Tech., AUT 100 kWth Wet Sewage sludge Höltl et al. (2009)
Tallinn Univ. of Tech., EST 60 kWth No Oil shale (planned) Loo et al. (2014)
Southeast Univ., Nanjing, CHN 50 kWth Wet Anthr, Bit, Petcoke Duan et al. (2011)
Yonsei Univ., Wonju, KOR 30 kWth No Wood pellet, Sewage sludge Jang et al. (2014b)
Zhejiang Univ., Hangzhou, CHN 30 kWth No Bit Mao et al. (2003)
a
AUT = Austria, CAN = Canada, CHN = China, DEU = Germany, ESP = Spain, EST = Estonia, FIN = Finland, GBR = United Kingdom, KOR = Rebublic of Korea, POL = Poland,
USA = United States
b
Thermal capacity of the unit specified by the operator.
c
Flue gas recycle mode: wet, dry, or both (wet and dry).
d
Anhtr = anthracite, Petcoke = petroleum coke, Bit = bituminous coal, Subbit = subbituminous coal, Lig = lignite.
e
Only one (first) reference is mentioned for finding more information of the unit.
80 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 20. Development path from small scale to industrial scale.
for circulating fluidized bed boilers, thus providing another option
for oxyfuel combustion of solid fuels.
In a CFB boiler, air is used as the comburent and fluidizing
medium. A key feature of this type of combustion is its good mixing
environment and capability to equalize the temperatures in the fur-
nace due to a large amount of fluidized bed material circulating in
the furnace. Typically, the temperature level within the CFB com-
bustor is about 850–900 ◦ C, which is lower than the combustion
temperature in the PF boilers. Another key feature of CFB is the
in-furnace SOx removal by limestone injection. Thus, external FGD
may not be necessary unless very high sulphur fuel is used.
In an oxy-CFB boiler, nearly pure oxygen is mixed with the
recycled flue gas and these serve as inlet gas instead of air. The inlet
oxygen concentration is controlled by adjusting the ratio of oxygen
to recycled flue gas. Due to the flexibility of the arrangement of
heat recovery inside the furnace and additional heat recovery
from the recycled solids, it is possible to increase the inlet oxygen
concentration and reduce the amount of recycled flue gas and con-
sequently reduce the physical size of the boiler and furnace (Hotta,
2013; Anthony, 2013; Hyppänen and Hotta, 2005). Thus, in an oxy-
CFB with 60% inlet oxygen, the cross-sectional area of the furnace
can be about 65% smaller compared to its air-fired counterpart
with the same gross output (Hyppänen and Hotta, 2005).
The oxy-CFB process has been studied in bench scale and pilot
scale devices. Table 4 presents the test facilities, which can be
found from open literature. A majority of the CFB pilots have a
thermal capacity of approximately 100 kWth. The smallest units
are for combustion tests of single particles or small fuel batches.
The largest unit size so far is a 30 MWth CFB operated by CIUDEN
(Lupion et al., 2013). The tested fuels are usually fossil fuels, which
are commonly used in energy production. In addition, wood and
other biomasses and sewage sludge have been applied in some
units. Most of the oxy-CFB pilots have nowadays the capability of
using either wet or dry flue gas recycle, thus, they can simulate the
real power plant conditions.
The ultimate goal of the research work is to develop the oxy-CFB
technology to industrial scale. For this purpose, interconnected
experimental and modelling work in different scales is essential
as illustrated in Fig. 20. In bench scale tests, different phenomena
are studied in well controlled environments and the acquired
knowledge is used for development of model theories and correla-
tions. These are then implemented to comprehensive larger scale
models, which can be validated based on pilot scale tests. Finally,
the design tools and process models can be applied to support the
design of industrial scale units and this way expedite the process
and minimize the risks related to scale-up of the new technology.
The power capacities in the recent conceptual studies have been
up to 300-600 MWe , i.e. compatible with the current maximum
capacities of air-fired CFBs (Abdulally, 2012; Myöhänen et al.,
2014; Weng et al., 2013).
3.1. Process configuration
Fig. 21 presents a simplified schematic flow diagram of the oxy-
CFB power plant (Myöhänen et al., 2014).
The main parameters to control the combustion are dependent
on the amount of oxygen and recycled flue gas; and how they are
introduced into the boiler. If the boiler needs to operate in both air-
fired and oxy-fired mode, oxygen levels in oxy-fired mode is chosen
to match the same thermal design in both operating modes. In such
cases, oxygen content is typically between 20% and 30%.
If the boiler will operate in oxy-mode only, the amount of
recycled flue gas could be lowered and consequently, the oxygen
content would be higher (i.e. in the range of 30–50%). This will lead
to lower gas flow rates; and consequently smaller furnaces and flue
gas channels could be used. This will therefore give some economic
advantages in terms of the CAPEX and OPEX of the boiler. On the
other hand, it should be noted that some tendency to produce local
hot spots in the combustor is possible due to the more intense com-
bustion in an environment with high oxygen level. Moreover, in a
smaller furnace, the total mass of solids is smaller, which reduces
the thermal storage capacity of the circulating bed and may increase
temperature gradients. An additional challenge is that with higher
oxygen content, the necessary internal heat exchanger panels need
to be installed in a smaller furnace.
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Turbine island
CFB
BOILER
Fuel
SCAH
Lime-
stone
Ash
Primary oxidant
Secondary oxidant
Fig. 21. Simplified block diagram of an oxy-CFB presenting wet flue gas recirculation after bag house and dry flue gas recirculation after flue gas condensing unit (FGC)
(Myöhänen et al., 2014).
In CFB combustion, the fluidizing gas can be fed into the fur-
nace through the grid in the bottom and from different locations
in the furnace walls. In air-fired boilers oxygen content is natu-
rally fixed at 21%, but in oxy-CFBs, oxygen levels can be adjusted
and controlled differently by modifying the ratio of oxygen and
recycled flue gas in different locations. This provides an addi-
tional flexibility to control combustion process for more optimized
performance for different boiler loads and fuels as well as load
changes.
In conventional air-fired CFBs, the combustion temperature
needs to be high enough for combustion reactions to proceed, but
low enough to prevent agglomeration of bed materials. Addition-
ally, when considering the NOx and SO2 emissions, an optimal
temperature for the CFBs is typically between 800 and 900 ◦ C.
For oxy-CFBs, it is expected that these operating parameters
will be mostly maintained. However, the mechanisms for sul-
phur capture by calcium sorbents will be somewhat different
due to high CO2 and H2 O concentrations in the furnace. Sul-
phur capture by direct or indirect sulphation is affected by the
temperature level; thus some adjustment to the optimal pro-
cess temperature may be necessary. The conditions will also
be affected by allowable sulphur concentrations limited by the
CPU.
Flue gas recycle (FGR) can be made wet or dry depending if recy-
cle is taken before or after the flue gas condenser stage as shown in
Fig. 21. In all recent concept designs, wet FGR is applied for main
fluidization streams while dry FGR is used for fuel feeding systems
and similar locations, where condensation needs to be avoided
(Abdulally, 2012; Eriksson and Cerezales, 2013; Myöhänen et al.,
2014; Supranov et al., 2011; Weng et al., 2013).
A wide variety of solid fuels can be burned in CFB boilers, as this
has been proven in air-fired industrial units. In addition, renewable
fuels, such as biomass can also be used up to 100% which will allow
negative CO2 emissions in a biomass fired oxy-CFB power plant
with CCS. Moreover, application of higher inlet oxygen concentra-
tion allows to use fuels with very high moisture content and low
heat value.
81
Dry FGR
CPU
Baghouse FGC
HRS
H2O etc.
Wet flue gas recirculation
Vent gas
Drying
Compression
Mixers Purification
H2O etc. CO2
Transport
Storage
ASU
Oxygen
preheater
3.2. Boiler design
The boiler design for CFB is dependent on combustion of the
fuel, fluid dynamics, heat transfer, and in-furnace desulphurization
of the flue gas. The following chapters present these phenomena in
more details.
3.2.1. Oxy-CFB combustion
The main phenomena, which affect the combustion of solid fuel
in a CFB furnace are evaporation of moisture, devolatilization, com-
bustion and gasification of char, gas phase reactions, and fragmen-
tation of fuel and char particles. In oxy-CFB, the share of CO2 and
H2 O is higher than in air-fired CFB. In addition, the concentration
of O2 and temperature can be locally higher, when operating with
higher inlet oxygen (i.e. lower flue gas recycle rate). The changed
conditions can affect most of the above mentioned phenomena.
The oxyfuel combustion has been studied more extensively
for pulverized coal combustion than for circulating fluidized bed
combustion. However, several of the main findings, i.e. effects of
increased CO2 and H2 O for PC combustion, are at least partially
valid for CFB combustion. The following chapters investigate the
different phenomena separately.
(a) Evaporation of fuel moisture and effect of flue gas recirculation
mode
The evaporation of fuel moisture occurs rapidly as the fuel
enters the CFB furnace. The mechanism of evaporation is not
affected by the gas atmosphere. The absence of atmospheric nitro-
gen and the recycling of flue gas increase the moisture content of
the flue gas. If wet FGR is used, the increased moisture in flue gas
may require increasing the flue gas temperature in the baghouse
to avoid acid dew point (Wall et al., 2012). In principle, the wet
FGR is thermodynamically more efficient due to smaller need for
preheating of the gas before feeding it back to furnace. Moreover,
the volume flow entering the flue gas condenser is smaller, thus
reducing the size of the condenser. On the other hand, for a given
82 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
oxygen concentration after furnace, a high moisture content
increases the ratio of O2 /CO2 , which means higher O2 requirement
per CO2 generated. In a study by Eriksson et al. (2007), the FGR
mode did not have a significant effect on the net efficiency, how-
ever.
(b) Devolatilization
During devolatilization, the volatile matter in the fuel is released
as gaseous species through the decomposition of fuel. The product
gases consist mainly of CO, CO2 , light and heavy hydrocarbons, H2 ,
and different sulphur and nitrogen compounds (e.g. H2 S, COS, CS2 ,
HCN, NH3 ). Devolatilization process is slightly endothermic and the
devolatilization rate is dependent on the particle temperature and
heating rate. The actual yield of devolatilized gases is often found
higher in fluidized bed environment than in the standard laboratory
tests, which is due to higher heating rate in hot fluidized bed and
longer residence time.
Saastamoinen et al. (2012) studied pyrolysis of various fuel
types in N2 and CO2 atmospheres in a bench scale BFB. The reac-
tor temperature was set to 850 ◦ C and the fuel samples were fed
in batches. More CO and H2 O were released during the pyroly-
sis in CO2 atmosphere compared to pyrolysis in N2 atmosphere.
This was explained by the Boudouard reaction (C + CO2 → 2CO),
reversed shift conversion (H2 + CO2 → H2 O + CO), and water-gas
reaction (C + H2 O → CO + H2 ).
Guedea et al. (2013) performed isothermal TG-tests of single
coal particles (three bituminous coals, lignite, anthracite, and
coke) under O2 /N2 and O2 /CO2 atmospheres at temperatures 800,
850 and 900 ◦ C. The fuel sample was dropped to the hot furnace,
thus, experiencing rapid pyrolysis. The total devolatilization time
was slightly longer in O2 /CO2 mixtures. This was explained by
the Boudouard reaction, which decreased the particle temper-
ature and thus slowed the devolatilization rate. Otherwise, the
devolatilization process was not affected by the gas atmosphere.
All in all, the devolatilization is similar in oxygen-fired and air-fired
conditions. The reported differences in the pyrolysis tests are due
to gasification reactions of char.
(c) Gasification and combustion of char during oxy-CFB combustion
After the devolatilization, the remaining char is burned in
the presence of oxygen and it may react with water vapour
and carbon dioxide in gasification reactions. With most solid
fuels, over 90% of the char consists of carbon. The oxidation
of char carbon produces carbon monoxide and carbon diox-
ide. The remaining species consist of sulphur, nitrogen, and
some hydrogen and oxygen. The combustion of these species
produces sulphur and nitrogen oxides and minor amounts of water
vapour.
The high CO2 and H2 O concentrations increase the gasification
reactions of char carbon: mainly the Boudouard reaction and water-
gas reaction. The gasification reactions of char increase the char
conversion rate, but on the other hand, these endothermic reactions
decrease the char temperature, which decreases the oxidation rate
of char. Thus, the increased gasification reactions actually decrease
the total combustion rate in oxygen-fired conditions.
The combustion rate of char increases as the oxygen concentra-
tion and temperature increase and the particle size decreases. The
reactivity of char is very much fuel-dependent: reactivity decreases
as the geological age of fuel increases. In pilot scale reactivity tests,
the effect of gas atmosphere has been relatively small as shown for
example in Fig. 22. The response times in flue gas oxygen concen-
tration show that the reactivity was clearly smaller with anthracite
than with bituminous coal, but not affected by the combustion
mode (Tourunen, 2012).
Fig. 22. Fuel reactivity in a 100 kWth oxy-CFB pilot (Tourunen, 2012).
The combustion and gasification of char in O2 /CO2 atmosphere
in a small scale BFB was studied by Scala and Chirone (2010). The
carbon combustion dominated the char conversion, but with high
temperatures (900 ◦ C) or low oxygen concentrations (<1%, vol), the
char gasification became significant as well.
In the bench scale BFB tests by Saastamoinen et al. (2012),
different fuel types were first pyrolyzed in N2 or CO2 atmospheres
and the remaining char was combusted by adding 10%-vol oxygen
to ambient gas. The combustion of char produced mainly CO2 .
It is clear that a large part of the CO could burn above the bed
and before the gas analyzer, thus, the values do not indicate the
actual CO2 /CO ratio from char combustion. The ratio was affected
by the fuel type: fuels with high char content (e.g. petcoke and
bituminous coal) produced more CO2 than the fuels with higher
volatile content (e.g. wood chips and straw pellets). The production
of CO was higher in CO2 atmosphere, which was probably due
to Boudouard reaction. The char combustion rate did not differ
significantly in O2 /N2 and O2 /CO2 atmospheres.
The main findings of different studies indicate that in oxyfuel
combustion conditions, the gasification of char increases; thus
it slightly decreases the particle temperature and combustion
rate of char. The ratio of produced CO vs CO2 is higher in oxyfuel
combustion, which is mostly due to gasification reactions.
(d) Fragmentation of char
The fragmentation of char affects the combustion process. Finer
particles burn faster, thus the combustion efficiency of chars with
higher fragmentation tendency is better. On the other hand, the
finer particles are easily elutriated, which could affect the combus-
tion profile inside the furnace and may increase the char content
in the circulating flow at the upper furnace. The primary frag-
mentation of char occurs as the fuel particles are introduced into
the furnace and the char structure breaks due to pressure of
devolatilized gases. The secondary fragmentation occurs during
combustion of char.
The fragmentation of char in an oxy-CFB was investigated by
Kosowska-Golachowska et al. (2012). Increase of inlet oxygen
concentration while keeping a steady bed temperature increased
both primary and secondary fragmentation. This is due to higher
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
particle temperatures and higher temperature gradients inside
the particle due to higher oxygen concentration surrounding the
particle. The similar effect was observed due to increase of bed
temperature. In a gas mixture of 21%O2 /79%CO2 , both fragmenta-
tion rates were slower than in air atmosphere. This was explained
by lower particle temperatures in O2 /CO2 mixture associated with
higher specific heat capacity of CO2 .
(e) Homogeneous reactions
The main homogeneous combustion reactions in a CFB are
oxidation of carbon monoxide, hydrogen, methane, and other
hydrocarbons. The hydrogen and hydrocarbons are generated
mostly during devolatilization, while the CO is produced during
combustion of char as well. In oxy-CFB combustion, the effect of
oxycombustion conditions on homogeneous reactions has not
been studied much. It is generally accepted that the water vapour
enhances the oxidation of CO. On the other hand, the high CO2
concentration may decrease the combustion rate of CO (Seddighi
et al., 2013). In oxy-CFB pilot tests, the CO concentration (ppm)
after the furnace is often higher but the actual CO emission (mg/MJ)
is lower in oxygen-fired vs. air-fired mode (e.g. Duan et al., 2014).
The higher concentration in oxygen-fired conditions is mostly
due to the absence of diluting nitrogen in the flue gas. Thus, in
order to get comparable values between air-fired and oxygen-fired
conditions, the emissions should be reported in relation to the
energy input (mg/MJ).
(f) Oxygen staging
In air-fired CFB, air staging is used for creating under stoichio-
metric conditions at the bottom of the furnace and consequently
reducing the NOx emissions. Oxyfuel combustion offers an alterna-
tive method by changing the oxygen concentrations of the primary
and secondary gases, which may bring additional advantages in
terms of the operation flexibility.
The oxygen staging has been investigated by Duan et al. (2011)
and Tan et al. (2014). In their studies, the total inlet concentration
was constant (30% and 50% respectively) and the oxygen concen-
tration of primary and secondary gas flows were adjusted while
keeping their gas flow rates constant. Increasing the oxygen con-
centration of primary gas increases the combustion rate at the
bottom of the furnace and thus improves the combustion efficiency
(as shown in Fig. 23). Naturally, the NO emissions will increase as
well.
98
96
Combustion efficiency (%)
94
92
90
88
86
10 20 30 40
Primary gas O2 (vol-%)
Duan et al. (2011a), Bituminous Duan et al. (2011a), Anthracite
Tan, L. et al. (2014), Bituminous
Fig. 23. Effect of primary flow O2 concentration on combustion efficiency. Data from
Duan et al. (2011a) and Tan, L. et al. (2014).
83
3000
2500
2000
Pressure (Pa)
1500
1000
500
0
0 5 10 15 20 25
-500
Height (m)
Air-fired, Full load Air-fired, Low load
Oxy (24% O2), Full load Oxy (24% O2), Low load
Fig. 24. Measured pressure profiles of air-fired and oxygen-fired combustion at
CIUDEN CFB (data from Kuivalainen et al., 2013).
3.2.2. Fluid dynamics
In oxygen-fired conditions, the gas density is higher and the vis-
cosity is slightly lower than in air-fired conditions due to changes
in the gas concentration. The changed gas properties may affect the
fluid dynamics of an oxy-CFB. The actual effects can be evaluated
from pilot experiments and modelling studies.
According to Varonen et al. (2012), the vertical suspension den-
sity profiles were fairly identical in air-fired and oxygen-fired tests
in Valmet’s 4 MWth unit. Similar result was also mainly supported
in the tests by Jang et al. (2014b).
Kuivalainen et al. (2013) presents pressure profiles of CIUDEN
CFB in air-fired and oxygen-fired conditions at different boiler loads
(Fig. 24). The differences are relatively small. Interestingly, the
effect of higher boiler load is seen in the air-fired mode, but not
in the oxygen-fired mode. It is possible that the differences were
more due to various other process parameters, which affect the
fluid dynamics in a CFB: the solid mass balance, primary/secondary
gas distribution, and the particle size of different feed materials,
which form the bed inventory (fuel ash, limestone, and make-up
sand).
In a computational fluid dynamics (CFD) model, the effect of
changed gas properties is taken accounted for, providing that the
applied drag models and turbulence models are valid. In a 2D study
by Zhou et al. (2013), the axial distribution of solids was not affected
by gas atmosphere. In a 3D study by Adamczyk et al. (2014), the
modelled pressure profiles were almost identical in air-fired and
oxygen-fired (32% O2 ) modes.
Based on the different experimental and modelling studies, the
fluid dynamics are not largely affected by the oxyfuel combustion
conditions as compared to its air firing counterpart.
3.2.3. Heat transfer
The heat transfer in oxygen-fired CFB can be different from
air-fired conditions due to higher heat capacity and thermal con-
ductivity of CO2 and H2 O and increased radiative heat transfer due
to higher concentrations of these radiative gases.
The higher heat capacity of gas decreases the temperature gra-
dients in oxygen-fired conditions. Moreover, the higher thermal
50 60
conductivity may affect the heat transfer. However, the convective
heat transfer inside a CFB is dominated by circulating solid parti-
cles, thus the effects of changed gas properties on heat transfer are
small. For example, in the early oxy-CFB tests by Alstom, there was
no significant difference in heat transfer to the furnace waterwall
test sections between air- and oxygen-firing (Nsakala et al., 2004).
84 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
1000
980
960
940
Temperature (°C)
920
900
880
860
840
820
800
0 5
Fig. 25. Measured temperature profiles in oxyCFB pilots. References: CIUDEN (Kuivalainen et al., 2013); Alstom (Nsakala et al., 2004); IET-CAS (Li et al., 2014).
The changed radiative heat transfer properties have been stud-
ied by modelling (e.g. Wang et al., 2011a; Bordbar et al., 2015;
Adamczyk et al., 2014). Based on the modelling results, the temper-
ature fields are slightly more uniform in oxygen-fired conditions.
However, because the radiative heat transfer between the particles
is dominating, the effect due to higher share of radiative gases is
small, at least in full load conditions. In the backpass of the boiler,
the effects due to higher heat capacity of the gas and increased
share of radiative gases are relatively larger and they need to be
considered in the thermal design (Bordbar and Hyppänen, 2013).
The practical effects of changed heat transfer properties can
be evaluated from the oxy-CFB pilot tests. When switching from
air-fired to oxygen-fired conditions, the furnace temperatures can
decrease by about 100 ◦ C due to higher heat capacity of the gas. This
effect has been noticed in all pilot tests (e.g. Zhao et al., 2012; Tan
et al., 2013; Duan et al., 2014). This can be controlled by increasing
the oxygen concentration in the oxygen-fired mode to approxi-
mately to 22–25% (Gomez et al., 2014b; Li et al., 2014).
Duan et al. (2011) presents measured temperature profiles with
air and different O2 /CO2 mixtures in a 50 kWth CFB pilot. With both
tested fuels (bituminuos coal and anthracite), the temperature level
is slightly lower in 21%O2 /79%CO2 mixture than in air and the tem-
perature increases as the oxygen concentration increases. Similar
results were reported by Jang et al. (2014b) for a 30 kWth unit com-
busting sludge and by Pikkarainen et al. (2014) for a 100 kWth unit
combusting mixture of anthracite and petroleum coke.
Fig. 25 compares measured temperature profiles of various oxy-
CFB pilots operated in air-fired and oxygen-fired mode. In the
CIUDEN pilot, the temperature profiles were very similar in both
modes at full load (Kuivalainen et al., 2013). In these tests, the
inlet oxygen concentration was 24%. In low load point, the furnace
temperature level was about 40 ◦ C lower in oxygen-fired vs. air-
fired mode, but this could have been due to other changes in the
operating conditions rather than due to oxygen-fired mode. In the
tests at Alstom, the temperatures were slightly higher in oxygen
fired test at 21% inlet oxygen vs. in air-fired test (Nsakala et al.,
2004). At higher inlet oxygen concentration, the maximum fur-
nace temperatures were clearly higher, as expected. In these tests,
the heat transfer surfaces had been added to the upper furnace,
which explains the decreasing temperatures in that section. In the
tests at IET-CAS, the temperatures at the bottom of the furnace
were smaller in oxygen-fired mode due to colder primary gas and
the cooling of the solids in the external heat exchanger (Li et al.,
CIUDEN, Air, Full load
CIUDEN, Air, Low load
CIUDEN, Oxy, Full load
CIUDEN, Oxy, Low load
Alstom, Air (A1)
Alstom, Oxy (B1, 21% O2)
Alstom, Oxy (C1, 36% O2)
Alstom, Oxy (C5, 50% O2)
IET-CAS 1 MWth, Air
IET-CAS Oxy (50% O2)
10 15 20 25
Height (m)
2014). The temperature gradient was steeper in the oxygen-fired
mode due to faster combustion reactions with high inlet oxygen
concentration.
When the oxy-CFB is operated at higher inlet oxygen concentra-
tion, the adiabatic combustion temperature increases and the heat
recovery must be increased to maintain the same bed temperature.
In several of the oxy-CFB pilots, the additional heat recovery inside
the furnace has been accomplished by increasing the heat transfer
surface area by removal of refractory linings (Gomez et al., 2014b),
adding new heat transfer sections (Nsakala et al., 2004), adjustable
bayonet tubes (Li et al., 2014), or by increasing the heat load of
the external heat exchanger in the return leg system (Gomez et al.,
2014b; Li et al., 2014).
In new large scale oxy-CFB designs, the surface area of the inter-
nal heat exchangers (e.g. hanging superheaters and wingwalls) can
be increased as shown in Fig. 26. However, the spacing between
the panels must be large enough so that the local temperatures do
not decrease too low and the heat transfer remains efficient. The
design of the bed temperature can be slightly higher during oxyfuel
combustion mode to ensure that complete calcination of limestone
could be achieved and to increase the heat flux to different surfaces
inside the furnace.
Because the total available heat transfer area inside the furnace
is limited, the role of external heat exchangers (EHE) is impor-
tant for operation with higher inlet oxygen concentration. The heat
transfer in EHE has been studied by modelling and by experiments
in a small scale BFB pilot (Bolea et al., 2012b; Bolea et al., 2014).
The differences between the measured heat transfer coefficients in
air-fired and oxygen-fired conditions were relatively small, which
indicates that the thermal design of these units can be based on
experiences from air-fired CFBs.
3.2.4. Sulphur chemistry and in-furnace capture of SOx
Similar to oxy-PC, understanding the fate of SOx in oxy-CFB is
essential to the design of the boiler and to prevent any problems to
the flue gas ducting and downstream equipment.
It is expected that the majority of the sulphur in the fuel is con-
verted to SO2 , and a small amount is converted to SO3 . However, the
sulphur chemistry in oxy-CFB combustion includes the release of
sulphur from fuel, formation of different sulphur species, and cap-
ture of sulphur via the sorbent injected into the furnace. The latter
brings the main differences to the sulphur chemistry because of
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 26. CFB furnace design for air-fired (left) and oxygen-fired (right) mode with 60% inlet O2 (Hyppänen and Hotta, 2005).
the inherent features of the process. These will be discussed in this
chapter.
In oxy-CFB combustion, the SO2 -concentration inside the fur-
nace and in flue gas depends on the following:
• The amount of SO2 , which is released from the combustion of fuel.
• The sulphur capture by the sorbent via the indirect and direct
sulphation reaction.
• The inherent capacity of the ash to capture sulphur species.
• The diluting effect of other gases (e.g. O2 and N2 in air-fired case
compared to CO2 , H2 O, O2 in recycled flue gas) in the furnace.
• The amount of recycled flue gas and the recycled SOx that could
enrich the concentration of the SOx in the furnace.
Without any sulphur capture employed, the SO2 concentra-
tion (reported in volumetric fraction – i.e. ppmv, %v or mg/Nm3 )
could easily be tripled during oxyfuel combustion with FGR. How-
ever, when the in-furnace sulphur capture is employed, this will
reduce the SO2 concentration in the furnace and flue gas. The reduc-
tion depends on the sulphur capture efficiency, which improves at
higher concentration of SO2 . Consequently, during oxyfuel combus-
tion, the SO2 concentration inside the furnace is only moderately
higher as compared to the SO2 concentration of its air counterpart.
In the past 10 years, several equipment suppliers and research
organizations has evaluated the fate of sulphur during oxy-
CFB combustion. These organizations include boiler companies
(Alstom, Foster Wheeler, B&W and Valmet – former Metso);
research organizations in North America (Canmet, University of
Utah), Europe (Czestochowa University of Technology, CIRCE, CIU-
DEN, ICB-CSIC, Lappeenranta University of Technology, University
of Stuttgart, VTT) and China (Southeast University).
85
(a) Sulphur release and formation of sulphur species (SO2 , SO3 , H2 S)
during oxy-CFB combustion
Sulphur in the fuel could be in the form of inorganic compounds
or organically bound sulphur. Majority of the sulphur in the fuel
will be released to the gas phase during combustion in the furnace.
At high temperatures and in the presence of high oxygen concen-
tration, the formation of SO2 is thermodynamically favoured. Thus,
in the combustion processes, the sulphur contained in the fuel is
assumed to be oxidized mainly to SO2 even though some effects of
process conditions have been reported (Czakiert et al., 2014; Duan
et al., 2014).
There are only few studies evaluating the formation SO3 in
oxy-CFB combustion. SO3 is formed thermally at high tempera-
tures (>1100 ◦ C) and catalytically at low temperatures (500-800 ◦ C).
It could be surmised that the latter mechanism would be more
favourable during CFB combustion as typical temperature is about
800-900 ◦ C.
The SO3 formation can be affected by concentration of SO2 ,
residence time, temperature profile, concentration of O2 , fly ash
composition, and concentration of NO2 and presence of catalysts.
There is a special interest of SO3 in the cold end since SO3 could
react with H2 O and form H2 SO4 at temperatures below 500 ◦ C (Fleig
et al., 2009).
The concentrations (reported as volume fraction – i.e. ppmv, %v
or mg/Nm3 ) of SO3 in oxy-CFB furnace could be higher than in air-
fired CFBs due to the missing nitrogen diluent in the gas, and the
higher oxygen concentration could also promote SO3 formation.
Ahn et al. (2011) compared SO3 formation in air- and oxygen-
fired CFBs, and they found that SO3 concentrations are higher
under oxyfuel combustion conditions than in air-fired conditions.
86 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125

However, on mass basis per unit of energy input, the levels of SO3
and SO2 should be similar or slightly higher for oxyfuel combustion
condition as compared to air fired condition. They did not see any
difference in the SO3 concentration when limestone addition was
used.
Czakiert et al. (2014) have also evaluated the SO3 formation in
their oxy-CFB test rig. In their earlier study, some SO3 was observed
locally; but in the later gas staging study, no SO3 was observed in
flue gas, inside combustion chamber or at the furnace outlet.
Hydrogen sulphide (H2 S) can be formed in the gas phase or
released from organic sulphur compounds if sub-stoichiometric
conditions exist. Typically, during combustion in excess oxygen
environment, the H2 S concentration should be insignificant (Fleig
et al., 2009).
(b) Capture of sulphur by the fuel ash

In air-fired CFB, fuel ash is known to consist of compounds that
are capable of capturing SOx during combustion. This depends on
the fuel type, composition of the ash and combustion condition. To
assess the capability of the ash to capture the SOx , the Ca/S ratio
in the fuel is an important indicator as calcium species plays an
important role in the sulphur capture chemistry.
The occurrence of self-desulphurization has also been verified
in smaller scale oxyfuel combustion tests with some indication of
enhanced effect in higher O2 concentration (Czakiert et al., 2014;
Duan et al., 2009).
(c) Capture of sulphur species by the sorbent
Sulphur capture has been carried out in fluidized bed boil-
ers by injecting calcium-containing sorbent (such as limestone or
dolomite) into the furnace where the sorbent is calcined and then
sulphated (as described in section “Oxy-PC”).
During the rapid calcination of CaCO3 , a porous CaO will be pro-
duced. On the other hand, during sulphation reaction of CaO, a hard
layer of CaSO4 will be formed in the particle surface. This should
hinder the reaction by the high diffusion resistance caused by the
CaSO4 layers; thus preventing the further utilization of any CaO
remaining inside the particle.
In Oxy-CFB furnace the temperatures are much lower than, e.g.
in Oxy-PC combustion and the partial pressure of CO2 may grow
higher than the equilibrium CO2 pressure over the limestone (i.e.
like in pressurized combustion), which will prevent the calcination
reaction of limestone. As a result, the sulphur capture could occur
via direct sulphation.
CaCO3 + SO2 + 1/2O2 → CaSO4 + CO2
At such conditions, calcium oxide will also react with CO2 to
create calcium carbonate.
CaO + CO2 → CaCO3
Fig. 27 presents the theoretical equilibrium of the limestone cal-
cination reaction as a function of CO2 partial pressure and reaction
temperature. In oxy-CFB combustion, the atmosphere is mainly
composed of CO2 and H2 O. The water content could be as high as
30% depending on the recycled flue gas – either wet or dry. Depend-
ing on temperature, the sulphur capture can occur either by indirect
sulphation or direct sulphation during oxyfuel combustion. Addi-
tionally, depending on the local conditions – i.e. in CFB solid loop
or inside the boiler, it is possible that reaction between solids and
gases could shift and change over to the other side of the calci-
nation equilibrium curve. Thus, both calcination and carbonation
reactions could occur simultaneously. Due to the re-carbonation,
the sulphur capture efficiency could be affected.
Fig. 27. Theoretical equilibrium of the limestone calcination reaction – temperature
vs. partial pressure of CO2 in surrounding gas. The range of operating conditions for
air and oxyfuel combustion in CFB are shaded in gray (Rahiala, 2013).
In air combustion condition, typical calcium conversion is about
30-40%, and sulphur capture is typically up to 90% for a full-scale
CFB boiler operating with Ca/S ratios of 2-2.5. In oxy-CFB com-
bustion, the recycled flue gas, concentration of the gas (CO2 , H2 O
and SO2 ), and temperature could impact the performance of the
limestone and sulphur capture process.
To assess the efficiency of the sulphur capture by the sorbent
during oxy-CFB combustion, the main areas of research are:
• Understanding the sulphur capture chemistry (i.e. direct vs indi-
rect sulphation reaction);
• Understanding the effect of H2 O to the sulphation reaction;
• Understanding the recarbonation reaction under oxyfuel com-
bustion condition with high CO2 composition.
Understanding of sulphur capture during
oxy-CFB combustion – direct and indirect sulphation reaction
Various studies have been undertaken to evaluate the sulphur
capture by the sorbent during oxyfuel combustion. However, the
reported results with regard to capture efficiency, calcium con-
version and SO2 emission have varied significantly across the
literature. This could be attributed to the different parameters that
(2) could influence the sulphur capture mechanism. To understand the
sulphur mechanism during oxyfuel combustion, the principle of
calcination and sulphation reactions in a conventional boiler should
be re-visited. This section presents an overview to the current state
of understanding on the sulphur capture during oxy-CFB combus-
(3)
tion reported in the literature.
Many laboratory scale studies under air- and oxygen-fired con-
ditions have focused their efforts in comparing direct sulphation
vs. indirect sulphation reaction and determining the superiority of
either mechanism during desulphurization. Typically, direct sul-
phation has been reported to create more porous product layer
than found in harder sulphate layer of indirect sulphation. This may
result to a better sorbent utilisation in the term even though the
reaction rate of direct sulphation is lower during the initial stages
of particle conversion.
In various small scale to large scale pilot plant studies, the
assessment of the sulphur capture is undertaken during the com-
bustion of fuel in the fluidized bed reactor. The performance is
observed to depend on several parameters which include:
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
• Process arrangements and operating parameters (e.g. O2 content
of the flue gas, temperature);
• Type of recycled flue gas used (e.g. real flue gas vs. simulated flue
gas, wet vs. dry);
• Calcium to sulphur ratio.
At ICB-CSIC (Spain), they have evaluated the sulphur capture
efficiency using a 3 kWth bubbling fluidized bed test rig with bot-
tled gases in addition to their smaller scale test equipment (de las
Obras-Loscertales et al., 2014). In their tests a better sulphation con-
version could be achieved with limestone when combustion con-
ditions favoured indirect sulphation. Thus, they suggested that the
optimum temperature for the sulphur capture is increased in oxy-
fuel combustion conditions as compared to the optimum temper-
ature for sulphur capture in air fired conditions. However, the sul-
phur retention with the dolomite was not significantly affected by
the combustion temperature (de las Obras-Loscertales et al., 2014).
At Southeast University (China), tests have been performed
using their 50 kWth CFB pilot, both with warm recycled flue gas and
with simulated recycling using bottled gases. They have evaluated
the mechanisms for sulphur capture during oxyfuel combustion
and concluded that could not determine whether direct or indirect
sulphation is dominant during combustion. Oxy-CFB conditions
seemed to result into a higher desulphurization efficiency than air
fired conditions with partially different process parameters (Duan
et al., 2014).
CIRCE (Spain) has also tested sulphur capture in air-fired
and oxy-fired combustion conditions in 95 kWth BFB pilot. They
reported that the highest SO2 capture efficiency could be achieved
by indirect desulphurization in the oxyfuel combustion conditions.
They also observed relatively high (90%) SO2 capture efficiency dur-
ing oxyfuel combustion tests; and the sulphur capture efficiency
also increased with increasing temperature (Bolea et al., 2012a;
Lupianez et al., 2013).
At CANMET (Canada), tests have been accomplished in a
100 kWth mini-CFBC pilot plant and 800 kWth oxy-CFB test rig.
Both pilot plants operate with actual recycled flue gas. In their
mini-CFBC tests the sulphur capture by direct sulphation was pre-
dominant during oxyfuel combustion. They did not report clear
differences in sulphur capture between air and oxycombustion
tests. In their 800 kWth test rig and maintaining a Ca/S = 3, they
have presented a sulphur capture efficiency of 76-82% during
oxyfuel combustion when subjected to higher temperature and
indirect sulphation. On the other hand, with the same Ca/S = 3,
the capture efficiency of 45-72% during oxyfuel combustion was
reported when subjected to a direct sulphation conditions (Tan
et al., 2012).
At VTT (Finland), tests have been undertaken in their 140 kWth
facility. They have consistently reported that a similar or better
sulphur capture efficiency have been achieved during oxyfuel com-
bustion conditions as compared to the sulphur capture efficiency
during air fired conditions. In their pilot scale tests, a real recycled
flue gas is used. Their tests indicated that both indirect and direct
mechanisms have been observed during the oxyfuel combustion
campaigns (Pikkarainen et al., 2014).
Alstom (USA) performed early tests using their 3 MWth CFB pilot
plant without recycling the flue gas. With petcoke firing and oper-
ating with furnace temperature at above 900 ◦ C, they reported a
sulphur capture efficiency of 98% during air firing and sulphur cap-
ture efficiencies in the range of 94-99% during oxyfuel combustion
without the recycled flue gas. When firing bituminous coal, the
sulphur capture efficiency was lower in oxyfuel combustion (with-
out flue gas recycle) conditions as compared to air-fired conditions
(Nsakala et al., 2004).
Recently, Valmet (former Metso – Finland) reported their results
when evaluating performance of the oxy-CFB combustion at their
87
4 MWth pilot plant. In their test conditions a similar or lower SO2
emissions were achieved during oxyfuel combustion as compared
to air combustion. Likewise, by controlling the amount of flue gas
recycled, they observed that SO2 emission was halved when tem-
perature increased during oxyfuel combustion. The improvement
to the sulphur capture efficiency was attributed to the change from
direct to indirect sulphation route during combustion (Varonen
et al., 2012).
At CIUDEN’s 30 MWth oxy-CFB pilot plant (Spain), the per-
formance of the CFB under air- and oxygen-fired combustion
conditions was evaluated. Their results showed that good sulphur
capture efficiency (over 95%) could be achieved during oxyfuel
combustion mode operating with Ca/S ratios between 1 and 3.
Using the same Ca/S ratio as comparison, they have noted that
the minimum SO2 emission was obtained during oxyfuel combus-
tion at relatively high temperature (around 880-890 ◦ C). Normally
at this temperature, the sulphur capture efficiency decreases for
conventional air fired CFBs (Gomez et al., 2014a).
In summary, based on the results reported from various pilot
tests – ranging from small to large scale, relatively good sulphur
capture could be expected in oxy-CFB combustion. This is con-
firmed from the results of CIUDEN’s pilot plant (which could well
represent the performance of commercial scale CFBs) achieving
good sulphur capture performance of >95%. In many occasions, it
could be concluded that sulphur capture efficiency during oxyfuel
combustion is optimum at higher temperature as compared to air
fired combustion. In this condition, the indirect sulphation could
be dominant.
Effect of water on sulphur capture during oxy-CFB combustion
Typically, the H2 O concentration in conventional air-fired CFB
is about is 4-20% depending on the moisture content of the fuel.
It should be noted that high moisture content in the fuel is quite
typical to fluidized bed combustion technology applications, due
to its capability to handle fuels with high moisture content. In oxy-
CFB combustion conditions, the H2 O concentration could be much
higher (at around 30-40%) especially if wet flue gas is recycled.
The potential impact of H2 O to the sulphur capture mechanism
during oxy-CFB combustion was initially raised by CanmetENERGY
(Wang et al., 2010). Since then, the influence of water vapour to
the sulphur capture mechanisms has been studied by number of
researcher groups. Most of these studies evaluated the influence
of water vapour under air fired conditions but some studies have
performed their tests under high CO2 concentration (i.e. favouring
direct sulphation reaction) conditions. Jiang et al. (2013) carried out
tests in the region where indirect calcination–sulphation occurs at
relatively high temperature and high CO2 concentration.
In general, most of the tests involved the use of tube furnace
(TF) or thermogravimetric analysis (TGA). All of the results from the
TFs and TGAs have indicated that calcium conversion is enhanced
when water vapour has been added in the gas mixture. Most of
these tests are evaluated at moisture content between 7% and 15%
which only represent conditions of conventional air fired CFBs. On
the other hand, the tests including the regions of oxy-CFB (up to
30–40% moisture content) seem to show that the increase in cal-
cium utilization efficiency seems not to be affected when certain
level of moisture content has been reached (Stewart et al., 2010;
Jiang et al., 2013; Duan et al., 2013).
Furthermore, Stewart et al. (2012) noted that it is possible to
incorrectly conclude and overhype the potential benefit of water
vapour to the sulphation reaction during laboratory scale experi-
ments. He also demonstrated that moisture has a stronger effect to
the indirect sulphation as compared to direct sulphation reaction.
Overall, the mechanism by which H2 O vapour enhances sulfur
capture has yet to be clarified.
88 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125

Re-carbonation of CaO

Recarbonation of CaO to CaCO3 in CFB combustion is important

and unwanted phenomena due to its tendency to produce agglom-
eration of bed materials and consequently reducing the availability
of the boiler. The phenomenon is tightly connected to the sul-
phation and calcination mechanisms described above. Additional
information will be presented in the Section 3.4. – “Agglomeration,
Fouling and Corrosion”.

3.3. NOx and trace elements

3.3.1. Formation and reduction of NOx and N2 O

One significant advantage of oxy-CFB technology over oxy-PC
technology is its lower NOx emissions. This advantage is possi-
ble due to lower operating temperature and the positive effects
of recycled flue gas (RFG) to lower flue gas NOx concentration in
CFB combustion. In oxy-fired CFB technology the source of nitro-
gen oxides is fuel nitrogen. In the flue gas the nitrogen is mainly in
form of elemental nitrogen and only less than 5% of fuel nitrogen is Fig. 29. Fuel-N to NO conversion ratios from different studies as a function of tem-
converted to NO and/or N2 O. perature. Blue symbols are indicating the results for oxy-firing and black symbols
The NOx concentration (ppm or mg/Nm3 ) in the flue gas of oxy- air-firing in the same study. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)
CFB combustion is usually similar or higher than that in CFB air
combustion. This is illustrated in Fig. 28. On the other hand, when
concentration is reported in the energy based mg/MJ or fuel-N to
NOx units, NOx is lower in oxy-fired combustion than that in air
combustion.
To understand the NOx formation, Fig. 29 illustrates the fuel-N
to NO conversion in both combustion modes. It can be observed
that the fuel-N to NO conversion ratio is increasing as a function
of temperature. In air combustion the reported values for fuel-N
to NO conversions are in general in the range of 4–13% with some
lower values of 2.1 and 2.6 from studies of Varonen et al. (2012)
and Hofbauer et al. (2014), respectively. In oxy-CFB combustion
the fuel-N to NO conversions are in general lower than in air com-
bustion and are in the range of 1–4% with some extreme low values
below 0.5% in a study of Varonen et al. (2012).
Ramos et al. (2013a) presented NOx and N2 O levels from
30 MWth CIUDEN demonstration plant as a function of Ca/S ratio

Fig. 30. Fuel-N to N2 O conversion ratios from VTT 100kWth oxy-CFB pilot tests.

for Anthracite and for Anthracite/Petcoke (70/30%) fuel blend. They

Fig. 28. NO emissions from different studies as a function of temperature. Blue sym-
bols are indicating the results for oxy combustion condition and black symbols air
combustion condition. The results are expressed as dry flue gas except results of
Ramos et al. (2013a) in which are as wet flue gas. (For interpretation of the refer-
ences to colour in this figure legend, the reader is referred to the web version of this
article.)
also presented comparative results demonstrating how the injec-
tion of ammonia could impact the NOx level in the flue gas when
using the same fuel. For both fuels used, increasing the Ca/S ratio
will increase the NO concentration. For N2 O concentration, the
trend is opposite in respect of Ca/S ratio. Ammonia injection has a
positive effect to NO concentration and neutral or increasing effect
to N2 O concentration (Ramos et al., 2013a). Varonen et al. (2012)
reported that using higher Ca/S ratio of 6 does not have an effect
to NOx emissions. This is contradictory to the results presented by
Ramos et al. (2013a).
Pikkarainen et al. (2014) and Tourunen et al. (2011) presented
N2 O results from VTT 140 kWth oxy-CFB pilot unit for different
fuels. From Fig. 30 can be concluded that fuel-N to N2 O conversion
ratios are decreasing when temperature increases for all fuels and
fuel blends. In tests of anthracite/petcoke fuel blend the significant
part of nitrogen oxides’ emissions were in form of N2 O which is
typical for high fixed carbon (low volatile content) fuels. The tested
oxygen staging had no significant effect on NO or N2 O emissions
(Pikkarainen et al., 2014).
Using the results of Pikkarainen et al. (2014) and Tourunen
et al. (2011), total nitrogen oxides’ (NO + N2 O) conversion ratios are
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 31. Fuel N to NO + N2 O conversion ratios from VTT 100kWth oxy-CFB pilot tests.
shown in Fig. 31. While the fuel-N to NO conversion has increas-
ing trend and fuel-N to N2 O has an opposite declining trend when
temperature is increasing, total nitrogen oxides’ (NO + N2 O) con-
version ratio is decreasing when temperature increases as seen in
the Fig. 31.
As a conclusion, oxy-CFB technology provides comparably lower
nitrogen emission levels below air firing conditions. Recycled flue
gas is reducing the nitrogen oxides’ emissions significantly and
values below 4% for fuel-N to NO + N2 O total conversion ratio can
be achieved using proper design and operation. As a comparison,
Pikkarainen et al. (2014) reported a value of 12% for fuel-N to
NO + N2 O conversion at CFB air combustion in similar test con-
dition. It should also be noted, that due to absence of diluting
nitrogen, the NO concentration levels at flue gas have been reported
to increase by Jia et al. (2010) and Duan et al. (2014) to the range
of 350–450 ppm in dry flue gas.
3.3.2. Trace elements
Currently, there exist only few studies evaluating the trace ele-
ments in the flue gas from the oxy-CFB boiler with real recycled
flue gas. All the current results presented in the literature are from
the results reported by CANMET using their 800 kWth oxy-CFB test
facility. Jia et al. (2013) presented stack gas sampling results for
mercury, other trace metals and volatile organics when firing bitu-
minous coal. In addition, Jia et al. (2012c) also presented similar
type of the results for trace metals and volatile organics when co-
firing various ratios of wood and bituminous coal.
Jia et al. (2013) showed the total mercury emissions from flue
gas in a range of 0.56–0.79 ␮g/m3 . They also presented the ratio of
oxidized mercury from total mercury emissions to be in a range of
∼80%. They stated that this is a welcome result since oxidized mer-
cury is easier to remove from the flue gas stream than elementary
mercury. In a study of co-firing wood and bituminous coal, the total
mercury emissions were even lower than for bituminous coal and
within the range of 0.11–0.29 ␮g/m3 . In addition, Jia et al. (2013)
reported the measurements for 27 other trace metal elements from
flue gas and according to the conclusions they considered that
metal emissions will most likely not be a concern when adopt-
ing oxy-CFB technology for power production. All the measured
concentrations were below Canadian national emission limitations.
In their evaluation of trace emission when co-firing coal and
wood, Jia et al. (2012c) detected small amount of aluminium, boron,
magnesium and sodium in a flue gas. Jia et al. (2013) also presented
the concentrations for 45 volatile organics. According to their
89
results, only small amounts of chloromethane, bromomethane, car-
bon disulphide, benzene and toluene were detected in the flue gas;
and almost all other organic compounds were below the detection
limit. They concluded that trace elements from oxy-CFB combus-
tion should have broader attention in the research community to
get wider perspective from this specific area of research (Jia et al.,
2013).
3.4. Agglomeration, fouling and corrosion
3.4.1. Agglomeration and recarbonation
The recarbonation phenomenon is known also in air-fired CFBs.
Due to its impact to the operation of the CFB boiler, the issue of
recarbonation in oxy-CFB combustion has been raised by several
researchers given that the high CO2 concentration during oxyfuel
combustion brings some additional challenges to this issue.
With a favourable temperature and CO2 concentration, the
CaCO3 could be calcined and CaO is formed. Thus if temperature
drops to below calcination temperature in the presence of suffi-
ciently high CO2 concentration, the unreacted CaO will react with
CO2 to reform CaCO3 . CaCO3 particles are known to stick together in
this reaction and this could cause fouling and formation of agglom-
erated chunks of materials that may not be suitable for normal
operation of the boiler. The potential places where agglomeration
could occur due to recarbonation within the CFB boiler are in the
cyclone, dipleg, sealpot and external heat exchanger (EHE). Simi-
larly, in oxy-CFB boiler, the loop-seal or the EHE may be fluidized
using CO2 or recycled flue gas; thus any occurrence of recarbonation
could cause defluidization which further increases the tendency for
agglomeration.
The recarbonation in oxy-CFB test was observed during the tests
done by Alstom in their 3 MWth pilot plant (Liljedahl et al., 2006).
Recarbonation issues were observed when they used pure CO2 as
fluidizing gas in the sealpot. To prevent any recarbonation, they
used air as a fluidizing gas in the sealpot instead of CO2 . In the test
carried out by Metso, in their 4–MWth pilot-CFB, the recarbonation
caused problems in circulation loop, when Ca/S-ratio was elevated
and bed temperature was over 870 ◦ C (Varonen, 2011). Later they
reported that the recarbonation problems were avoided when the
test were accomplished in the safe operating window in oxy-mode
(Varonen et al., 2012). However, no clear recarbonation issues have
been reported by Foster Wheeler or CIUDEN during their tests at
CIUDEN’s 30–MWth pilot plant (Lupion et al., 2013; Gomez et al.,
2014b).
The effect of water has been reported to influence the recarbon-
ation process. Wang et al. (2008) studied fly ash carbonation and
observed higher carbonation conversion ratios when H2 O is present
as compared to the tests without H2 O in the temperature region
they examined. They also noted that carbonation could occur even
in low temperatures (i.e. ∼250 ◦ C) if water is present as compared
to the occurrence of fly ash carbonation at temperatures greater
than 400 ◦ C if water is not added.
The simultaneous and sequential capture of SO2 and CO2 in the
reactions of calcination, carbonation, sulphation have been studied
during the development of both carbonate looping process (Ryu
et al., 2006) and oxy-CFB (Wang et al., 2011b). In general, the results
showed that the sulphation hinders the carbonation of CaO and SO2
capture will be enhanced with cyclic behaviour of limestone. In
addition, H2 O seemed to have an enhancing effect on the reactions.
The recarbonation issue is a phenomenon which should be taken
into account when designing the boiler. Different options for the
preventing recarbonation should be considered. The agglomeration
tendency could be affected by the temperature and gas atmosphere
in different regions of the CFB hot loop. To prevent any agglomera-
tion and recarbonation, it is essential to maintain the fluidizing and
90 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
flow conditions that will avoid any defluidization and the occur-
rence of any stagnant regions within the loop.
3.4.2. Fouling
In the convective pass, the recarbonation of CaO and the
stickiness of particles it produces may cause fouling. Also, the
carbonation reaction can increase the hardness and strength
of the deposits thus making it more difficult to remove (Wang
et al., 2008). Consequentially, any deposits could reduce the heat
transfer efficiency; and create issues during boiler operation and
maintenance (e.g. plugging, corrosion, structural damage).
Fly ash deposition during oxy-CFB combustion has been inves-
tigated by using the bench-scale test equipment without FGR by
Zheng et al. (2013) and Wang et al. (2014). In both studies the
temperature controlled ash deposit probe were used and deposi-
tion propensity and chemical compositions of ash deposits were
reported. Zheng et al. (2013) and Wang et al. (2014) reported that
deposition propensity was effected by combustion atmosphere.
When comparing the chemical compositions of ash deposits
formed under oxyfuel combustion and air combustion, the results
are comparable (Zheng et al., 2013; Wang et al., 2014). In a study of
Wang et al. (2014) the sum of CaO and MgO in the ash deposits was
increased with increasing Ca/S ratio during oxyfuel combustion.
Wang et al. (2014) also found a high correlation between deposi-
tion propensity and the sum content of Na2 O + K2 O during oxyfuel
combustion, suggesting that the initial stages of ash deposition is
strongly depended on alkali metal content. In their experiments,
no correlation was found between deposition propensity and sum
content of CaO + MgO. Thus, based on the studies, recarbonation
has a potential to cause fouling of the heat transfer surfaces in the
convective pass of the boiler. However, that has not been clearly
shown and no clear effects have been reported from the operation
of the larger oxy-CFB pilots.
3.4.3. Corrosion
Only limited studies have evaluated the corrosion issues during
oxy-CFB combustion. In various pilot tests undertaken, the corro-
sion in the cold end of the boiler is not a focus of research; hence no
results have been reported. The main focus of work to date has been
in the reporting of the SO3 concentration and its potential impact
to the corrosion.
Ahn et al. (2011) studied the SO3 levels in their 330 kW oxy-
CFB test facility at the exit of the cyclone section. The temperature
levels in their sampling point were reported to be in a range of
960–1060 K. They concluded that SO3 concentrations were higher
for oxy-firing vs. air-firing; however, on a normalized mass basis
the emissions were similar for both cases. In their experiments, the
temperatures in oxy-firing were slightly higher than in air-firing
case. The measured SO3 concentration levels were less than 5 ppm
for air-firing and in a range of 5–60 ppm for oxy-firing. Amount of
the limestone added to the process did not correlate to the SO3
concentrations (Ahn et al., 2011).
Tan et al. (2013) studied SO3 levels in their 800 kWth pilot
scale oxy-CFB test facility. Their measurements are representing
the backend SO3 concentrations at the temperature level of 100 ◦ C.
They reported very low SO3 concentrations when firing coal, or co-
firing of wood and coal. The measured SO3 concentrations were
below 3 ppm.
3.5. Oxy-CFB with high inlet O2 concentration and low recycled
flue gas
Increasing the inlet oxygen concentration by reducing the
recycled flue gas ratio leads to an increase in the adiabatic combus-
tion temperature and a decrease in the gas flow rate through the
furnace. This operating option is attractive because it could have the
Fig. 32. Hot loop share of total heat duty and O2 input share for the Polish coal as
the function of the adiabatic combustion temperature (Saastamoinen et al., 2006).
potential to decrease the size and capital cost of the CBF boiler. The
auxiliary power consumption is also reduced, because of smaller
gas flow rates, which then improves the net efficiency of the power
plant. In addition, the higher inlet oxygen concentration increases
the combustion rate at the bottom of the furnace, which is likely to
increase the combustion efficiency.
However, there are several challenges to ensure that boiler will
operate reliably. It is important to have controlled conditions at
the bottom of furnace and prevent any sintering of bed materials
and agglomeration due to the local high temperature that may be
caused by high oxygen concentration. In order to avoid sintering
of the bed material, the furnace temperature with typical fuel used
should be controlled to below 1000 ◦ C. Consequently, a higher share
of the total heat recovery needs to be carried out in the hot loop:
inside the furnace, cyclone, and the return leg system as shown in
Fig. 32.
Due to smaller gas flow rate, the cross-section of the furnace is
smaller in order to maintain the required fluidization velocity. This
reduces the heat transfer surface area of the furnace walls in rela-
tion to the volume and cross-section. The heat transfer surface area
can be increased by internal heat transfer elements, e.g. wingwalls
and hanging superheaters, but there are limits on how densely the
heat exchanger panels can be placed and still have efficient heat
recovery and avoid erosion. In PC boilers, the heat transfer prob-
lems are the main reason for hindering the application of higher
inlet oxygen concentrations. In a CFB boiler, additional heat recov-
ery is possible by placing fluidized bed heat exchangers to solid
recycle loop. Thus, the furnace temperature and the metal temper-
atures at heat transfer walls remain essentially unchanged, which
makes it possible to use similar heat exchanger materials as with
low inlet oxygen concentration (Fig. 33).
Another important topic related to higher inlet oxygen concen-
tration is the ability to burn fuels with very low calorific value.
4. Oxyfuel combustion for gas turbine applications
Natural gas combined cycle (NGCC) power plants are the most
efficient fossil fuel fired power plants reaching net efficiencies of
around 60% (LHV). Fired with natural gas, the low carbon content of
the fuel results in specific CO2 emissions of approx. 350 gCO2 /kWh
(i.e. for 60% net efficiency in NGCC configuration). This is less than
half of the value for coal-fired power plants (i.e. ∼780 gCO2 /kWh
for hard coal at ∼45% net efficiency or ∼925 gCO2 /kWh for lignite at
∼42% net efficiency). Due to the low nitrogen and sulphur contents
in the fuel, it is also favourable regarding the emissions of SOx
and NOx . By using CCS technologies, the emissions of NGCC power
plants can be further reduced far below 100 gCO2 /kWh.
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Max
Membrane wall temp. (°C)
-20 OXY-CFB-300 (1st gen)
-40 OXY-CFB-600 (2nd gen)
-60
-80
-100
-120
0 10 20 30 40
Height (m)
Fig. 33. Modelled metal temperatures in relation to maximum allowed metal tem-
perature with low (OXY-CFB-300, 24-vol%) and high (OXY-CFB-600, 40-vol%) inlet
oxygen concentration (Myöhänen et al., 2014).
To consider the application of CCS to a NGCC power plant, it is
essential to note that the CO2 content in the exhaust gas is lower
for a gas turbine (approx. 4%v) as compared to a conventional coal
fired power plant (approx. 14%v). This is caused by a high amount of
excess air that is needed to control the temperature at the turbine
inlet. Thus, the use of post-combustion CO2 capture (via chemical
absorption) could be penalized due to the high volume of flue gas
to be treated even if the CO2 content could be increased to approx.
8%v using a flue gas recycle. Modifying the gas turbine to operate in
oxyfuel combustion could be an opportunity whereby the flue gas
produced mainly consists of CO2 and H2 O.
Besides natural gas combustion, the gasification of coal allows
to operate gas turbines with coal-based fuels. Within the context
of CCS technologies, this pathway is broadly covered with pre-
combustion CO2 capture (via physical absorption), which is covered
in a different paper in this Special Issue. However, the operation of
oxyfuel gas turbine plants with coal derived syngas is an alternative
option for CO2 mitigation from coal.
4.1. Oxyfuel for gas turbines
The oxyfuel combustion for conventional coal-fired power
plants is characterized by the modification of the combustion pro-
cess when firing a mixture of highly enriched oxygen and recycled
flue gas. This should impact the combustion behaviour and heat
transfer to the water steam side of the boiler. However, the actual
power cycle, i.e. the Rankine cycle, remains more or less the same
considering working fluid and cycle parameters.
In gas turbines, the oxidizing medium and the exhaust gases
pass through its own power cycle – a Joule or Brayton cycle. Due to
the different fluid properties the requirements for the oxyfuel cycle
are somewhat different to the air-case. On the one hand this makes
the modification of an air blown gas turbine to an oxyfuel gas tur-
bine more complex as it involves the compression and expansion
in turbomachines as well as the oxyfuel combustion on elevated
pressure. On the other hand, it offers more options for optimiza-
tion and the possibility of new cycles especially designed for the
use with oxyfuel specific working fluids.
The different processes that are possible for oxyfuel gas turbines
influence the requirements to the components of the process like
turbomachines, combustors and heat exchangers as well as the oxy-
fuel specific parts such as the air separation unit (ASU) and CO2
processing unit (CPU). Due to the combustion at high pressure,
the supply of high pressure oxygen is necessary. Depending on the
process chosen the required pressure differs in a wide range. The
CPU is also affected by different conditions at which the flue gas
91
is extracted from the process. It is also expected that the ASU and
CPU are the main energy consuming parts of the oxyfuel GT pro-
cess. Additionally, the influence of the chosen power cycle and its
parameters result in a significant difference in the gross efficiency
of the plant which is also significant for the efficiency penalty of
the process (Bolland et al., 2003).
4.2. An overview of the cycles
Gas turbines are operated with high excess oxygen due to the
fact that a high amount of air is needed to keep the turbine inlet
50 temperature within material limits. In oxyfuel operation, the com-
bustion is close to stoichiometric conditions as recycled CO2 can
be used for temperature control and as excess oxygen has to be
produced with high power consumption by the ASU. This results
in a higher flue gas recycled ratio as compared to oxy-PC coal fired
power plant.
Another difference to coal is that the hydrogen content of the
fuel is significantly higher than for coal. The stoichiometric combus-
tion of methane with oxygen results in an exhaust gas consisting
of 67% water on a molar basis. Therefore, the oxyfuel cycles for gas
turbines can be divided into two groups that are distinguished by
the recycled substance to moderate the temperature in the pro-
cess. Because of the different thermodynamic properties this has
a strong effect on the cycle performance and on the components
needed in the cycle.
4.2.1. CO2 -based cycles
The most obvious solution for oxyfuel gas turbine applications
is the so-called semi closed oxygen combustion combined cycle
(SCOC-CC) or oxyfuel combined cycle (OCC) that was originally
presented in 1992 by Bolland and Sæther (1992). Starting with a
natural gas-fired combined cycle power plant (NGCC) the modifi-
cation is analogue to the oxyfuel power plant for coal fired steam
power plants. The key components of the plant remain the Brayton
cycle gas turbine and the heat recovery steam generator (HRSG)
with a Rankine cycle. The gas turbine has to be modified to the
oxyfuel conditions whereas the HRSG has only minor difference to
the air-blown case. The exhaust gas from the HRSG is cooled and
partly recycled to the gas turbine for cooling purpose. Due to the
cooling, most of the water is condensed and thus the recycle stream
consists mainly of CO2 . To retain the turbine inlet temperature of
air-blown gas turbines recycle ratios of approx. 90% are necessary
while the remaining flue gas can be further processed to storage
conditions.
Other proposed cycles are based solely on high pressure CO2
without a bottoming water steam cycle. These cycles are character-
ized by an intercooled or isothermal compression to supercritical
pressures and high internal recuperation. The cycles can be
described as combined Rankine and Ericsson cycles. The differences
between the cycles are mainly the number of expansions and the
different pressure levels at the top and the bottom of the cycles. A
first kind of this cycle was proposed by Yantovski et al. (1993) for
the use at enhanced oil recovery (EOR) within the OCDOPUS project.
The cycle was developed to the COOPERATE (Yantovski et al., 1995)
and the MATIANT cycle (Mathieu, 1998). Modified configurations
are the Ericsson-like E-MATIANT and the CC-MATIANT using a bot-
toming steam cycle, which is basically the same as the SCOC-CC
but with internal recuperation (Houyou et al., 2000). The recently
presented Allam cycle (Allam et al., 2013) that is demonstrated by
NET power is based on the same principle. Due to the use of high
pressure CO2 as working fluid, the produced CO2 can be extracted
from the process already at storage conditions.
92 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
4.2.2. Water-based cycles
The approach of the water-based cycles is to use the condensed
water of the exhaust gas instead of the CO2 for the cooling of
the combustion cycle. One of the investigated cycles is the water
cycle or CES cycle named after Clean Energy Systems, Ltd. (CES).
CES has made the detailed cycle development (Anderson et al.,
1999), although the basic idea was already proposed by Bolland
and Sæther (1992). The cycle is based on a so-called gas generator
that burns a hydrocarbon fuel with oxygen at high pressure. The
temperature is controlled by evaporating liquid water injected to
the combustor which generates a working fluid that consists by vol-
ume of approx. 90% steam and 10% CO2 . The mixture is expanded
in a Rankine-like cycle through a triple pressure turbine and water
and CO2 are then separated by condensation.
A more complex approach to a water-based cycle is the Graz
cycle which was originally developed as an internal combustion
steam cycle for hydrogen as a fuel in the 1980s. It was modified to
the combustion of hydrocarbons with carbon sequestration (Jericha
and Fesharaki, 1995). It uses two recycle flows to moderate the
combustor temperature. The characteristic feature of the cycle is
that the heat of the exhaust gas after the first expansion is used to
generate high pressure steam in an HRSG. The high pressure steam
is expanded in a steam turbine and then used as the cooling medium
for combustion and turbine. The exhaust gas from the HRSG is split
into two streams. One of the streams is compressed and serves as
the second cooling medium for the combustion. The remaining part
passes a low pressure turbine part with additional expansion and
the separation of water and CO2 . Earlier publications (Sanz et al.,
2004) refer to this cycle as S-Graz cycle (High Steam Content Graz
Cycle) in differentiation to an earlier version of the Graz cycle with a
pure CO2 recycle instead of exhaust gas from the HRSG thus leading
to a significantly higher CO2 content in the working fluid.
4.3. Review of the leading oxy-GT cycles
As discussed in the previous section, there are several variants
for oxy-GT cycle. In this paper, the following leading oxy-GT cycles
will be reviewed in details:
• SCOC-CC cycle
• Allam cycle
• CES cycle
• Graz cycle.
The review will consist of the discussion on the following areas:
• Thermodynamic cycle
• Combustion and emissions
• Turbomachinery
• Additional equipment.
4.3.1. Semi-close oxygen combustion-combine cycle (SCOC-CC)
Although the SCOC-CC process is very close connected to the
generic combined cycle process, there are significant differences
between the processes. A process flow sheet of the SCOC-CC
is shown in Fig. 34. Basically, the only differences between an
SCOC-CC and an NGCC are the pressurized oxygen stream to the
combustor and the recycle with condenser going back to the
compressor instead of air. However, compared to the air-blown
process there are significant changes in the composition of the
working fluid. Due to the high air-to-fuel ratio of air-blown gas
turbines, the working fluid consists mainly of nitrogen and oxygen
with some amount of water and CO2 after combustion. The drying
and recycle of the exhaust gas in the oxyfuel case causes a shift
from the nitrogen-based working fluid to a CO2 -based fluid. As
the addition of the oxygen takes place in the combustor at near
Fuel
Oxygen
C T ST G
Steam
Cond.
cycle
H2O
Fig. 34. Simplified flow sheet of the SCOC-CC according to Bolland and Sæther
(1992).
stoichiometric conditions, the O2 -content is also much lower
than in the air-blown case. The changing properties, e.g. the ratio
of specific heats, lead to a much higher optimum pressure ratio
of the oxyfuel gas turbine process to achieve similar exhaust
gas temperatures and cycle efficiencies as in the air-blown case.
Although the bottoming steam cycle has a higher output at lower
pressure ratios there is also an increased optimum pressure ratio
for the SCOC-CC (Bolland and Mathieu, 1998). The high pressure
ratio and the different working fluid require the design of new
gas turbine components. Kvamsdal et al. (2006) evaluate that
the high pressure combustor for hydrocarbon fuels in a CO2 /O2
environment is the most critical part regarding technical maturity.
The compressor (C) and turbine (T) for the gas turbine are also
challenging whereas the HRSG, the steam turbine (ST), and the
recycle condenser (Cond.) are considered as technically mature.
(a) Thermodynamic evaluation
Due to the number of studies regarding the SCOC-CC, there is a
variety of results for the thermodynamic evaluation of the process.
The main focus of the published results is on the behaviour of the
oxyfuel gas turbine.
Oxyfuel gas turbine
The efficiency of combined cycle power plants depends on the
technology level of the gas turbine which is often connected with a
certain turbine inlet temperature (TIT). For a given TIT and fixed
steam cycle parameters there is an optimum pressure ratio for
the combined cycle efficiency. With a rising pressure ratio the
gas turbine efficiency increases and the exhaust gas temperature
decreases. This reduces the efficiency of the bottoming steam cycle.
The gas turbine efficiency and the turbine exit temperature depend
on the ratio of specific heats. The ratio of specific heats for CO2 is
lower than that for air so the different working fluid in the SCOC-CC
has an effect on the optimum pressure ratio. In an early study by
Bolland and Sæther (1992) an optimal value of 30 has been shown.
Yang et al. (2012) calculate the optimum pressure ratio to 60 for
1400 ◦ C and 90 for 1600 ◦ C TIT, respectively. At the optimal pressure
ratio the exhaust gas temperature is similar to that of the air-blown
case. Fig. 35 shows the results of the study for a 1400 ◦ C class gas
turbine for a generic NGCC and an SCOC-CC – the gain in net effi-
ciency between the pressure ratios of 40 and 60 is rather small. The
flat optimum causes a high sensitivity to the assumptions taken in
the respective study. Several authors chose a lower pressure ratio
than this optimum value resulting in a higher exhaust gas tempera-
ture but only a small drop in efficiency. For this reason the pressure
ratio for the SCOC-CC is considered to be in the range of 30–40 for
a combustion outlet temperature between 1300 and 1400 ◦ C prior
to the mixing of cooling flows. In the most recent studies, the over-
all net efficiency of the process is estimated to be between 46 and
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 35. Efficiency of SCOC-CC and generic combined cycle (CC) for a combustor
outlet temperature of 1400 ◦ C for different pressure ratios (PR) (Yang et al., 2012).
49% for a 1400 ◦ C class oxyfuel gas turbine. This leads to net effi-
ciency losses to the respective reference case of 8–11%-pts (Dillon
et al., 2005; Kvamsdal et al., 2007; Riethmann et al., 2009; Corchero
et al., 2011; Thorbergsson et al., 2012; Dahlquist et al., 2013). Due to
the external compression of the oxygen, the gross efficiency of the
SCOC-CC is generally higher than that of the conventional NGCC. As
the energy for the compression of the oxygen is accounted within
the supply system of the oxygen there is a higher specific energy
demand compared to atmospheric fired boilers.
For the thermodynamic evaluation of gas turbines the effect of
blade cooling has to be taken into account. Several authors include
cooling models into their gas turbine models. The fraction of cool-
ing flow to the compressor inlet flow is found to be similar or less
for oxyfuel gas turbines at the same pressure ratio compared to the
air-blown turbines (Jordal et al., 2003; Jonsson et al., 2005). Yang
et al. (2012) show comparable results for an oxyfuel gas turbine
if the cooling duty of the first stage is scaled to the latter stages.
Though the heat capacity of the cooling fluid and the hot gas are
more favourable in the air-blown case, the lower compressor outlet
temperature in the oxyfuel case reduces the amount of cooling gas.
With a rising pressure ratio the compressor outlet temperature
and thus the cooling duty increases. However, the same authors
show that at low pressure ratios the hot gas temperature in the
latter stages of the turbine is significantly higher due to the lower
ratio of specific heats resulting in higher blade temperatures. Their
study suggests that the cooling duty of oxyfuel gas turbines is
much higher if the gas turbine does not operate at the optimum
pressure ratio. Sammak et al. (2013a) conclude that considering
aerodynamic effects on the oxyfuel turbine leads to an increased
blade surface thus more cooling is required.
HRSG
The influence of oxyfuel combustion on the HRSG in considered
to be relatively small in comparison to the gas turbine. Therefore,
in many studies the same HRSG concept as in the reference case
is used, e.g. a three pressure cycle with reheat (Dillon et al., 2005;
Kvamsdal et al., 2007; Yang et al., 2012). This means that the HRSG
is optimized for the exhaust gas temperature of the air case which
is in most cases below 600 ◦ C. If the exhaust gas temperature of
the oxyfuel gas turbine should reach this temperature the pressure
ratio must be near the optimum value. As stated before most of the
studies chose lower values for the pressure ratio which results in
higher exhaust gas temperatures. A higher exhaust gas tempera-
ture reduces the need for multiple pressure levels in the HRSG. So
Dahlquist et al. (2013) chose a two pressure cycle for their gas tur-
bine with an exhaust gas temperature of 620 ◦ C at a pressure ratio
93
of 34 although their calculated optimum value was 47. According
to Riethmann et al. (2009) the use of a triple pressure reheat cycle
would increase the net efficiency by 0.6%-pts in comparison to a
dual pressure cycle used within the ENCAP project at a gas tur-
bine pressure ratio of 40 and an exhaust gas temperature of 638 ◦ C.
Besides the higher exhaust temperature, the HSRG is affected by
the different properties of the exhaust due to its high CO2 con-
tent. Dahlquist et al. (2013) show that the specific heat capacity
of CO2 is non-linearly dependent on the temperature in the range
of the HRSG temperatures. Furthermore, in the high temperature
region of the HRSG the specific heat capacity is higher than in the
air case but drops to lower values if the temperature decreases. This
behaviour is favourable to achieve high HRSG efficiencies because
it allows to reach a colder HRSG outlet temperature. For a single
pressure cycle the HRSG exit temperature is around 10 ◦ C lower in
the oxyfuel case if the exhaust gas temperature is the same, for a
dual pressure it is around 6.5 ◦ C lower (Dahlquist et al., 2013).
Corchero et al. (2011) use a single pressure steam cycle in their
model. The achievable maximum net efficiency of the combined
cycle is generally lower compared to other published values, but
the effect of changing the pressure ratio between 20 and 60 is
lower than 0.5%-pts.
Recycle
In the HRSG the exhaust gas is cooled close to its water dew
point. The recycle stream to control the turbine inlet temperature
is then further cooled to condense most of the water. Due to
this recycle stream, the inlet conditions of the compressor are
not determined by the ambient conditions but by the design
parameters that can be optimized. It is known for conventional
gas turbines that the efficiency decreases with a higher ambient
temperature. Therefore, many authors set the compressor inlet
temperature to a low value around 20 ◦ C (Dillon et al., 2005; Yang
et al., 2012; Thorbergsson et al., 2012). Corchero et al. (2011) show
that increasing this temperature can have a positive effect on the
overall efficiency because the water content increases the heat
that is available for the steam cycle. Dahlquist et al. (2013) vary the
recycle temperature between 25 and 80 ◦ C leading to an increasing
efficiency up to 60 ◦ C by approx. 0.2%-pts. At a higher recycle
temperature the efficiency dropped. The optimum is not very
significant so a preferred range between 40 and 70 ◦ C is concluded.
For the variation, the pressure ratio has been adjusted to keep
the exhaust gas temperature constant as the water content and
thus the ratio of specific heats varies. Another difference to other
studies is a preheater after the condenser to reduce the relative
humidity at the compressor inlet to 80%. Riethmann et al. (2009)
investigate the supercharged SCOC-CC process, i.e. the compressor
inlet pressure was varied while keeping the pressure ratio con-
stant. The results show that the efficiency of the overall process
decreases with supercharging factor of 3 and 10 by 0.1%-pts and
0.5%-pts, respectively. However, they suggest that supercharging
has a positive effect on the part-load behaviour of the process as
the process can be operated with a constant pressure ratio and a
constant exhaust gas temperature at the same time.
Reheat cycles
Fiaschi et al. (2009) investigated an SCOC-CC with sequential
combustion. The cycle is called MATIANT cycle in their study as
it is derived from the MATIANT-CC but without recuperation. As
the sequential combustion principle needs already high pressures
their cycle operates at a gas turbine inlet pressure of 110 bar. The
study considers the influence of cooling on this type of process.
Because of the high pressure in the gas turbine it is assumed that
conventional cooling methods are not applicable. In this case the
94 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
gas turbine is cooled by a split flow of IP steam from the bottoming
cycle in a closed cycle. At a top temperature of 1300 ◦ C the process
reaches an efficiency of 55.4% without cooling and 54.1% with
cooling accounted, respectively. However there is no reference
process given for comparison of the efficiencies. Mletzko and
Kather (2014) consider the sequential combustion process based
on the GT26. If the high pressure ratio necessary is not achievable,
the efficiency could be increased by improving the heat recovery
either by increased steam parameters or a recuperated gas turbine
which would be even closer to the MATIANT-CC as the process
mentioned before. The results show that at a pressure ratio of
60 the efficiency loss compared to the reference process can be
reduced from 9.3%-pts to 8.7%-pts with both optimization options.
If the pressure ratio is kept at approx. 30 as in the reference process
the efficiency loss would be 10.8%-pts. In this case the effect of the
recuperated gas turbine reduces the loss by 1.7%-pts whereas the
increased steam parameters only reduce the loss by 1.0%-pts. The
pressure losses of the recuperator are crucial regarding the use of
this process.
Influence on ASU and CPU
The SCOC-CC process assumes that the oxygen is delivered at
high pressure, i.e. it is added directly to the combustor section. This
means that the pressure has to be at least 30–60 bar depending
on the respective case. There is no detailed investigation on the
oxygen supply process specific to the SCOC-CC process. Dillon et al.
(2005) assume a pumped LOX cycle, but most authors use specific
energy demands of near-atmospheric oxygen production with
subsequent compression, e.g. Kvamsdal et al. (2007), Thorbergsson
et al. (2012). Yang et al. (2012) use a combination of a pumped
LOX cycle to a fixed pressure and additional compression for
varying the pressure ratio. In general an oxygen purity of 95%
is assumed that leads to CO2 purities of approx. 90% (Kvamsdal
et al., 2007). Yang et al. (2012) investigate the effect of reducing
oxygen purity to 90%. They show that not only the CO2 purity is
reduced by 10% but also the net efficiency of the process is slightly
decreased. The effect is more obvious at extremely high pressure
ratios. Further purification of the CO2 is not investigated in detail
by most of the studies and they only consider the energy necessary
for compression from atmospheric pressure to pipeline conditions.
Ulizar and Pilidis (1997) describe an SCOC-CC with a pressure
ratio of 60 in which all of the recycle is compressed and the flue
gas is split at high pressure reducing the need for compression to
storage. Shao et al. (1995) show a highly integrated system of ASU
and CPU for an SCOC-CC. As a main part of the integration the flue
gas is condensed against cold oxygen from the ASU.
(b) Combustion and emissions
The operation of gas turbine combustors at oxyfuel conditions
is significantly different from that of an air-blown gas turbine.
The near-stoichiometric combustion is a major difference to the
air case. Therefore, it is challenging to achieve complete fuel burn
out and thus low CO emissions. The O2 /CO2 working fluid affects
the combustion process because of differences in reactivity and
stability. The different composition also affects the heat transfer
properties of the working fluid. Because the working fluid still
contains small amounts of nitrogen the NOx emissions cannot be
neglected (Sundkvist et al., 2014).
Emissions
As the exhaust gas of an oxyfuel plant is used for sequestration
the demands for these emissions are different from exhaust that is
vented to the air. On the one hand CO-emissions are not that critical
Fig. 36. Equilibrium CO-concentration for methane combustion with CO2 /O2 and
air (Amato et al., 2010).
as in the air-blown case as it will be sequestered along with the CO2
but it is still important in point of fuel use. On the other hand O2
emissions have to be avoided as they increase the energy demand.
Both CO and O2 can also be important regarding corrosion. Due to
the separate addition of oxygen, the equivalence ratio ϕ or oxygen
excess ratio  = 1/ϕ can be adjusted independently of the required
flame temperature that is controlled by the recycle stream. The
equivalence ratio has to be a trade-off between the CO emissions
and O2 emissions. Amato et al. (2010) show that the equilibrium
concentration of CO in atmospheric oxyfuel combustion is approx.
two orders of magnitude higher than in the air-case as shown in
Fig. 36. Though low emissions of CO and O2 are favoured at low
flame temperatures, a kinetic approach revealed that the equilib-
rium concentrations are not reached at a fixed residence time of
40 ms. Higher pressure reduces the equilibrium concentration due
to Le Chatelier’s principle and leads to faster reaction rates. Richards
et al. (2005) investigate the CO emissions of an oxyfuel gas turbine
combustor with a combined network of perfectly stirred reactor
and a plug flow reactor (PSR/PFR) model. For a recycle stream con-
sisting mainly of CO2 at 10 bar and a flame temperature of 1650 K
the equilibrium concentration of 200 ppmv is reached in 20 ms for
ϕ = 0.98 (Richards et al., 2005). Experimental results from an ideal-
ized atmospheric lab-scale gas turbine combustor showed that CO
emissions were insignificant for ϕ < 0.95 but then increased more
rapidly as for combustion with air (Williams et al., 2007). Glarborg
and Bentzen (2008) show that the reaction of CO2 with atomic
hydrogen leads to a drastic increase of CO concentrations in the
flame zone. This could lead to near-burner corrosion. Due to the
cooling rates of typical power plant furnaces, there are no prob-
lems with increased CO emissions anticipated. Reactor network
calculations by Sundkvist et al. (2014) result in CO concentrations
of approx. 500 ppm at the end of the combustor excess oxygen of
0.5% and lead to not desirable further reaction in the turbine section
reducing the emissions to 400 ppm. Significantly less CO emissions
and more stable conditions in the turbine are achieved with higher
oxygen excess.
Williams et al. (2007) measured the emissions of NOx at
atmospheric conditions for different fuels including methane and
different syngas compositions. With 1 vol% N2 in the oxidizer
they observed the lowest emission for methane with 0.5 ppmv
for 30 vol% O2 and 2 ppmv for 34 vol% O2 , respectively. The higher
value for higher O2 concentration is due to a higher flame tem-
perature. Beside the flame temperature the NOx emissions are
linked to the fuel nitrogen and the fuel specific concentration
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
of O-atoms in the flame. Methane proved to be favourable in all
aspects compared to syngas.
Combustion stability
Kutne et al. (2011) investigate the combustion stability of
methane at oxyfuel conditions using a gas turbine burner that
was designed for atmospheric methane combustion with air.
They show that the O2 content in the oxidizer has a strong effect
on the flame stability. Because of the lower flame temperature
and the lower laminar flame velocity the oxygen content has to
be higher than in air to achieve stable combustion behaviour.
In contrast to this the equivalence ratio is of minor importance.
However, if near-stoichiometric conditions in combination with
an increased oxygen content of 30 vol% in the oxidizer are applied
the flame temperature is too high for gas turbine inlet conditions.
It is concluded that a redesign of gas turbine burners is necessary
for oxyfuel conditions. Both Kutne et al. (2011) and Williams
et al. (2007) report that below 22 vol% oxygen it was not possible
to achieve stable combustion for methane for their respective
burners. Williams et al. (2007) achieve flame stability for lower
oxygen concentration with syngas fuels especially for high hydro-
gen contents. Andersson et al. (2006) report that combustion in
a gas-fired 100 kW test rig with 21 vol% O2 in CO2 leads to sup-
pressed flame development and poor burn-out rate compared to
air-blown flames. Similar combustion behaviour as in the air-case
was achieved at 27 vol% O2 .
Heat transfer
Regarding the heat transfer Andersson et al. (2006) show that
the radiation intensity of oxyfuel flames is approx. 30% higher
than in the air case at the same temperature. Besides the high CO2
content in the working fluid the reason is seen in different soot
levels in the flame. Similar results from numerical calculations
are presented by Ditaranto et al. (2006). However, they report
that the radiation effect is reduced at the combustor walls due
to a high level of re-absorption by CO2 in the oxyfuel cases. They
suggest to inject CO2 as a diluent for cooling the combustor walls.
Amato et al. (2010) use the higher radiation levels to explain the
higher difference between the adiabatic and the measured flame
temperature in the oxyfuel case compared to the air case.
(c) Turbomachinery
The different properties of the working fluid itself and the
required pressure ratio of the SCOC-CC cause the need of newly
designed turbomachinery for the process, e.g. the lower speed
of sound in CO2 requires reduced velocities to achieve dynamic
similarity. Ulizar and Pilidis (1998) estimate a penalty of 10% if
existing equipment is used. As a countermeasure to allow the
use of existing gas turbine technology Treibs and Alekseev (2013)
propose the addition of light gases like helium and neon to adjust
the thermodynamic properties of the working fluid close to those
of air. However, there are some studies giving a preliminary design
of new turbomachinery for oxyfuel gas turbine applications. As
the steam cycle of the SCOC-CC is similar to a conventional NGCC
the steam turbine is considered to be within the current design
practise (Sanz et al., 2008). For this reason this part is not discussed
further in this section.
Recycle compressor
The compressor is generally believed to be the more critical part
of the gas turbine. Roberts and Sjolander (2005) experimentally
investigated the influence of working fluids with different ratios of
95
specific heats, namely air, CO2 , and argon, on a single stage radial
compressor. They showed a significant effect on the pressure ratio,
the surge behaviour and the isentropic efficiency of the compres-
sor. Dahlquist et al. (2014) estimate that the lower viscosity of CO2
reduces the profile loss of the blades.
Within the ENCAP project the design of turbomachinery for an
SCOC-CC with a gross output of 400 MWe is conducted by Woollatt
and Franco (2009) using an in-house software package. The gas
turbine had a shaft power of 275 MW and a pressure ratio of 40.
Based on conventional combined cycle gas turbines a single shaft
design with 3000 rpm has been chosen. The main challenge for
the compressor is that the high density of the working fluid causes
a small annulus area. A trade-off has to be made between short
blades resulting in high clearance losses and lowering the mean
radius at the outlet thus leading to an increased number of stages.
The reason more stages are needed is that a decreasing blade speed
leads to a lower stage enthalpy rise at a given loading coefficient. In
the study a design with 24 stages is selected. It can be shown that
a compressor for this pressure ratio could be designed by staying
within the common limits of compressor design and operates at
industrial levels of loading coefficient and surge margin. However,
Sanz et al. (2008) report a design for the same pressure ratio
under similar assumptions resulting in 19 stages. A possible way
to reduce the number of stages at a given loading coefficient is to
increase the blade speed by increasing the rotational speed. In a
single-shaft design for power generation a gear between turbine
and generator is needed. Sammak et al. (2011) present a prelimi-
nary compressor design for a geared mid-sized SCOC-CC at approx.
100 MWe with a pressure ratio of 37 and 18 stages at 5200 rpm
at comparable loading coefficients as Woollatt and Franco (2009).
It is remarked that the number of stages is very sensible to the
allowable hub-to-tip ratio, i.e. the blade length at the compressor
outlet. Reducing the allowable value from 0.92 to 0.90 results in
additional two to four stages. A design for higher pressure rapidly
leads to more stages making the single-shaft design less attractive.
Higher pressure ratios can be reached with a twin-shaft design.
Ulizar and Pilidis (1998) propose a configuration of low-pressure
compressor with a pressure ratio of 7 connected to a low-pressure
turbine and the generator at 3000 rpm and a high pressure com-
pressor turbine combination with a compressor pressure ratio of
8 resulting in an overall pressure ratio of 56 realized with a total
of 21 stages. Thorbergsson et al. (2012) present a conceptual twin-
shaft design based on the same assumptions as in Sammak et al.
(2011). The compressor has 14–16 stages running at 7200 rpm
driven by a separate turbine. The generator is connected to a power
turbine. The compressor efficiency increases with the number of
stages because the stage loading of the latter stages is reduced, also
reducing the clearance losses.
For the realization of all oxyfuel processes the use of existing
equipment would be favourable. Therefore, Woollatt and Franco
(2009) evaluate if an existing 22-stage compressor would be feasi-
ble to operate under oxyfuel conditions with some modifications.
They estimate that using the same compressor with modified
blade geometries would result in comparable surge margins as
conventional industrial compressors and efficiencies as a new-
designed compressor although some values are outside the normal
design range of the used correlations. If the compressor remains
unchanged dynamic similarity can be attained for the first blade
row by increasing the mass flow by 19% and lowering the rota-
tional speed by 25%. Under these conditions a 50 Hz compressor
is estimated to be operable at 2400 rpm and a pressure ratio of 30
leading to a reduced efficiency by 1.5%. A 60 Hz compressor is oper-
able at 3000 rpm at slight over speed with a pressure ratio of 26.6
and 4% lower efficiency.
Besides the aerodynamic effects Sanz et al. (2008) expect no
need for using highly advanced compressor materials or cooling
96 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 37. Schematic view of the OXY-GT combustion system (Sundkvist et al., 2014).
due to low exit temperatures and low centrifugal loads. Attention
has to be paid to the water saturated inlet flow as condensing
droplets could cause erosion.
Gas turbine
The design of the turbine stages can also be divided to the single
and twin-shaft designs. Woollatt and Franco (2009) and Sammak
et al. (2011) present turbines for single-shaft design at 3000 rpm
and 5200 rpm, respectively. Both designs have 4 stages and similar
loading coefficients. Due to the higher power output assumed in the
study of Woollatt and Franco (2009), the diameter of the turbine is
twice the value of Sammak et al. (2011). Both studies aim to achieve
an outlet Mach number of 0.5–0.6. This leads to good diffuser per-
formance and keeps the root stress level in the range of current
design practice. As in the compressor considerations the study of
Sanz et al. (2008) showed significantly different stage numbers. For
the turbine 8 stages are estimated.
The turbine for the twin-shaft configuration described by
Thorbergsson et al. (2012) is presented by Sammak et al. (2013b).
The compressor turbine consists of 2 stages at 7200 rpm. The power
turbine has 3 stages for a rotating speed of 4800 rpm making a
total of 5. Reducing the speed of the power turbine to the genera-
tor speed of 3000 rpm would result in additional 2 turbine stages.
This is in line with the design of Ulizar and Pilidis (1998) that has 2
stages for the compressor turbine and 6 stages for a power turbine
at 3000 rpm and a pressure ratio of 56.
Sanz et al. (2008) estimate that the higher number of turbine
stages increases the cooling duty which in turn reduces the
efficiency. Furthermore, the cooling with recycled CO2 needs
to ensure that soot or ash accumulation in the cooling paths is
avoided. Hammer et al. (2009) investigate the heat transfer on the
1st vane row of an oxyfuel gas turbine using heat transfer correla-
tions. They estimate that the effect of higher Prandtl numbers of
the working fluid is compensated by lower Reynolds numbers. The
radiative heat transfer of the working fluid is relatively low com-
pared to the convective heat transfer. However, the radiative part
could strongly increase if the turbine parts are directly exposed to
thermal radiation of the flame.
(d) Additional equipment
Besides the oxyfuel gas turbine that needs to be newly designed
the other components of the process are considered generally as
state-of-the art as shown by Franco et al. (2006) and Kvamsdal
et al. (2006). The HRSG and other components of the bottoming
water steam cycle are standard technology, but some differences
in the fluid properties of the exhaust gas need to be considered.
The exhaust gas condenser operates at atmospheric pressure.
However, the condensation behaviour of gas/steam mixtures and
corrosion issues have to be taken into account. Dahlquist et al.
(2013) propose a spray tower design with surface enhancing plates
as the exhaust condenser. The condenser also acts as a scrubber
to remove impurities from the working fluid. Therefore, a water
treatment has to be included. According to Ulizar and Pilidis
(2000), the operation, start-up and part-load does not exceed the
state-of-the-art equipment.
(e) Demonstration activities
The GASSNOVA funded OXY-GT project is a partnership of
Siemens and Nebb Engineering together with SINTEF and Lund
University. The overall aim is to develop a commercial scale SCOC-
CC demonstration plant in the range of 100 MWe . The current
project status has yet completed the first of three phases consist-
ing of a feasibility study and the development and testing of a
combustion system. The anticipated second phase of the project
is the operation of a small scale pilot plant at Lund University
(Sundkvist et al., 2014). According to recent press releases (Olsen,
2014) the combustor has been tested successfully until February
2014 but the upcoming stages of the project have been put on hold
by Siemens due to the current market situation. However, SIN-
TEF is planning a pilot gas turbine in Trondheim in the range of
100 kW.
Sundkvist et al. (2014) present a combustor concept developed
by Siemens within the OXY-GT project as shown in Fig. 37. This
design should be tested at the HIPROX facility of SINTEF. The fuel
is injected through fuel pegs at the inlet of a swirl generator. The
recycled working fluid is split at a ratio of around 0.5 to the burner
and to the dilution zone. The working fluid to the burner is mixed
with the oxygen in a mixing dome upstream to the swirler. The
amount of working fluid through the burner is determined to have
similar laminar flame velocity as in the air-case thus higher tem-
peratures are needed. The remaining working fluid serves to reach
the outlet temperature of an air-blown combustor.
4.3.2. Allam cycle
The Allam cycle, the MATIANT cycle and their predecessors are
based on semi-closed CO2 cycles without a bottoming steam cycle.
A major characteristic of these cycles is the supercritical condition
of the CO2 at the upper pressure level. Instead of using a bottoming
cycle an internal recuperator heats the compressed working fluid
by cooling the turbine exhaust. Fig. 38 shows that the part down-
stream of the recuperator is basically the same for all processes. The
exhaust gas leaving the recuperator is further cooled to condense
the combustion water. The compression to the upper supercritical
pressure level is realized by an intercooled compression while
the last stage operates either in a liquid or dense supercritical
state. The additional CO2 from the combustion can be extracted
from the process at high pressure for transport. Fig. 38 shows
the proposed flow sheet of the MATIANT cycle (Mathieu, 1998).
The supercritical high pressure turbine (HPT) for CO2 has inlet
conditions like a conventional Rankine steam cycle. The recycled
CO2 is heated solely by recuperation. At the time of proposal the
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125 97

MATIANT cycle Allam cycle

Fuel Fuel

...
Oxygen Oxygen
Intercooled
Compressor
G HPT IPT LPT G HPT G

Cond.
ASU waste heat
H2O CO2

Fig. 38. Simplified flow sheets of the MATIANT according to Mathieu (1998) and Allam-Cycle according to Allam et al. (2013).

authors assumed that higher inlet temperatures at supercritical 1600

pressures would be a technological barrier for the process. The
1400
outlet stream of the supercritical turbine is heated to gas turbine
inlet conditions at an intermediate pressure level. For heating the 1200
remaining available heat from the turbine exhaust gas is used

Temperature in K
followed by an internal combustion. The expansion is separated 1000
in two turbines (IPT and LPT) with another internal combustor as
800
reheat. The heat of the LPT exhaust gas is used in the recuperator.
The proposed cycles of the OCDOPUS project (Yantovski et al., 600
1993) and the Allam cycle (Allam et al., 2013) have a more simple
400
approach from the process perspective. The supercritical fluid is
fed directly to the combustor after recuperation. The hot gas is 200
expanded in a single step through the supercritical CO2 turbine. Allam MATIANT OCDOPUS
Compared to conventional gas turbines it is operating at high 0
-1500 -1000 -500 0 500 1000 1500
absolute pressures but low pressure ratios. As shown in Fig. 38,
Specific entropy in J/(kg K)
the Allam cycle waste heat from the ASU serves as additional heat
input to the recuperator. Because of the recent demonstration
Fig. 39. Temperature-entropy-diagram for OCDOPUS, MATIANT and Allam cycle
activities regarding the Allam cycle, this chapter will focus on this (pure CO2 ).
cycle. However, due to the recent proposal and the development
by an industrial consortium detailed and objective research on the
process is scarce. supercritical CO2 to the same temperature as the turbine outlet is
(a) Thermodynamic evaluation around 200 kJ/kg higher. According to the authors this gap can be
filled by integration of waste heat from the air compressors of the
ASU. The additional heat input reduces the amount of fuel needed
Yantovski et al. (1993) calculate the net efficiency of the in the process. Allam et al. (2013) show that the additional heat
proposed OCDOPUS cycle to approx. 34-36% at a turbine inlet input reduces the energy supplied by the fuel by approx. 25%.
temperature of 1023 ◦ C. The pressure levels are 100 bar of the
supercritical part and 7 bar in the low pressure section. The Reheat cycle
MATIANT cycle as presented by Mathieu (1998) achieves a net effi-
ciency of 44%. The assumed inlet conditions are 600 ◦ C at 300 bar In addition to the basic Allam cycle, Allam et al. (2014) propose
for the supercritical turbine and 1300 ◦ C for the subcritical turbines a cycle design with reheat. This bottoming part of the cycle
at 40 bar and 9.7 bar, respectively. The lowest cycle pressure is is very close to the bottoming part of the MATIANT cycle. The
atmospheric pressure. Allam et al. (2013) claim a net efficiency of working fluid is expanded from 30 bar directly to atmospheric
approx. 59% for the Allam cycle which is comparable to combined pressure. The authors report a net efficiency of 57.5% for the
cycle power plants without carbon capture. In contrast to the reheat cycle thus a slight reduction to the basic cycle. However,
OCDOPUS cycle the upper process pressure is reported to be in the the specific power output of the process increases by the factor
range of 200–400 bar and the pressure ratio of the supercritical 2.5. Additional components needed for the process are the second
turbine is between 6 and 12. An example is given with pressures combustor and turbine plus a second compressor to bring the fluid
of 300 bar and 30 bar for upper and lower pressure, respectively. back to the pressure of 30 bar. It is reported that the expansion
The turbine inlet temperature is 1150 ◦ C. A temperature–entropy- to 1 bar and the additional amount of working fluid caused by
diagram for pure CO2 in Fig. 39 shows the operating ranges of the the second combustion enable the process to operate the recu-
cycles in comparison. The values are determined with Aspen Plus perator with low temperature differences without additional
using the Peng-Robinsom/Boston-Mathias property model using heat.
data from Yantovski et al. (1993), Mathieu (1998) and Allam et al.
(2013). Influence on ASU and CPU

Heat integration
The major gain of the Allam cycle is that the properties of the
working fluid allow the integration of a significant amount of
waste heat to achieve low temperature differences at both ends of
the recuperator heat exchanger (Allam et al., 2013). The heat avail-
able for recuperation from the exhaust gas is approx. 800 kJ/kg.
Due to the non-ideality of CO2 , the heat needed to pre-heat the
In contrast to other processes the main compressor and the
booster compressor of the ASU have no or significantly less inter-
coolers and are operated mostly adiabatically. The compressed air
is then cooled by integrating the heat in the CO2 cycle. The higher
compressor duty is compensated by the higher cycle efficiency as
most of the energy is kept within the process. Allam et al. (2013)
consider that high oxygen purity of at least 99.5 vol% is necessary
because the process is assumed to operate without further gas
98 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
processing. Although the combustion pressure is higher than
200 bar the authors claim that oxygen outlet pressure of 30–80 bar
from a conventional pumped LOX ASU is sufficient. The oxygen is
mixed with a split stream from the compressor of the CO2 cycle
and then compressed separately to the combustor pressure. The
reheat process presented in Allam et al. (2014) does not need an
integration of ASU waste heat. Therefore, in this case an optimized
ASU with intercooling is used.
(b) Combustion
Allam et al. (2013) do not give more detailed information about
the combustion process. In conventional gas turbines pre-mixed
combustion is applied to reduce NOx emissions but is sensitive
to vibration issues. Therefore, a diffusion burner is proposed
where fuel and oxidizer are supplied separately. Due to the low
nitrogen concentration in the working fluid, the NOx emissions
are considered to be not as critical as in conventional plants.
Oxygen concentrations of 15-30% in the oxidizer are assumed to be
feasible. The remaining working fluid is injected after combustion
to achieve the combustor outlet temperature.
(c) Turbomachinery
The supercritical CO2 turbine has a low pressure ratio com-
pared to conventional gas turbines and steam turbines. However,
the absolute pressure is high like in advanced steam turbine. This
requires a completely new design. Allam et al. (2013) describe a
combination of steam turbine technology and gas turbine technol-
ogy. The turbine has a double shell construction as in advanced
ultra-supercritical (A-USC) steam power plants. The blades are
cooled by cold CO2 using convective cooling. Film cooling is
regarded not necessary because of the lower temperatures than
in advanced gas turbines and the high heat transfer coefficients
of CO2 . High temperature resistant forged Ni-based material has
to be used in the very high temperature sections. Ni-based parts
and alloys with lower temperature resistance are welded together
where it is feasible regarding the temperature levels.
Compared to the turbine section the compression and pumping
of supercritical CO2 is considered as technically mature as com-
parable operating conditions are achieved in EOR applications
(Wright et al., 2013; Allam et al., 2014).
(d) Additional equipment
The recuperative heat exchanger is one of the major features of
the Allam cycle. At the hot end of the heat exchanger the tempera-
ture is approx. 750 ◦ C at a high pressure difference between hot and
cold side. Wright et al. (2013) estimate that tubular heat exchangers
in this operating region will need solution strengthened or precip-
itation strengthened Ni-alloys. The heat exchanger type proposed
by Allam et al. (2013) is a plate-fin type that is already commer-
cially available in stainless steel. It can be used for the sections of
the heat exchangers with temperature levels below 550–600 ◦ C. For
higher temperatures Ni-based alloys, e.g. alloy 619, are proposed.
The production of Ni-based parts is reported to be in development.
An alternative for ultra-high-pressure heat exchangers are diffu-
sion bonded heat exchangers from plates with chemically etched
flow channels.
Because the lowest pressure in the cycle is 30 bar, the coolers
and the condenser operate at significantly higher pressures than
in the other cycles.
(e) Demonstration activities
The demonstration of the Allam cycle is realized by NET Power
LLC in cooperation with the Shaw Group, Toshiba Corporation
Fuel
Oxygen
P-116
Gas HPT IPT LPT G
generator
Cond.
H2O CO2
Fig. 40. Simplified flow sheet of the CES cycle according to Anderson et al. (2010).
and Exelon Corporation. According to Allam et al. (2013), the
project includes the construction and operation of a 50 MWth
demonstration plant as well as studies for the construction of a
commercial Allam cycle plant in the 500 MWth range. In 2013,
Toshiba Corporation (2013) confirmed the successful testing of
the newly developed combustor for the project at pressures up to
300 bar. Just recently, Toshiba Corporation (2014) announced that
they will deliver the first-of-a-kind supercritical CO2 turbine and
the combustor for the 50 MWth demonstration plant which shall
be located in Texas, USA. The equipment shall be delivered in early
2016 with commissioning of the plant expected later that year.
4.3.3. Clean energy system (CES cycle)
The water cycle or CES cycle is based on an internal combus-
tion Rankine cycle. The cycle configuration as given by Anderson
et al. (2010) is shown in Fig. 40. The gas generator, i.e. the main
combustor, burns natural gas with oxygen at high pressure. Liquid
water is injected to moderate the temperature. Due to the evapora-
tion of the water, the working fluid consists approx. 90% of steam.
The working fluid is then expanded in a steam turbine like HP tur-
bine (HPT). After the expansion to an intermediate pressure the
working fluid is reheated by an additional combustion of fuel with
oxygen. The inlet temperature of the second turbine is compara-
ble to conventional gas turbines although the working fluid is still
mainly steam. Through the IP turbine (IPT) and the LP turbine (LPT)
the steam mixture is expanded to vacuum condenser pressure. The
main difference between the proposed process schemes regards
the configuration of the low pressure part. In the presented case
the condenser separates CO2 and water at vacuum conditions. The
liquid water is then recycled to the gas generator. The water is pre-
heated by the LP turbine exhaust gas. The remaining flue gas can
be further processed to storage conditions.
Although the cycle efficiency is considered to be lower or at
most similar to other concepts at comparable conditions (Bolland
and Sæther, 1992; Kvamsdal et al., 2007; Gou et al., 2006), the most
demonstrations activities have been performed. Regarding the
maturity of the cycle Kvamsdal et al. (2006) conclude that despite
technological development is necessary, no major breakthrough is
required.
(a) Thermodynamic evaluation
The range of the efficiencies presented for the CES cycle varies
in a broad range. Early studies by Bolland and Sæther (1992) esti-
mate an efficiency of 34%; whereas the first proposal of the cycle by
Anderson et al. (1999) suggest an achievable efficiency of 56% and
67% for short term and long term development respectively. How-
ever, the ASU power is not considered as a loss but as operating cost
like the fuel and later studies reveal lower values. The parameters
of the short term option are 871 ◦ C and 82.7 bar at the HP turbine
inlet, 1427 ◦ C and 8.27 bar at the IP turbine inlet and a condenser
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 41. Sensitivity of the CES cycle to a) the turbine inlet temperature and b) the condenser pressure (Bolland et al., 2001).
pressure of 0.83 bar. However, Bolland et al. (2001) calculate an
efficiency of 52% for the short term option using the same values.
The net efficiency is 40.5% with consideration of the ASU power.
Furthermore, they estimate a maximum long term net efficiency of
50–53% if all process parameters are increased significantly above
the technology level of conventional equipment.
Starting from the values given above, Bolland et al. (2001) per-
formed a sensitivity analysis for different parameters. Fig. 41 shows
the results for the HP turbine inlet temperature and the condenser
pressure which are determined to have the highest influence on the
process efficiency. A Variation of the HP turbine inlet temperature
between 600 and 1400 ◦ C results in a change in net efficiency of
approx. 8%-pts. The condenser pressure has an influence of 9%-pts
when varied between 0.1 bar and atmospheric pressure. The pres-
sure level of the gas generator is only of minor importance as an
increase from 80 to 200 bar only results in a 3%-pts change in effi-
ciency. Anderson et al. (2008) report mainly the strong dependency
of the IP turbine inlet temperature. Tak et al. (2010) show that a
higher condenser pressure leads to a higher CO2 purity after the
condenser and lower CO2 compression power but still an overall
reduced efficiency.
Most of the later studies assume a HP steam of approx.
80–105 bar and 600–900 ◦ C. The IP inlet temperature is in the
range of 1200–1500 ◦ C and the condenser pressure between 0.05
and 0.15 bar. This results in a net efficiency between 43 and 47%
(Martinez-Frias et al., 2002; Gou et al., 2006; Kvamsdal et al., 2007;
Haines et al., 2006).
Hustad et al. (2005) present a cycle configuration within the
ZENG project that uses solely state of the art technology. The
HP and IP temperature is 565 ◦ C and 705 ◦ C for a steam turbine
and an uncooled gas turbine, respectively. As the heat transfer in
the condenser is reduced by the CO2 /steam mixture, a condenser
pressure of 0.08 is assumed to achieve a reasonable size. The ASU is
integrated by heating and expanding a split of the waste nitrogen
steam. This process reaches a net efficiency of 38%.
Advanced cycle design
Hustad et al. (2005) propose an optimized design for the appli-
cation of existing equipment as mentioned above. The HP steam
parameters are increased to 150 bar and 600 ◦ C while the main fea-
ture is a comparatively high IP outlet pressure of 3 bar at 390 ◦ C. An
HRSG generates pure steam at 1.6 bar and 356 ◦ C. This pure steam
can be expanded to a lower condenser pressure of 0.03 bar. Further-
more, the CO2 has a lower steam content and compression power
is reduced. Additionally, the ASU is much stronger integrated into
99
the process than in the base case. The optimized process reaches a
net efficiency of 45%.
Marin et al. (2003) show the efficiency gains of cycle options
with strong integration of the waste nitrogen stream of the ASU
and a second reheat combustor are around 3%-pts.
Gou et al. (2006) investigate two advanced cycle configurations
where pure HP steam is generated and expanded before the inter-
nal combustion. These processes are similar to the MATIANT flow
sheet but with water/steam as working fluid. The net efficiency
can be increased from 44% to 50%. Haines et al. (2006) propose the
application of the CES cycle in hybrid cycles. External steam from
renewable (or nuclear) sources is used instead of water as the
cooling agent. The maximum efficiency gain is 6%-pts as compared
to their reference case.
Influence on ASU/CPU
The oxygen pressure needed in this cycle has to be around
100 bar for addition into the gas generator. A second oxygen stream
is needed at the IP level for the reheat combustor. Hustad et al.
(2005) use an ASU with an outlet pressure of 30 bar for the reheat
combustor and an additional compressor to reach the gas generator
pressure. As mentioned before the integration of the waste nitro-
gen stream is possible in some configurations (Marin et al., 2003;
Hustad et al., 2005). The required oxygen purity is dependent on
the requirements regarding the CO2 purity.
The CPU of the basic cycle needs more compression energy
because the CO2 is extracted from the vacuum condenser. Due
to the low condenser pressure, the water content of approx. 40%
in the CO2 has to be reduced by intercooled compression with
condensation (Hustad et al., 2005). Alternatively, a condensation
at higher pressure reduces the effort for the CPU. Anderson et al.
(2008) propose a catalytic reaction with additional fuel to remove
any excess oxygen from the combustion.
(b) Combustion and emissions
The CES cycle needs two different types of combustors. The
first one, e.g. the gas generator, realizes the combustion of fuel
and oxygen with liquid water as the cooling agent whereas the
second combustion occurs in a steam/CO2 working fluid without
evaporation. Fig. 42 shows the schematic cross section of both
combustors. The gas generator is divided in multiple sections.
In the first section, fuel is burned with oxygen. According to
Anderson et al. (2008) the injected water in this section moderates
the temperature to 1650–1750 ◦ C. In the downstream section
100 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 42. Scheme of a) the gas generator (Smith et al., 2000) and b) the reheat combustor (Chorpening et al., 2005) of the CES cycle.
more water is injected to match the inlet temperature of the HP
turbine (600–900 ◦ C). This results in a steam rich working fluid
of approx. 90% steam and 10% CO2 by volume. The working fluid
of the reheat combustor is the expanded exhaust gas from the
gas generator. The desired outlet temperature is in the range of
1200–1400 ◦ C like in conventional gas turbine combustors. Hollis
et al. (2012) report that two injection concepts are investigated. On
the one hand the fuel can be injected into a premixed oxidizer in a
swirler like in conventional gas turbine combustors. On the other
hand there is a direct injection system with platelet technology
that directly injects several streams of oxygen and fuel resulting
in many small combustible regions. A part of the working fluid is
fed to the combustion zone for rapid cool down. Further cooling is
realized by a dilution flow.
Emissions
The emission behaviour of the CES cycle is mainly investigated
by means of the reheat combustor. However, within the demonstra-
tion activities of the gas generator emissions of 5–80 ppmv CO and
0.3–4 ppmv NOx (dry conditions, corrected to 15% O2 ) are reported
(Anderson and Bischoff, 2006).
As the reheat combustor is more comparable to a gas turbine
combustor it can be compared to a combustor with CO2 recycle.
Richards et al. (2005) calculate the equilibrium concentration of
CO in the CES cycle combustion products to be 5–7 times lower
than for CO2 moderated combustion. At 1650 K, 10 bar and ϕ = 0.98
the equilibrium concentration of 12 ppmv is reached in 4 ms. For a
CO2 recycle, 200 ppmv in 20 ms are reported as in Section 4.3.1(b).
However, the emissions of the CES cycle based on dry conditions
are by a factor of 10–12 higher due to the high steam content of the
working fluid.
Experimental results by Chorpening et al. (2005) show lower
CO emissions than the adiabatic equilibrium considerations. This is
explained with the sensitivity of the equilibrium to heat losses. The
CO emissions on dry basis stay below 100 ppmv if an equivalence
ratio of less than 0.93 is chosen. Higher equivalence ratios lead to
a sharp increase of the emissions to 400 ppmv at ϕ = 0.96. Richards
et al. (2005) also report the sharp increase at equivalence ratios
higher than 0.94 in the same combustor. However, their CO values
are significantly higher because the oxygen content in the work-
ing fluid is chosen higher. The higher temperatures lead to higher
equilibrium concentrations.
The measured NOx emissions in the experiments by Chorpening
et al. (2005) exceeded the analyser range of 20 ppmv (dry). Nitro-
gen purge flows in the apparatus are seen as the cause. Richards
et al. (2005) show values between 3 and 18 ppmv at dry conditions.
Combustion stability
The combustor as presented by Chorpening et al. (2005) was
designed for an outlet temperature of 1205 ◦ C. Adiabatically, a
steam to oxygen ratio of 8:1 is needed. The temperature is not
sufficient for stable combustion. Therefore, 20% of the total steam
are added downstream in a dilution zone. Due to water cooled
walls of the experimental apparatus, stable combustion was
achieved at lower steam to oxygen ratios of 5.6:1. No oscillations
were observed during the tests.
(c) Turbomachinery
The turbine section of the CES cycle consists of 3 turbine sections
like in a conventional steam power plant. Depending on the inlet
conditions, the HP and LP turbine are considered as a conventional
or advanced technology steam turbine. Because of the high outlet
temperature of the reheat combustor, the IP turbine is significantly
different to a steam turbine but comparable to a gas turbine with
advanced materials and cooling technology (Anderson et al., 2008).
Therefore, most of the research focusses on this part of the process.
Furthermore, the IP turbine delivers approx. 50% of the total power
of the process (Anderson et al., 2014). Anderson et al. (2008) present
three generations of the IP turbine:
The first generation uses existing equipment based on the GE
J79 gas turbine. No compressor is needed for the CES cycle thus the
existing compressor is removed and a thrust compensation system
is installed. This increases the output power of the turbine from 10
to 40 MWe . The combustor cans can be either removed or used as
reheat combustors. A turbine inlet temperature of 760 ◦ C is chosen
to avoid blade cooling. The turbine runs at the same speed as in the
air case.
The second generation is based on the Siemens SGT-900 with
turbine inlet temperatures of around 1150 ◦ C. The removal of
the compressor leads to an increased output of 150 MWe . Newly
designed reheater cans replace the combustor cans. An exit guide
vane is used to deswirl the outlet stream. As in other oxyfuel gas
turbines the temperature drop is lower than in the air case. This
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
requires a reduced inlet temperature, advanced materials, or cool-
ing of the last stage. The higher specific heat of the working fluid
causes higher power output at the same conditions as in the air case.
Lower inlet temperature or a higher rotational speed is needed to
keep the aerodynamic behaviour of the turbine.
The third generation of the CES cycle is presented with all three
turbines. The HP turbine will operate at higher temperatures than
conventional steam turbines. It is proposed to use gas turbine alloys
and coatings for these turbines. The design goal for the IP turbine
is 1760 ◦ C. This poses the most technical challenges because it is
much higher than the state-of-the-art for gas turbine conditions.
The proposed design achieves 40 bar pressure drop in 7 stages.
Advanced material and cooling technology is needed. Therefore,
special alloys and coatings have to be developed. A thrust piston is
used to overcome the rotor thrust. The same considerations as for
the HP turbine can be made for the LP turbine. Due to the high vol-
umetric flows at low pressure, a quad-flow turbine arrangement is
proposed.
Anderson et al. (2010) indicate higher corrosion rates for
CO2 /steam environments because water is hindering the forma-
tion of protective oxide scales. Uncoated alloys show a reduction
in strain life behaviour. In contrast, only minor effects are observed
on coated alloys.
(d) Additional equipment
The CES cycle does not need much additional equipment besides
the two combustors and the turbomachinery. In the basic cycle
mainly a condenser for separating the CO2 /steam mixture. A low
condenser pressure is challenging because of the higher heat trans-
fer resistance of the mixture compared to pure steam (Hustad et al.,
2005). Additionally, a preheater for the water that is injected to the
combustor is needed.
If advanced designs are used more heat exchangers can be
necessary. If a separated LP steam cycle is used the CO2 /steam
condenser serves as an HRSG at elevated pressure and a more
conventional condenser for pure steam is needed for the LP steam
cycle.
(e) Demonstration activities
CES is the leading company for development and demonstration
of the cycle in partnership with Siemens Energy, Inc. and Florida
Turbine Technology, Inc. (FTT). The demonstration activities cover
mainly the examination of the two combustors and the IP turbine.
For the reheat combustor and the turbine existing equipment is
used according to the first and second generation turbines for the
CES power plants.
The early development and demonstration activities were
focussed on the gas generator, i.e. the primary combustor. Anderson
et al. (2008) give an overview of the development starting with the
proof-of-principle on the basis of a 110 kW lab-scale gas reactor
between 1999 and 2001. Subsequently, a 20 MWth gas generator
was developed and operated at conditions from 20% part load to
full load, a temperature range from 316 to 1649 ◦ C, and pressures
from 75 to 106 bar. CES bought and refurbished the idle 5 MWe Kim-
berlina power plant near Bakersfield, CA for further testing. The gas
generator was connected to the existing turbine generator of the
plant. It was started more than 300 times and operated more than
1300 h in total. Up to 2.7 MWe have been fed to the grid during
the tests. In 2008 a 170 MWth gas generator was commissioned for
testing of the CES oxyfuel turbine equipment.
In the final report of the gas generator tests, Anderson and
Bischoff (2006) report corrosion rates due to the oxyfuel work-
ing fluid to be around 0.1 mm/a at turbine inlet conditions and
0.03 mm/a at condenser conditions for stainless steels. Carbon
101
steels showed significantly higher rates of 1.5 mm/a and 1.3 mm/a,
respectively.
Anderson et al. (2010) performed further testing regarding the
reheat burner that is used to heat the working fluid to IP turbine
inlet temperature. A modified single combustor can of the J79 gas
turbine was operated in a test rig. The modification was mainly
the addition of two oxygen injectors to the mixing dome of the
combustor can. The combustor achieved stable combustion only
under high oxygen excess. Furthermore, high CO emissions, high
core temperatures, and ignition problems led to the conclusion that
a redesign would be necessary for efficient oxyfuel combustion. In
a later study a combustor can from the second generation SGT-900
is used (Anderson et al., 2014). The combustor has an improved
oxygen injection system using a direct injector instead of air-fuel
swirler nozzles as briefly described in Section 4.3.3(b). The results
showed no combustion instabilities during the test runs. Pressure
losses and temperature uniformity were achieved below the design
goals. Ignition occurred at high working fluid to fuel ratios of 80:1,
a maximum was not determined. Regarding the use of alternative
fuels the concentration of CO2 in working fluid and fuel was var-
ied, showing sustainable combustion up to 80 vol% CO2 content.
However, it is considered that some redesigns are necessary. Par-
ticularly, the original combustor liner was damaged at high loads
due to areas of high temperature.
The testing of the IP turbine was announced in 2008 by Anderson
et al. (2008) with the first generation J79-based gas turbine with an
air-brake as power consumer. The 170 MWth gas generator deliv-
ered the working fluid. No reheat combustors were used during
the tests. According to the final report (Hollis et al., 2012) the test-
ing facility was extended by an electric generator and a 6 MWe load
bank. In 2011 no-load test with 77 starts and a total of 1 h operating
time were performed in a first phase. During the second phase, load
conditions including 4 hot starts with another hour accumulated
operating time were examined. In preparation for the second gen-
eration turbine test an extended test plan was set up with more than
3 operating hours regarding risk mitigation, i.e. simulated synching
to grid, oscillation troubleshooting and over speed control.
In 2011 CES purchased a used SGT-900 unit that was modified
for oxyfuel operation. The resulting OGT-900 turbine was tested
with the 170 MWth gas generator and was connected through the
generator to a simulated grid with load banks. Short duration tests
at low pressure and temperature have proven the controllability
of the turbine by regulation of the WF stream and the generator
excitation (Anderson et al., 2014). Further tests, e.g. IP turbine with
reheat combustors, have been set on hold indefinitely due to budget
limitations of the project.
Hustad et al. (2005) present a concept study within the ZENG
project by Lyse Energi and CO2 Norway that proposed a 40 MWe
demonstration plant be located in Risavika, Norway using only
components that were ready for commissioning. However, the
project was not realized.
4.3.4. Graz cycle
In contrast to the other cycles considered, the Graz cycle has two
recycle streams to the combustor. One of the recycle streams is pure
steam. The other recycle stream is dependent on the chosen vari-
ant of the Graz cycle. The two main configurations are compared
by Sanz et al. (2004). The first variant has a CO2 rich working fluid
because of using a pure CO2 recycle stream after condensation of the
water. The second variant has a higher steam content in the working
fluid because the recycle stream is split before condensation. The
high steam content Graz cycle, often referred to as S-Graz cycle, has
a significant higher efficiency at the same conditions (Sanz et al.,
2004; Kvamsdal et al., 2004, 2007). Therefore, this work focusses
on the latter configuration as it is shown in Fig. 43. The combustion
of fuel and oxygen takes place at 40 bar and is cooled by the two
102 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fuel
Oxygen
HPT IPT LPT G cycle. Jericha et al. (2007) report a net efficiency of 53.1% compared
Cond.
...
HRSG
H2O CO2
Fig. 43. Simplifed flow sheet of the Graz cycle according to Sanz et al. (2004).
recycle streams. The steam rich exhaust gas is expanded to approx.
atmospheric pressure in the IP turbine (IPT) and cooled in an HRSG.
Around 45% of the HRSG outlet stream are further expanded in an LP
turbine (LPT) to vacuum conditions where the water is condensed.
The resulting CO2 rich flue gas can be processed to storage condi-
tions. The water is used as feed water for the HRSG. To close the
mass balance, the water from the combustion is removed from the
process. The steam from the HRSG is expanded in a conventional
HP steam turbine (HPT) to the combustor pressure and then used
for cooling purposes. The remaining 55% of the working fluid that
do not pass the LP turbine are compressed with intercooling and
recycled to the combustion chamber.
Kvamsdal et al. (2006) consider the two recycle streams to
cause higher operational challenges than for the other cycles.
The combustor technology requires a technological breakthrough
whereas the turbines are comparably mature except for the high
temperature turbine.
(a) Thermodynamic evaluation
The net efficiency of the presented Graz cycle is calculated to be
several percentage points higher than the SCOC-CC and the water
cycle by several authors (Kvamsdal et al., 2007; Sanz et al., 2008;
Thorbergsson et al., 2012). The presented overall net efficiency of
the cycle is in the range of 48.7–52.6%. The cycle parameters do
not vary much in the different studies. In general a HP steam pres-
sure of 180 bar, a combustor pressure of 40 bar and a condenser
pressure of approx. 0.05 bar is assumed. The HP steam temper-
ature is approx. 550 ◦ C and the combustor outlet temperature is
1400 ◦ C. The variations in net efficiency are mainly due to different
assumptions for the energy consumption of the O2 supply and CO2
processing. Bolland et al. (2001) show that the influence of the con-
denser pressure is very significant as in the CES cycle. At condenser
pressures below 0.1 bar there is an optimum due to the necessary
compression of the CO2 (Sanz et al., 2005).
The higher efficiency compared to the CO2 rich Graz cycle is
explained by Sanz et al. (2004) with the fact that most of the
vaporization heat is kept in the cycle and not rejected in the
condenser. A further advantage is a lower achievable condenser
pressure. Despite the higher compression duty for the recycle
stream this results in an efficiency gain of approx. 3%-pts.
HRSG
Sanz et al. (2005) evaluate the effect of different HRSG config-
urations. The cycle is basically considered with a single pressure
HRSG. The results show that a double pressure HRSG leads to a
slightly reduced efficiency. If a natural circulation HRSG is used
the steam pressure is limited. This results in a loss of 0.6%-pts.
Advanced cycle designs
One improvement of the cycle approaches the LP section sim-
ilar to the CES cycle. It avoids the vacuum condensation of the
CO2 /steam mixture. The condensation takes place at higher pres-
sure and the heat is used for a pure steam cycle. To achieve a positive
effect on the efficiency the atmospheric CO2 /steam mixture is com-
pressed to approx. 2 bar. The heat of compression is used in the LP
to 52.6% in their base case.
An intercooled CO2 compression to pipeline pressure can be
integrated for feed water preheating. According to Sanz et al. (2005)
the efficiency gain would be around 0.8%-pts. This configuration
leads to a significant increase of complexity.
Jericha et al. (2008) present an advanced 600 MWe cycle with
increased pressure ratio of 50 and combustor outlet temperature
of 1500 ◦ C with a net efficiency of 54.4%. Sanz et al. (2010) present
an IGCC Graz cycle claiming 45% net efficiency compared to 39% for
a pre-combustion plant.
On the basis of the Kimberlina demonstration plant for the
CES cycle, Sanz et al. (2011) propose a Graz cycle for near term
deployment based on the GE J79 gas turbine. It has no HP and LP
turbines and just one recycle compressor. The calculated efficiency
is 25.4% for the first generation Graz cycle compared to 22.2% for
the first generation CES cycle.
Influence on ASU/GPU
The oxygen pressure needed for the combustion is comparable
to the SCOC-CC. Therefore, a similar ASU can be assumed. Again
the O2 purity has to be matched to the requirements concerning
the CO2 purity. The influence on the GPU is similar to the CES cycle
because of the low condenser pressure.
(b) Combustion
Jericha and Göttlich (2002) propose a combustor design for
the Graz cycle. This design was proposed for the CO2 -based Graz
cycle but Jericha et al. (2007) still use the same combustor design
in the cycle with high steam content. It consists of an annular
combustion chamber with 6 burner arrangements in rotational
direction. Each burner arrangement consists of 4 burners. A direct
injection of fuel and oxygen creates a central combustion zone.
A steam vortex is wrapped around the combustion zone for
rapid cooling. The remaining cooling medium, i.e. pure CO2 or
steam/CO2 , is injected in the annulus and mixed in the rotational
flow. Additionally, Sanz et al. (2005) refer to the combustion
study by Chorpening et al. (2005) as described in Section 4.3.3(b),
because of the similarity of the CES reheat burner to the Graz cycle
combustor.
(c) Turbomachinery
The Graz cycle needs complex arrangement of turbomachinery
due to the number of compressions and expansions of different flu-
ids. Jericha et al. (2007) propose a two shaft design for a 400 MWe
plant (see Fig. 44). The intercooled compressor for the recycle
stream (C1 and C2) is driven by the first 2 stages of the high temper-
ature turbine (HTT) and runs at a high speed shaft with 8500 rpm.
C1 needs special care due to the high speed of the first blade but
can be completely uncooled. The first 7 axial stages can be built
from ferritic steel. A Ni-based radial stage is used as last stage to
the intercooler. C2 and the HTT are cooled by steam. The power
generating part of the HTT has 5 stages and is directly coupled to
the generator speed of 3000 rpm. Steam is used for cooling and also
for thrust compensation. The 4-flow LP turbine is coupled on the
other side of the generator.
The high pressure steam turbine is not shown in Fig. 44. It is
considered as a standard high-speed back-pressure turbine with
approx. 50 MWe that is available on the market. It can be coupled
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 44. Turbomachinery layout for 400 MWe Graz cycle (Jericha et al., 2007).
with a gear to the LP turbine shaft or a separate generator. The CO2
compressors are driven by external motors.
Woollatt and Franco (2009) show an alternative design for C1
and the HTT. The high speed shaft runs only at 5200 rpm and with a
solely axial compressor. While the turbine section is similar to the
design by Jericha et al. (2007) as mentioned above, the compressor
consists of 14 stages instead of 8.
The 600 MWe design as proposed by Jericha et al. (2008) has an
additional geared compressor stage C0 upstream of compressor C1.
Apart from that the configuration remains the same.
A more complex approach is used for a smaller Graz cycle plant
with 100 MWe output presented by Sanz et al. (2004). In contrast to
the higher output plant an arrangement with 3 speed levels is used.
All turbomachines of the cycle are included in the arrangement.
The design is considered as feasible because gears are available
in this output range. Thorbergsson et al. (2012) propose a similar
configuration and estimate that a single shaft design would lead to
approx. 36 stages.
(d) Additional equipment
For the Graz cycle several additional heat exchangers are neces-
sary. The HRSG is similar to conventional applications regarding
the pressure and temperature levels. Only one pressure level is
required thus the complexity is rather low. The compression of the
recycle stream requires additional intercooling equipment.
The considerations concerning the condenser are comparable to
the CES cycle. The proposed layout for the intercooled compression
of the CO2 with separate LP steam cycle requires two condenser
parts.
4.3.5. Alternative oxyfuel combustion cycles for gas turbines
The oxyfuel combustion cycles considered up to now are always
based on an external ASU which is mostly assumed to be cryogenic.
Fuel and oxygen are combusted within the cycle and the exhaust
gas is expanded through a turbine. However, some concepts exist
where the air separation is included in the gas turbine cycle. In these
cases alternative air separation methods are applied that operate at
the high pressure level of the gas turbine cycle. These cycles include
membrane and/or advanced reactor technology and are considered
to have a high degree of immature technology (Kvamsdal et al.,
2006). Therefore, only a brief overview will be given here.
Many of the alternative concepts are based on oxygen conduct-
ing membrane technology at high temperature, i.e. ion transfer
membranes (ITM) or mixed conductive membranes (MCM). The
conductivity of these membranes is based on oxygen ions that are
transferred with a difference in partial pressure. Habib et al. (2013)
give a review on ITM technology for oxyfuel gas turbine applica-
tions.
103
The ZEITMOP cycle as shown by Yantovski et al. (2006) is an
example for an integrated membrane based air separation. In this
case compressed air is fed to an ITM where oxygen is separated.
The oxygen is then used for burning fuel in a combustion chamber.
The exhaust gas is used in a cycle similar to the MATIANT cycle
concept. The oxygen depleted air is expanded in a separate turbine.
Considering this turbine and the air compressor there is no positive
power output generated. The power is produced by the exhaust
gas cycle thus the ZEITMOP cycle is an example for an integrated
membrane based ASU. However, the air separation remains divided
from the power generation process. Yantovski et al. (2006) show a
maximum cycle efficiency of 46%.
In the Advanced Zero Emissions Plant (AZEP), a membrane
based reactor substitutes the combustion chamber of an air blown
gas turbine. Among others, the process is described by Sundkvist
et al. (2004) where air is compressed to approx. 18 bar and
enters the reactor. In the reactor the air is first preheated to
around 800–900 ◦ C. At this temperature the ion transfer mem-
brane becomes active. During the oxygen depletion the air is further
heated to approx. 1200 ◦ C. The hot oxygen depleted air is then
expanded through a power generating turbine and an HRSG. The
actual oxyfuel combustion takes place at the permeate side of the
membrane. The hot CO2 /steam exhaust gas can either be used in
the HRSG or a separate turbine. Afterwards the stream is separated
into CO2 and water in a condenser. The allowable turbine inlet tem-
perature is higher than the limitation of the MCM reactor outlet
temperature. An additional combustor leads to a higher process
efficiency but at the cost of some CO2 emissions if fossil fuel is
used. The efficiency of the cycle for the 400 MWe range is approx.
50% and 53% without or with additional combustion, respectively
(Sundkvist et al., 2004).
A similar approach is used in the SOFC/GT process. Instead of the
MCM reactor a solid oxide fuel cell (SOFC) is integrated into the gas
turbine process. As the CO2 /water exhaust gas from the SOFC still
contains some amount of fuel, CO2 capture for this process requires
an afterburner. According to Maurstad et al. (2005). The best option
is a second SOFC at a low or negative operating voltage. The
efficiency of the process could reach 67%. Due to the SOFC, the appli-
cation is limited to small scale applications up to approx. 20 MWe .
5. Technology status and TRL
5.1. Current status of development for oxy-PC and oxy-CFB
Fig. 45 presents the historical progression in the development
of oxyfuel combustion for coal fired power plants.
Over the past 10 years, there are many success stories in the
implementation of integrated large scale pilot plants and testing of
various components and operational considerations. These include:
104 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 45. Historical progression of oxyfuel combustion technology from small pilot scale facilities to projects at demonstration scale.
• Vattenfall’s Schwarze Pumpe Pilot Plant (30 MWth ) which suc-
cessfully completed testing various components (from boiler to
CPU) of oxyfuel combustion (Burchhardt, 2009; Burchhardt et al.,
2013). This is now being decommissioned.
• Total’s Lacq Pilot Project (30 MWth ) which successfully retrofitted
a gas fired steam generation plant and has achieved storing nearly
51,000 tonnes of CO2 in a depleted gas reservoir (Copin, 2013).
This is now being decommissioned with post-CO2 storage MMV
still on-going.
• CIUDEN’s Technology Development Platform which consists of
30 MWth oxy-CFB and 20 MWth oxy-PC facilities. The test made
in the 30 MWth oxy-CFB facilities enables the validation of the
design for the Compostilla’s OxyCFB300 Project (Otero, 2013).
Currently, testing is still on-going implemented through various
EC funded projects.
• HUST’s 35 MWth pilot plant facility is now being commissioned
(Zheng, 2013, 2014). This envisioned the demonstration of oxy-
fuel boilers with results from this facility feeding into the design
validation of the Shenmu Project.
Next step towards commercialization is to demonstrate this
technology at utility scale. A number of demonstration projects for
oxyfuel combustion have been progressed. Nowadays, we have one
success story to tell in the form of a “mini-demonstration” of the
technology (i.e. Callide Oxyfuel Project in Australia) and currently
one active large scale demonstration project (i.e. White Rose Project
in Europe) remaining at this scale. Other projects have been put on
hold for various reasons or are still at its early stage of planning.
The status (as of June 2015) to the different large scale demon-
stration projects are summarized below:
• Development status in North America:
◦ FutureGen 2.0 (Humphreys, 2013) was a re-powering project
based on oxyfuel combustion technology (announced in 2009).
This project is led by FutureGen Industry Alliance in collabora-
tion with B&W and Air Liquide (as technology providers). The
project reached an advance stage of development. They have
successfully obtain all the necessary permits, completed the
FEED and undertaken various site preparation activities (for the
power plant, and CO2 transport and storage). FID is expected
by early 2015. However, this project is now put on-hold after
the US DOE suspended all its major activities starting February
2015.
◦ Shand-2 Clean Coal Project (300 MWe PC – announced in 2007)
(Stobbs, 2007) led by Saskspower (Canada) was put on hold (in
2008) due to the projected cost and concern for the amount of
CO2 produced might be more than what the oil industry could
use.
◦ Various projects based in the USA that did not progress and
put on hold (in 2009) due to not receiving the funding from
the US DOE Clean Coal Power Initiative. These include: B&W
(McCauley, 2009) led project for Black Hills Corp. (100 MWe PC)
in Wyoming; Praxair/Foster Wheeler led projects for Holland
Board Public Utilities (78 MWe CFB) in Michigan (Shah et al.,
2009) and for Jamestown Board of Public Utilities (50 MWe CFB)
in the state of New York (Bonaquist et al., 2008).
• Development status in Europe
◦ White Rose Project (Hackett, 2014) is the only remaining
large scale demonstration project and if realized could be the
world’s largest supercritical oxyfuel combustion power plant
at 426 MWe (gross). The UK CCS Demonstration Programme
has awarded the consortium whose members consists of Drax
Power, Alstom, Linde and National Grid to proceed with the
FEED activities. FID is expected after completion of FEED by
late 2015 or early 2016.
◦ Janschwalde Project (announced in 2008), led by Vatten-
fall (Stromberg, 2011) is aimed to demonstrate the world’s
first 250 MWe supercritical oxy-PC boiler firing lignite. It has
received EEPR grant from the European Commission and
submitted application to the 1st round of NER300 funding com-
petition. The project reached advance stage of development (i.e.
completion of FEED and RFP from various equipment suppliers).
Unfortunately, this project was put on hold (in 2011) due to the
lack of clarity to the CCS regulations in Germany.
◦ Compostilla OxyCFB300 Project (Martinez-Jubitero and
Gutierrez-Cerezales, 2013) led by Endesa, CIUDEN and Foster
Wheeler (now Amec FW) is aimed to showcase the world’s
first 300 MWe Oxy-CFB. It received the EEPR grant from the
European Commission to undertake the FEED and the demon-
stration of the oxy-CFB technology at CIUDEN Technology
Development Platform. However due to regulatory instabil-
ity and adverse economic environment, the project did not
proceed to Phase II and was put on hold (in 2013).
◦ Other oxyfuel projects that only reach the feasibility study
or early stage of planning include the Mori-Pori Power Plant
Project (Kiyama et al., 2011) led by Fortum and TVO (Finland)
which involves the retrofitting of 565 MWe pulverized coal
fired power plant with oxyfuel combustion; and ENEL’s planned
demonstration of 350 MWe pressurized oxyfuel combustion
technology (Benelli et al., 2014).
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Table 5
Assessing the technology readiness level of oxyfuel combustion for coal fired power plants with CCS.
TRL TRL phase name for R&D initiatives Phase for facility development
9 Full-scale commercial deployment Commercial
8 Sub-scale commercial demonstration plant Demonstration
7 Pilot Plant Industrial Scale Pilot
6 Component prototype demonstration Industrial Scale Pilot
5 Component prototype development Industrial Scale Pilot
4 Laboratory component testing Bench
3 Analytical ‘proof of concept’ Bench
2 Application formulation Bench
1 Basic principles observed Bench
• Development status in Asia and Australia
◦ Callide Project (Australia) (Spero, 2011) is currently the
largest operating oxyfuel combustion power plant producing
a nominal 30 MWe (PC) and could be classified as “mini-
demonstration” of the technology. The project involves the
retrofitting of the boiler with oxyfuel combustion and ∼12% of
its flue gas being fed into the CPU. The project has achieved an
important milestone of reaching nearly 11,000 operating before
being decommissioned (by March 2015).
◦ Youngdong Project (South Korea), led by KEPRI (Kim et al., 2011)
is aimed to retrofit a 100 MWe PC power plant involving the
conversion of downshot boiler to wall fired boiler firing Indone-
sian coal. FEED study has been completed. However, due to
regulatory uncertainty and funding concern, this has now been
put on hold.
◦ In China (Zheng, 2013, 2014), currently announced projects
include the 200 MWe (PC) Guohua’s Shenmu Project (Shanxi
Province) where FEED study is being progressed; whilst
350 MWe (PC Cogen) Datang’s Daqing Project in Heilongjiang
Province and the 350 MWe (PC) SIEG Project in Shanxi Province
completed their feasibility studies, but have not progressed to
the next implementation phase.
5.1.1. Technology readiness level
The status of oxyfuel technology for coal fired power plant can be
assessed by using the “Technology Readiness Levels” (TRL) system
which is shown in Table 5. This system was developed by NASA and
recently adopted by the Electric Power Research Institute (EPRI) to
compare the different CCS technologies.
The TRL’s, as defined in Table 5, provides a ranking from 1 (bench
scale basic principles) to 9 (commercial deployment).
From Fig. 45, the majority of the oxyfuel projects before 2005
(i.e. below ∼5 MWe in scale) are considered to be of TRL-5 or lower,
effectively testing each component separately. Projects prior to
2005 have focused mainly on assessing the combustion perfor-
mance.
On the other hand, large scale burner testing undertaken by var-
ious OEMs such as B&W’s (30 MWth ) CEDF test rig at Ohio, Doosan
Babcock (40 MWth ) “Oxy-Coal UK” test rig at Renfrew, Alstom’s
(15 MWth ) BSF test rig at Connecticut – have achieved TRL-5/6; as
these facilities normally are considered as “partially integrated sys-
tem” (i.e. including testing of boiler, flue gas cleaning and oxygen
delivery system).
Large scale pilot plant projects such as Vattenfall’s Schwarze
Pumpe, Total’s Lacq Pilot Project and CIUDEN’s oxy-CFB Pilot rep-
resent an achievement to TRL-6, whereby all components (boiler,
flue gas cleaning, ASU, CPU) are tested as an integrated system.
Callide Oxyfuel Project is considered a large scale pilot plant and
represents the next achievement to TRL-7 demonstrating the use
of oxyfuel technology with electricity generation.
Any future large scale demonstration projects that could be
realized such as the White Rose Project would represent an achieve-
ment of TRL-8, whereby the technology would be proven at a scale
105
Oxyfuel projects
White Rose Project
Callide Oxyfuel Project
Schwarze Pumpe Pilot Plant, Lacq Pilot Plant, CIUDEN’s TDP Pilot Plants
Various large scale burner test facilities(i.e. B&W, Alstom, Doosan Babcock)
equivalent to commercial deployment, though yet to be economi-
cally viable.
At present, oxyfuel combustion technology for coal fired power
plant still aspires to achieve TRL-8 level of technology readiness
within 2016-2020.
5.2. Current status of development and TRL of oxy-GT
The application of oxyfuel combustion technology to a gas tur-
bine is considered more complex than the development of oxyfuel
combustion for coal fired power plants. In gas turbines, the oxi-
dizing medium and the exhaust gases pass through its own power
cycle – a Joule or Brayton cycle. This involves the compression and
expansion in turbomachines as well as the oxyfuel combustion at
elevated pressure.
In the literature, there are several cycles proposed or under
development. However, only the CES Water Cycle and Allam Cycle
have achieved Technology Readiness Level of TRL-5 or 6.
As of June 2015, the status of development could be summa-
rized:
• Clean Energy System (CES) Cycle – having demonstrated the main
components of the gas turbine technology from a nominal scale
equivalent to 12 to 220 MWe (in California, USA). This represents
an achievement of TRL-5/6.
• Allam Cycle – Development of this technology is led by Net
Power. The construction of 25 MWe prototypes is on-going (in
Texas, USA). This technology could achieve a TRL-5 once start
up, commissioning and demonstration has been successfully real-
ized.
6. Lessons learned – large scale pilot and demo projects
Fig. 46 presents the roadmap and the current status of develop-
ment for Oxy-PC and Oxy-CFB. It is clearly indicated that to be able
to commercialize this technology by 2020, a full scale oxyfuel com-
bustion power plant should be deployed between 2016 and 2020.
This chapter presents some of the achievements and key learnings
during the operation of the different large scale oxyfuel combustion
pilot plants worldwide.
6.1. Vattenfall’s Schwarze Pumpe Pilot Plant (Germany)
6.1.1. Facility description
Vattenfall’s 30 MWth oxyfuel pilot plant has provided the most
extensive information on oxyfuel combustion at semi-commercial
scale. It is situated next to the Schwarze Pumpe Power Plant in
Brandenburg, Germany. It has achieved around 18,000 of operating
hours with more than 13,000 h in oxyfuel combustion mode.
The facility (Burchhardt and Griebe, 2013; Burchhardt et al.,
2013; Stromberg et al., 2009) is designed for flexible operation
suited to test the different components of oxyfuel combustion
technology and its integration to the ASU and the CPU. Fig. 47 shows
the overall process of the pilot plant.
106 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125

Fig. 46. Technology roadmap of oxyfuel combustion for coal fired power plant with CO2 capture.
(Adapted from Santos, 2014).

Fig. 47. Block flow diagram of Vattenfall’s Schwarze Pumpe Pilot Plant (Stromberg, 2009).
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
The pilot plant consists of a hopper from which the pre-dried
lignite or coal (pulverized) is fed. The steam generator is a natural
circulation boiler with a single top-mounted 30 MWth pulverized
fuel (PF) burner. This includes the evaporators, two superheaters
(SHE), five economizers (ECO) and a gas heat exchanger (GHE) – as
shown in Fig. 47. The furnace/boiler is equipped with the possibility
for direct injection of sorbent for in-furnace SOx removal, and a by-
pass duct for the possibility for ammonia injection in the SCR for
NOx removal (it should be noted that the SCR was not evaluated
during its operation).
The flue gas processing units consist of an ESP that removes
the fly ash from the flue gas (operating at 170 ◦ C), the flue gas
desulphurization (FGD) based on a wet scrubber using limestone
as sorbent, and a flue gas condenser (FGC) that cools the flue gases
to about 30 ◦ C and condense out the water before being fed into the
CO2 processing unit (CPU) or the CO2 compression and liquefaction
plant. The capacity of the FGD is designed to accommodate the flue
gas during oxyfuel combustion (but not design to handle the entire
flue gas flow during air firing).
The primary recycled flue gas delivers the coal from the hopper
to the burner. This is taken after the FGC; preheated up to 80 ◦ C
with humidity ranging between 4 and 30% and SOx content of 20
and 300 mg/Nm3 .
The secondary recycled flue gas is taken after the ESP. This is
preheated from 170 to 250 ◦ C in the GHE. The oxygen is mixed with
the flue gas directly (i.e. pre-mixed mode), or could be introduced
via the individual registry of the burner (i.e. expert mode), or a
combination of both (hybrid mode) – as shown in Fig. 4.
It is important to note that warm/hot recycled flue gas used as
secondary RFG has about 28-30% humidity and SOx content in the
range of 7000–11,000 mg/Nm3 . Vattenfall (Faber et al., 2011) noted
that by using warm/hot recycled flue gas should improve the overall
efficiency; and after more than 10,000 h of operation, all the heated
surface within the furnace were inspected and indicating there is
no significant impact due to corrosion even these boiler tubes are
subjected to very high concentration of SOx .
The ASU is a standard GOX 6000 plant which produces the
required gaseous oxygen (GOX) on-line with a purity of 99.5%. A
backup system in the form of a LOX-tank and an evaporator has
been installed. This arrangement enables increased load changes
up to 10%/min.
The CO2 liquefaction plant is designed to produce a liquid CO2
product having 99+% purity suitable for truck transport. The target
recovery is design to exceed 90%. The raw flue gas from the FGC
Fig. 49. Comparison of burner’s operating envelope with varying operating mode (Burchhardt et al., 2013).
107
Fig. 48. Picture illustrating the flames of the Doosan Babcock OxyCoalTM burner
during start-up operation (Sturgeon et al., 2013).
enters the CO2 plant at a design concentration of 77% CO2 (wet)
and ∼30 ◦ C. (Note: CO2 plant is capable of handling a raw flue gas
having a CO2 composition in the range of 50-90% CO2 .)
6.1.2. Lessons learned
(a) Burner and boiler operation
Schwarze Pumpe Pilot Plant (Burchhardt and Griebe, 2013) has
successfully tested 5 different burners during its operation from
2008 to 2014. This consists of 2 burners from Alstom, 1 burner from
Hitachi Power, 1 burner from Doosan Babcock and 1 burner from
Bobcock Borsig Service (BBS). These burners are shown in Table 2.
The development programme led by Vattenfall succeeded in
demonstrating the different burners’ performance with regard to
its combustion stability and flexibility – i.e. start up, turn down, and
shut down. Fig. 48 demonstrates the capability of burners to start
up from air firing mode and switch to oxyfuel combustion mode.
A key component of the different test undertaken is to develop
the parameters for burner controls. One of the primary objectives is
to understand the burner operating envelope. In particular, it could
be demonstrated that by using the expert or hybrid mode, the con-
trol of oxygen injection through individual burner registry allows
the burner to achieve the minimum possible excess O2 in the flue
gas and at same time maintaining burner performance and good
combustion quality (an example of these results demonstrating
how burners are evaluated is shown in Fig. 49).
One of the key parameters in the operation of the boiler is
the control of the heat transfer profile during oxyfuel combustion.
Fig. 50 demonstrated that the heat transfer profile during oxyfuel
combustion could be similar to the heat transfer profile during air
firing.
Also demonstrated are the performance of the different burners
with respect to NOx , CO and carbon-in-ash. All the burners tested
108 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 50. Boiler’s heat balance at 93% load – vattenfall’s schwarze pumpe pilot plant (Burchhardt et al., 2013).
Fig. 51. NOx and CO profile of Alstom Burner at vattenfall’s schwarze pumpe pilot
plant (Kluger et al., 2011).
at Schwarze Pumpe has succeeded in achieving emissions perfor-
mance required in terms of NOx and CO (as illustrated in Fig. 51).
(b) Flue gas processing units
The performance of a full-scale ESP was evaluated at the Vat-
tenfall oxyfuel pilot plant in Schwarze Pumpe. These are reported
in various papers (Bäck et al., 2011; Porle et al., 2012). During oxy-
fuel combustion, the ESP operation was smoother and showed a
∼50% higher level of voltage, i.e. ∼65 kV, when compared to the ESP
operation during air firing. The variability of both current and volt-
age was significantly lower than for air firing. No back corona was
observed. These were attributed to higher moisture content in the
flue gas. Measurements taken downstream of the ESP assessing the
particle size distribution, ash resistivity and gravimetric analysis
were reported to be similar to both operating mode. Performance
of the ESP when operating in oxyfuel combustion mode have
reached a dust collection efficiency of >99.9% – which is also sim-
ilar to the performance of the ESP when operating in air firing
mode.
The FGD (Faber et al., 2011; Schmidt and Karl, 2010) installed at
the pilot plant is based on limestone forced oxidation wet scrub-
ber process using tray absorber technology. The main task involves
the removal of SO2 , SO3 , HCl, HF, any residual dust and other
trace elements in the flue gas. Operation of the FGD during oxy-
fuel combustion requires a nitrogen free, CO2 enriched flue gas.
The dilution of the flue gas should be minimized, thus the forced
oxidation tank converting any remaining CaSO3 to CaSO4 is sepa-
rate from the main FGD column. SOx removal has been reported
to achieve greater than 99.5% with a very high inlet SOx con-
centration (∼7000–11,000 mg/Nm3 ). It was also reported that a
guaranteed removal of >98% for HCl and HF; at least 50% removal
of Hg; and at least 75% removal of SO3 have been achieved during
operation.
The FGC (Yan et al., 2009, 2013; Faber et al., 2011) at the
Schwarze Pumpe Pilot Plant consists of a 2 stage direct contact
coolers based on liquid spray technology with alkali wash. The
main purpose is to cool the flue gas and remove most of its mois-
ture prior to its delivery to the CPU. The use of alkali wash provides
a polishing step for SOx and other acidic components removal.
Based on the experience from Vattenfall’s Schwarze Pumpe Pilot
Plant (i.e. where FGD is used upstream), the SO2 concentration
entering the FGC is small and the removal efficiency was observed
to be between 94 and 98% at pH between 6 and 7 (Yan et al., 2009,
2013).
(c) CO2 processing unit
CO2 liquefaction plant within Vattenfall’s Schwarze Pumpe Pilot
has demonstrated the capability for high CO2 recovery and to pro-
duce high purity CO2 .
The main CO2 processing unit at Vattenfall Schwarze Pilot Plant
consists of external refrigeration package using NH4 as refrigerant,
mercury adsorbent (activated carbon bed), a screw compressor,
molecular sieve, BAHX, CO2 recycle compressor, and a rectifica-
tion/stripper column. The liquefaction plant has achieved greater
than 90% recovery. The liquid CO2 produced is at 15 bar with purity
of greater than 99.9+% (Ritter, 2011).
In addition to the main CO2 liquefaction plant, 2 other technolo-
gies primarily evaluating the NOx and SOx removal in the flue gas
are tested. This includes Linde’s LICONOX process and Air Product’s
Sour Compression Process. These technologies are described in var-
ious papers and conference proceedings (Ritter et al., 2013; White
et al., 2013).
6.2. Total’s Lacq Pilot Plant (France)
6.2.1. Facility description
Total’s 30 MWth gas fired oxyfuel pilot plant has provided a
wealth of experience and information to the integration of CO2
capture, transport and storage. This is the first large scale facility
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 52. Block flow diagram of Total’s Lacq Pilot Plant (Copin, 2013).
worldwide that is dedicated to capture CO2 from oxyfuel com-
bustion plant and store in a depleted gas field (i.e. complete CCS
integration).
The CO2 capture facility (as shown in Fig. 52) consists of
the steam generation plant, a small standard ASU delivering
240 tonnes/h of O2 with purity ranging from 95 to 99.5%, flue gas
condenser to cool the flue gas down to 30 ◦ C, and the CO2 processing
unit (consisting of the CO2 compressor and dehydration unit).
The steam generation plant and its associated CO2 capture facil-
ities (i.e. ASU and CPU) are situated in Lacq, southwest of France.
Gaseous CO2 is transported via 27 km pipeline at a pressure of
∼27 bar; and injected into a depleted gas field situated in Rousse at
pressure of ∼50 bar.
Lacq Project has achieved more than 11,000 operating hours and
succeeded in transporting and storing of ∼51,000 tonnes of CO2 .
The project ceased to operate in March 2013. Post-monitoring of
the storage site is currently on-going.
The project is based on the retrofit of a gas fired steam gen-
erator/boiler producing ∼40 tonnes/h of steam (at 60 bar and
420-450 ◦ C). The boiler was built in 1957 and was revamped by
Alstom to be retrofitted with oxyfuel combustion using 4 × 8 MWth
low NOx burners (as shown in Fig. 5) provided by Air Liquide
(Marcano et al., 2011; Pham et al., 2012; Copin, 2013). Perfor-
mance testing of the boiler was undertaken by Total, Air Liquide
and B&W (Pham et al., 2012). The boiler is operated at slightly
above pressure (i.e. 550 Pa/0.08 psi) to minimize any air ingress.
The flue gas condenser consists of a venturi scrubber cooling the
flue gas (mainly consists of ∼45% H2 O and ∼45% CO2 ) from 200 ◦ C
to 90 ◦ C and then quenched in a water spray tower cooling further
the flue gas down to 30 ◦ C before being fed to the CO2 compressor.
The CO2 compressor is a 3 stage reciprocating compressor suit-
able for wet and sour service. Flue gas from the flue gas condenser
is mixed with a recycled product CO2 from the dehydration unit
to reduce dryness of the feed gas of the compressor thus preven-
ting any corrosion due to HNO3 . The dehydration unit consists of
109
standard TSA/molecular sieve. Dry nitrogen from the ASU is used
for the regeneration of the molecular sieve.
The gaseous CO2 is delivered to the pipeline nearly bone dry (i.e.
<10 ppm H2 O) with a purity between 91 and 93%. Other non-CO2
components included in the product CO2 are O2 (5-7%), N2 (1-3%),
Ar (0.5-1%), CO (<10 ppm) and NOx (mostly NO2 at ppm level).
The pipeline is an existing carbon steel NG pipeline (Ø
8 in./12 in.) reconditioned to CO2 pipeline. No corrosion issue expe-
rienced due to the dryness of the product CO2 .
The storage site consists of a CO2 booster compressor (com-
pressing the gas to 50 bar) and a single injection well (Rousse 1).
The CO2 storage reservoir is a depleted gas field with a depth of
4500 m with 3% porosity.
6.2.2. Lessons learned
In general, the objectives of the project were successfully
attained:
• Proven the technical feasibility of an integrated CO2 capture-
transport-geological storage chain
• Testing and validating oxyfuel combustion facility based on a
30 MWth steam generator/boiler
• Collecting the data needed to design the boiler for future scale up
(200 MWth )
• Developing a method for characterizing the storage reservoir
• Defining a method for monitoring the integrity and environmen-
tal impact of a CO2 storage site
• Developing research programmes with the academic community.
(a) Burners and boiler operation
The Lacq’s steam generator (Marcano et al., 2011; Pham et al.,
2012) has successfully tested the performance of 4 burners in 2 × 2
front wall arrangements. It has succeeded in operating the burners
within the required parameters for:
110 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125

Table 6 • Recycling of a proportion of the dry product CO2 into the com-
Steam generator/boiler performance at 35t/h load Total’s Lacq Project (Pham et al.,
pressor feed.
2012).

Air combustion Oxyfuel The original target for the dehydration unit is set to achieve
combustion
50 ppm H2 O. However, the TSA/molecular sieve installed has been
Excess O2 (%v – wet basis) 2.60 2.60 operating at less than 10 ppm without any issue (Lockwood et al.,
Excess air equivalent (%) 3.98 3.98 2014).
Flue gas from combustion as by-products 37,650 9,957
(kg/h) (d) Other key learnings – CO2 storage and public engagements
Recycled flue gas (kg/h) – 27,693
Flue gas recycle ratio – 2.78 Environmental monitoring
Flue gas leaving the economiser (◦ C) 194 204
Boiler efficiency (%HHV basis) 82.62 87.37
Heat transfer profile During the project, the monitoring of key indicators such as
Furnace absorption 47.90 47.31
Superheater absorption 16.06 16.16 • soil gas – measurements of CO2 , CH4 , C isotopes and inert gas
Economiser absorption 5.30 5.90
Furnace screen + boiler bank absorption 30.74 30.63 during winter and summer;
• chemical and mineral content of perched aquifer;
Note: For the heat transfer profile – the absorption is referred to the “%” of total
• pH, conductivity, and carbonate and bi-carbonates content of
boiler absorption excluding heat losses
shallow and deep saline aquifers;
• standard bio-indicators of surface water (i.e. nearby rivers) and
• Start up (in air mode), turn down (in oxyfuel mode) and shut its chemical and mineral content; and
down (in air and oxyfuel mode) • annual inventory of fauna and flora
• Burner controls – recycled flue gas and oxygen
• Heat transfer profile were taken to cover a full suite of environmental monitoring of
• Emissions (CO and NOx ). the geosphere (0–80 m below the surface of the Earth), biosphere
(0–10 m above the surface) and atmosphere (0–2000 m above the
The performance of the boiler during air and oxyfuel combustion surface of the Earth) in order to establish background information
mode could be summarized in Table 6. and develop surveillance tools.
NOx emissions from the boiler was reported at around 500 ppmv During the operation of the project, it was reported that environ-
@ 3% O2 in the flue gas (dry basis)/∼0.055 kg/MWh at full load. mental data collected have no deviation to the baseline information
It should be noted that most of the NOx are formed from the N2 gather prior to the start of operation [2009]; no CO2 leaks were
(∼0.4%) in the NG since air ingress is minimal (i.e. boiler is operated detected and changes to the background CO2 concentration moni-
slightly above pressure) and O2 delivered to the boiler is at 99.5% tored were consistent with climate variations (heat, humidity, etc.).
purity (i.e. nitrogen free O2 ). CO is generally controlled to less than It was concluded that CO2 storage in the depleted gas field at Rousse
10 ppm – i.e. Marcano et al. (2011) reported 4 ppm CO measured has no impact to the ecosystems.
at 92.5% CO2 and 5.6% O2 . Currently, post-CO2 storage monitoring is on-going until 2016.

(b) Flue gas processing unit Storage integrity

The flue gas processing unit (or flue gas conditioning unit) con-
sists of the venturi scrubber (this was included due to the initial
intention to fire the boiler with heavy oil thus the venturi scrubber
should also remove any dust and particulate matters), water spray
tower and L/G separator.
The water spray tower is originally set to deliver the flue gas
at around 50 ◦ C. However, due to the problem encountered at
the compressor during the early stage of the operation, this has
been re-adjusted downward to 30 ◦ C. The L/G separator was also
modified to ensure more efficient mist removal (thus preventing
any carryover of moisture to the compressor).
(c) CO2 processing unit
The CO2 processing unit at Lacq consists of the CO2 compressor
and dehydration unit.
One of the important learning gained at Total’s Lacq project is
understanding the NO to NO2 conversion during compression. The
initial problem encountered involves the acid corrosion attack on
the suction side/cast iron cylinder of the 1st stage compressor. This
has been resolved by the following remediating actions:
• Reducing of the flue gas temperature entering the CO2 compres-
sor down to 30 ◦ C.
• Redesign of the L/G separator to ensure efficient mist removal.
• Slightly increasing the temperature of the 1st stage compressor
to minimize any condensation.
The Lacq project validated their methods for selecting and
qualifying a CO2 storage site. Various monitoring tools were tested
at the Rousse site and many subsurface modelling studies were
conducted between 2007 and 2010, before the start of injection.
One of the lessons learned from the pilot related to the well
integrity was that CO2 enhances the mechanical properties of the
cement, a key component critical to integrity of the injection well.
Public engagement
During the project Total developed and implemented methods
to foster clear understanding of the stakes of the CO2 pilot among
local residents, elected representatives, citizens’ groups, govern-
ment officials and local businesses. In addition, scientific visitors
were welcomed and many presentations were delivered at various
conferences.
6.3. CIUDEN’s Technology Development Programme Facilities
(Spain)
6.3.1. Facility description
CIUDEN’s CCS Technology Development Plant (TDP) has been
developed as part of the Spanish Government’s initiative to drive
CCS technologies towards commercialization. The test facility for
the CO2 capture is situated at Ponferrada, northwest of Spain;
beside Endessa’s Compostilla Power Plant.
CIUDEN’s facilities consist of large scale test rigs for oxy-PC
(20 MWth ), oxy-CFB (15–30 MWth ) and a small scale biomass gasi-
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125 111

Fig. 53. Block flow diagram of CIUDEN’s TDP CO2 Capture Facilities (Otero, 2013).

Table 7 The flue gas processing unit used during oxy-CFB operation con-
Main operating parameters of CIUDEN’s oxyfuel combustion facilities (Lupion et al.,
sists of the bag filter and the flue gas condenser (consisting of water
2013).
quench tower and NaCO3 scrubbers). The CPU consists of the flue
PC boiler CFB boiler gas filter, compressor, dehydration unit, and cold box. The CPU is
Dimension (m) 24 × 7.6 × 4.5 21 × 2.7 × 2.4 capable of handling 160 TPD of CO2 in the warm part and 10 TPD of
Thermal duty – max. load in 20 30 CO2 in the cold part of the CPU.
oxyfuel combustion (MWth)
Coal flow rate (kg/h) 3350 5469
Oxygen (kg/h) 6600 8775 6.3.2. Lessons learned
Flue gas recycle (kg/h) 17900 25532 (a) Oxy-CFB boiler
Flue gas flow (kg/h) 26400 28800
Steam (t/h) 25.0 44.6
P (bar)/T (◦ C) 30/420 30/250 The primary objective of the project is to demonstrate the oper-
Limestone (kg/h) – 720 ation of the oxy-CFB boiler. The main purpose is aimed to validate
Burners 4× Horizontal or 2 Vertical –
the design of future 330 MWe SC-Oxy-CFB Power Plant for OXY-
CFB-300 Compostilla Project with an intention of commercializing
this technology.
The CFB boiler at CIUDEN facility can be tested in two main
fier (1 MWth ) – as shown in Fig. 53. Associated to these facilities
operating ranges:
include a number of flue gas processing units (SCR, bag filter, FGD)
and CO2 processing unit. Additionally, a close loop CO2 pipeline
• Air & Oxyfuel flexible operation (Flexi-Burn) with MCR fuel heat
transport test rig is also incorporated.
The parameters for the PC and CFB boilers when operating in input capacity of 14.5 MWth in air mode and 15-20 MWth in oxy
oxyfuel combustion mode are summarized in Table 7. mode
• Oxyfuel mode with high inlet oxygen conditions at 20-30 MWth .
The main achievement of CIUDEN’s TDP CO2 capture facilities
is the development and demonstration of the large scale Oxy-CFB
pilot plant. The development is led by CIUDEN in collaboration with Various test programmes have been undertaken and these
Endessa and Amec Foster Wheeler. include the evaluation of following parameters:
The 30 MWth CFB facility is a first of kind world class facility;
which is designed to test CFB combustion using either air or a mix- • Temperature level of the bed at various heights (i.e. low, medium
ture of nearly pure oxygen and recycled flue gas as oxidant. The CFB and high level)
boiler is natural circulation, balanced draft boiler that includes the • Excess O2 concentration
combustion chamber, cyclone (solid–gas separation), loop seals, • Oxidant concentration
fluidized bed heat exchanger (INTREXTM ), superheaters, evapora- • Fluidization velocity
tors and economizer. • Flue gas recycle flow
Limestone is injected to control SOx emissions and make-up • Sorbent at the bed.
sand is used, when needed, to maintain the proper bed character- • Bed inventory: normal or high
istics. The CFB also includes provisions for NH3 injection (i.e. SNCR) • Pollutant emissions as a result of varying operating conditions
at the top of the cyclone for NOx reduction, and fly-ash reinjection. • SO2 abatement
112 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 54. Transition (air-oxy-air) during Flexi-Burn® operation of the oxy-CFB boiler (Lupion et al., 2013).
• Corrosion/fouling/agglomeration.
The test programme also includes the evaluation of the fuel
flexibility under oxyfuel combustion condition. This includes fir-
ing of anthracite, bituminous, sub-bituminous, petcoke and various
blends. Provisions for co-firing of coal and biomass are also included
in their test programmes.
The CFB process performs quite similarly in both air and oxyfuel
combustion modes. Successful operation of the oxy-CFB boiler has
been demonstrated. This includes successful start-up, turn down,
shut-down and operation mode switching (as illustrated in Fig. 54);
and maintaining of a stable combustion within the furnace have
been achieved.
In terms of operating the CFB boiler, the following could be
concluded (Ericsson and Alvarez, 2014):
• Furnace temperatures can be controlled by the oxidant’s O2 level,
a feature not present in air firing.
• The control system as a whole need to be designed carefully due to
multiple process interfaces present. For instance, it is important
to avoid disturbances in the low-pressure gas streams between
the main process islands.
• A high combustion temperature seems to be beneficial with
anthracite as well as with anthracite/petcoke blend. Generally
speaking, the combustion efficiency seems to be similar in both
operating modes.
• Anthracite ash is not friable, but it maintains the same size dis-
tribution caused by the crushing. Achieving the correct particle
size distribution is vital for the optimal hot loop performance of
the boiler.
• No significant fouling or corrosion was observed in the CFB hot
loop and heat recovery area.
• No clear issues occurred due to re-carbonization of CaO. How-
ever the conditions in the fluid bed heat exchanger were not
fully representative of large scale units due to a low solids outlet
temperature.
• Extensive sealing efforts were required in the flue gas path during
the commissioning phase, thus demonstrating the importance of
the air ingress issue. Gas leakages in either direction may be a
source of corrosion problems and/or may cause health and safety
issues in the working environment.
• In the solids conveying systems, replacing air with other gases
involves a risk of reduced availability unless moisture related
issues are carefully controlled.
• The CFB boiler can be integrated with the CPU and operated in a
safe and reliable way with both stationary and transient condi-
tions.
In terms of emissions, the following could be concluded (Ramos
et al., 2013a, 2013b):
• Better than expected SOx capture during oxyfuel combustion has
been observed. Greater than 95% SOx capture has been achieved.
• Level of limestone utilization between air and oxyfuel com-
bustion is not the same due to differing requirements. In air
combustion mode, limestone utilization is higher as SOx removal
requirements is governed by the environmental limits and this
is only achieved by limestone injection. On the other hand, lime-
stone utilization in oxyfuel combustion mode could be lowered
due to better capture efficiency (i.e. higher sulphation rate due to
higher SOx concentration); and further SOx removal (i.e. polish-
ing step) could be done downstream of the boiler (i.e. at the FGC
and CPU).
• NOx emissions (reported as ppmv) is reported to have same
level for both air and oxyfuel combustion mode. In terms of NOx
(reported as kg/MWh), the emissions during oxyfuel combus-
tion should be lower as compared to the emissions during air
combustion.
• Increasing limestone utilization could increase NOx emissions.
• N2 O is expected to be lower during oxyfuel combustion due to
higher bed temperature as compared to N2 O emissions during
air combustion.
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 55. Block flow diagram of Callide Power Plant (Yamada et al., 2013). FDF – forced draft fan, GRF – flue gas recycle fan, IDF – induced draft fan, PAH – primary air/gas
heater, SAH – secondary air/gas heater, FGLPH – flue gas low pressure heater, ASU – air separation unit, CPU – CO2 processing unit.
• NH4 injection is effective in reducing NOx emissions but not N2 O
emissions.
(b) Flue gas and CO2 processing units
At CIUDEN, the flue gas and CO2 processing units (Lockwood
et al., 2014) have achieved more than 2500 h for the warm part and
more than 1500 h for the cold part. They have successfully demon-
strated the integration of these processes to the oxy-CFB boiler. Air
ingress management at the warm part of the CPU is noted to be
crucial to the efficiency of the CO2 processing units.
The flue gas conditioning units when operating the oxy-CFB
boiler consists of the bag filter, water quench tower and Na2 CO3
scrubbers. Na2 CO3 is used in scrubbers to remove SOx down to less
than 1 ppm. It was also reported that nearly all of the dust were
removed by the quench and scrubbers. The CO2 Processing Unit
consists of the flue gas filter, low pressure dehydration unit, CO2
compressor and the cold box.
The design for the low pressure dehydration unit is based on 3
vessels system operating at relatively low pressure. This is not a
typical design as it is aimed to test alternative system where flue
gas is dried at lower pressure consequently requiring more adsor-
bent. Critical to this system is that SOx and other acidic components
should be less than 10 ppm to prevent any corrosion issues. By hav-
ing a bone dry flue gas at low pressure should limit the NO to NO2
conversion to a minimum thus preventing any formation of the
HNO3 and/or H2 SO4 during compression. Operating experience at
CIUDEN reported that the drying unit has achieved a dew point of
−100 ◦ C, more than sufficient to the requirements of the cold box.
Around 10% of the dried flue gas (equivalent to ∼15% of the flue
gas fed into the quench tower) is compressed in a reciprocating
113
compressor (to ∼20 bar) and the rest of the flue gas are vented.
The size of the cold part of the CPU was determined by CAPEX
optimization.
The cold box is using closed loop CO2 cycle for its refrigera-
tion requirement. Partial condensation is achieved by cooling the
flue gas (with a minimum temperature at ∼−50 ◦ C). To remove
all O2 and NOx , a distillation column is used. The liquid CO2
product (∼10 TPD) could achieve a purity of 99.9+% with other non-
CO2 components consisting of NOx (<10 ppm), SOx (<0.1 ppm), O2
(<10 ppm), H2 O (<1 ppm) and Ar/N2 (balance).
6.4. COSPL’s Callide Oxyfuel Project (Australia)
6.4.1. Facility description
The Callide Oxyfuel Power Plant is the world’s first coal-fired
power plant to operate with oxyfuel combustion technology and
the largest demonstration of this technology to date. It is located
near Biloela, Queensland (Australia).
Callide-A Power Plant was built and commissioned in 1965.
This consists of 4 units with a nominal capacity of 30 MWe each.
The power plant has been recommissioned in 1998 and put into
storage. Unit 4 was retrofitted with oxyfuel combustion. It was suc-
cessfully commissioned in 2012 (i.e. ASU in January 2012, Boiler in
May 2012, CPU in September 2012, and full demonstration started
in December 2012). It has achieved more than 10,000 operating
hours and around 5500 h in oxyfuel combustion mode delivering
electricity and capturing CO2 in real power plant scenario.
114 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 56. Transition between air and oxyfuel combustion mode and vice versa (Yamada et al., 2013).
The scope of the plant retrofit includes the following:
• Refurbishment Callide-A Unit No. 4
• Installation of 2 new IHI burners
• Retrofit of various oxyfuel combustion components and associ-
ated equipment (i.e. ducting, DCC or water removal unit, PAH,
SAH, FGLPH, and others)
• Installation of 2 × 330 TPD Air Separation Units (ASUs) with >98%
O2 purity
• Installation of a 75 TPD CO2 capture plant (processing around 12%
of the total flue gas).
Fig. 55 shows the simplified schematic flow diagram of the Cal-
lide Power Plant (Unit 4) before and after the retrofit.
The boiler is equipped with 3 bitter mills to feed the coal to the
burners. The boiler has 6 burners in 3 × 2 front wall arrangements
(with 4 burners in service). 2 new IHI burners were installed to
replace the old burners in the middle row. The boiler is a 2-drums
type boiler without reheater that produces steam at 460 ◦ C and
4300 kPa (∼43 bar), and the steam turbine delivers electricity at
132 kV.
Two trains of air separation units at a nominal 330 TPD of O2 per
train was installed. This is based on standard flow sheet design and
installation. The ASU could deliver 9300 Nm3 /h gaseous oxygen at
>98% purity. The oxygen is injected into the windbox by nozzles to
ensure a balance O2 distribution to all the burners.
The CPU at 75 TPD CO2 is designed to process up to 17% of the
flue gas. The size was determined by the smallest centrifugal com-
pressor available in the market.
6.4.2. Lessons learned
One of the great achievement of this project is that it has
successfully demonstrated that oxyfuel combustion could be
retrofitted in a coal fired power plant.
(a) Boiler and burners operation
Callide Oxyfuel Project (Yamada et al., 2013; Spero et al., 2013a,
2013b) has successfully tested the performance of the boiler and
burners within the required parameters for:
• Start up (in air mode), turn down (in oxyfuel mode) and shut
down (in air and oxyfuel mode)
• Boiler and burners controls – recycled flue gas and oxygen
• Heat transfer profile
• Emissions (NOx , SOx , CO and trace elements).
Fig. 56 demonstrated a smooth transition during the switch
from air to oxyfuel combustion mode and vice versa. Reliable mode
change is achievable within 1–1.5 h. Turndown from 30 MWe to
24 MWe has been demonstrated during oxyfuel combustion mode.
Various mill patterns and burner operation has been evaluated.
It was noted that mill performance has no significant difference
when operating in air or oxyfuel combustion mode. Combustion
efficiency as indicated by carbon in ash and CO emission are
reported to be lower during oxyfuel combustion.
Heat transfer profile during oxyfuel combustion is similar to air
firing at inlet O2 of 27%. Fig. 57 illustrates the heat absorbed by
the boiler for air and oxyfuel combustion. It could be noted that
heat absorbed is slightly lower by 3-4% and this is attributed to the
impact of the FGLPH.
It is worthwhile to note that Callide Oxyfuel Combustion is a
design for Australian power plants specification. Given that the coal
used has low sulphur and ash content, the flue gas processing units
only consists of the fabric filter (i.e. particulate removal) and does
not have any DeNOx and DeSOx plant. The flue gas fed to the CPU is
cooled by using water quench and alkali scrubbers (i.e. SOx removal
polishing step).
Typical SO2 and SO3 emissions (reported as ppm with correc-
tion) from the boiler are generally the same in both air and oxyfuel
combustion. SO3 in the flue gas have been measured after the boiler
and after the SAH. Concentration of SO3 (reported as ppm) mea-
sured is generally higher, but is not detectable after the fabric filter.
NOx emissions (reported as ppm with correction) are observed to
be lower. However, NO2 to NO ratio is significantly higher during
oxyfuel combustion.
Important to highlight the benefit of having an established
research programme funded by ANLEC R&D (Li et al., 2012;
Morrison et al., 2012; Nelson et al., 2013) have undertaken a
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
Fig. 57. Heat transfer profile of the boiler (Yamada et al., 2013).
detailed measurements of criteria pollutants (such as NOx , SOx )
and trace elements after the boiler and within the different part
of the CPU. Information gathered should provide a good under-
standing to the fate of these gas species and trace elements during
oxyfuel combustion – should have an important contribution to
the safety and other environmental considerations.
(b) Flue gas and CO2 processing unit
The flue gas and CO2 processing units (Lockwood et al., 2014)
consist of the (a) water quench and low pressure scrubber, (b) flue
gas filtration devices, (c) CO2 compressor, (d) dehydration unit, (e)
cold box.
NaOH is used in the low pressure scrubber. This should remove
most of the remaining acid components – HCl, HF, SOx , etc. to a
level below 10 ppm. Additionally, it is also effective at reducing any
particulates (between 10 and 100 ␮m) to below 1 mg/Nm3 .
The flue gas compressor is a 4 stage integrally geared centrifugal
compressor. This type of compressor is a representative to what
will be used in a large plant. Intercoolers are installed after stage
2 and stage 4. Condensate collected from the cooler has a pH < 1.
No significant corrosion has been observed in the compressor or
coolers.
The cold box consists of the BAHX, deNOx rectifying column,
flash column and a distillation column. The compressed dried flue
gas is first scrubbed with liquid CO2 to liquefy any remaining NO2
in the gas. Then the flue gas is cooled in BAHX and bulk of the inerts
(N2 , O2 and Ar) are separated in the flash column. An additional
distillation column is used to further purify the CO2 to remove any
remaining inerts and bring down the O2 content down to <10 ppm.
The liquid CO2 product (∼75 TPD) could achieve a purity
of 99.95% with other non-CO2 components consisting of NOx
(<2.5 ppm), SOx (< 0.1 ppm), O2 (<10 ppm), H2 O (<1 ppm) and Ar/N2
(balance). Overall recovery rate of the CPU is reported at 85%.
115
Bulk of the refrigeration is based on evaporation and expansion
of the liquid CO2 (principle of auto-refrigeration cycle). Additional
NH3 refrigeration cascade system is used to liquefy the gaseous CO2
from the cold box.
6.5. Large scale demonstration projects
There are several large scale demonstration project that have
reached an advance stage of development where detailed FEED has
been completed. Several of these projects have been put on hold.
These include
a) Vattenfall’s Janschwalde Project;
b) CIUDEN/Endessa’s Compostilla OxyCFB300 Project;
c) KEPCO’s Young Dong Project; and
d) FutureGen 2.0 Project.
Positive financial investment decisions (FID) to these projects
were not reached due to several reasons which include the lack of
regulatory framework, public acceptance and/or financial closure.
Background information and engineering design proposed for these
projects have been presented in various conferences.
As of writing this paper, White Rose Project is the only remaining
project that could have the potential to be realized by the end of
this decade. FEED study is currently on-going. FID should be made
towards end of 2015 or early part of 2016. Background information
are presented in various presentations; however, process overview
and engineering design is not yet available in the open literature.
6.5.1. Key messages
Below are some of the messages taken from the experiences
gained from operating large scale pilot plants and developing early
commercial demonstration project(s):
116 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
• One of the key messages from this review paper is that oxyfuel
combustion technology is mature and ready for demonstration.
• Large utility scale demo project, such as White Rose Project, is
critical in order to demonstrate that the technology will work
over the time scale typical to a real power plant operation (often
involves several decades).
• Long term operation is crucial to demonstrate and validate under-
lying technology and operating principles. Some of the issues
specific to oxyfuel combustion technology that could be validated
only by long term operation include:
◦ Air ingress management
◦ Corrosion management
◦ Power plant integration (with ASU and CPU)
◦ Process control optimization.
• The commercial deployment of oxyfuel combustion technology is
important to allow equipment vendors to provide performance
guarantees that could underpin any financial investment deci-
sions.
• Oxyfuel combustion technology is an “All or Nothing” CCS option
– as partial CO2 capture is not a possibility.
• Government incentive is important to realize a First-of-a-Kind
(FOAK) power plant. First generation FOAK oxyfuel power plant
should have the financial security (bankability) that could cover
the additional operating cost of CCS.
Regulator support is necessary. Specific to this technology, it is
essential that regulation should not set operation limits (such as
Product CO2 purity and/or CO2 capture rate) that could hinder any
large scale demonstration project.
7. Summary and concluding remarks
This review has primarily focussed on three different group of
technologies namely: (a) oxy-PC, (b) oxy-CFB and (c) oxy-GT tech-
nologies; and presented the current state of the art development
in these areas.
7.1. Oxy-PC
Oxy-PC combustion has progressed from the fundamentals of
particle ignition and flame dynamics to impurity control and cor-
rosion mechanisms. The properties of CO2 are intrinsically different
from N2 and as such impart characteristic (yet predictable) impacts
on combustion conditions. The CO2 rich combustion environment
has been shown to delay ignition of coal particles and alter the char
burnout with additional gasification reactions. Ultimately, this has
affected burner design and operation, with the rate of recycled flue
gas and O2 injection providing both complications and an opportu-
nity for flexibility in controlling flame aerodynamics, ignition and
furnace heat transfer. The flame instabilities caused from delayed
ignition and lower flame temperatures have been countered by
using oxidant (burner) flows with higher O2 concentration than air
– typically between 27 and 35%. In this respect, the construction
and operation of large oxyfuel combustion facilities by technology
providers has resulted in burner designs suited to the technology.
Radiative properties of oxyfuel flames are different from air-
fired combustion due to the high CO2 and H2 O concentrations and
altered flame shape. However, current adjustments to flame and
heat flux modelling for oxyfuel combustion have been validated up
to 30 MWt scale and applied to design of larger units.
Large pilot testing has also allowed the evaluation of high
temperature corrosion mechanisms and mineral transformations
under oxyfuel combustion (e.g. slagging and fouling). Much of
the early uncertainty in deposit formation in oxyfuel combustion
rested on the uncertainty in operating conditions mainly associated
with the oxyfuel flame (e.g. recycle ratio, level of impurities, particle
trajectory, and char burnout). With improved modelling and larger
scale testing, these factors have become less significant. Deposition
studies have revealed larger extents of sulphation in deposited ash
particles in oxy-firing primarily related to higher SO2 concentra-
tions. This has linked corrosion mechanisms with the level of gas
impurity control, with specific attributes largely coal specific rather
than based on firing mode. The specific influence of CO2 on steel
alloys has been identified to cause enhanced carburization result-
ing in an incomplete oxide scale. Low chromium steels appear to
be permeable to CO2 , while higher partial pressures of H2 O vapour
tend to reduce this carburization impact. Overall, the combination
of higher impurity levels and CO2 /H2 O suggest that corrosion is an
issue in oxyfiring which requires consideration of boiler material
and design as well as operation.
The extent of gas impurity formation in oxyfuel combustion has
been shown to be similar to that of air-firing, however the effect of
recycle and extent of flue gas cleaning have a number of important
impacts throughout the plant due to their different concentrations.
Without cleaning, SO2 /HCl concentrations have measured up to 4
times that of air-firing causing higher corrosion rates, higher acid
dew point temperatures and interactive effects with mercury in
the flue gas. With cleaning, these concentrations are similar to air-
firing but result in a small efficiency penalty from cooler recycle
conditions. The lower emission rate of NOx in oxy-firing has been
well characterized and arises from the “re-burning” influence of
recycled NO passing back through the flame.
Mercury and its removal in oxy-firing presents a unique case
in that cleaning can occur concurrently in other impurity control
units (e.g. fabric filter/ESP, FGD), however the primary reason for
its removal is due to its corrosion impacts at the back-end CO2
liquefaction plant. In general, oxy-firing conditions support higher
oxidation of elemental mercury but its overall removal is depend-
ent on specific plant configurations and type of fuel.
The impact of oxy-firing on impurity control devices is sub-
tle, with experience in operation drawn from a number of large
scale pilot plants. In this respect, conventional equipment used in
air-firing can be used with only minor design changes; an exam-
ple being the use of a separate oxidation chamber in wet FGD’s
to avoid air ingress. However, impurity removal within the CO2
processing unit (CPU) is also possible, particularly for NOx and Hg,
along with cryogenic inert removal (O2 /N2 /Ar). These CPU clean-
ing concepts have been tested at large pilot scale but the optimum
cleaning shared between the boiler block and CPU has yet to be
established. Overall, impurity formation and control in oxy-firing
has been identified as a significant issue with potential solutions
established.
Operationally, the air separation unit, boiler block and CO2
processing unit must be integrated but the added complexity
requires specific consideration during start-up, shut down and pro-
cess trips. In general ASU’s and air-fired boilers are both considered
mature technology and their operation is well known. The liquefac-
tion of CO2 is based on mature technology but the specific design
and operation have yet to be commercially proven. The boiler block
may be started on air firing but transition to oxy-firing can only
occur if the ASU is operational. As a cryogenic process, the initial
cool down may take days before providing O2 for combustion. Tran-
sition from air to oxy mode has been shown to take 30 min or less
and this has been verified at pilot scale. Compression and liquefac-
tion of CO2 may begin when the CO2 content reaches a minimum
concentration to enable liquefaction to occur.
The past decade has provided valuable operational experience
of integrated oxyfuel systems in a number of large scale pilot plants.
Further experience is now needed on a large scale demo plant to
move this technology to the next level. It is essential to have this
next step in order to improve efficiency and identify integration
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
opportunities that could help reduce parasitic losses of the ASU
and CPU.
7.2. Oxy-CFB
Oxy-firing in circulating fluidized beds has received less atten-
tion than pulverized fuel combustion. However, oxy-CFB has
several advantages in comparison with oxy-PC:
• Offers higher flexibility for different fuels – i.e. large variation of
solid fuels can be used with only simple fuel preparation.
• Fuel feeding is based on simple devices, thus it does not need for
new design for burners.
• Capable of in situ sulphur capture in the furnace by using lime-
stone.
• Intrinsically a low NOx emission boiler due to lower combustion
temperature.
• With possibility to install external heat exchangers, thus provid-
ing flexibility for adjusting the heat balance, amount of recycled
flue gas and fuel conditions.
• Capable of burning in a higher O2 concentration and lower RFG,
thus savings on CAPEX could be achieved by having a smaller
boiler for the same output.
• Burning with higher O2 concentration could also extend the fuel
range (especially burning of low grade fuel).
• Combustion of 100% biomass is also possible in a CFB providing
a pathway for bio-CCS and thus a significant CO2 sink.
In the last ten years, technology development has been rapid.
Different experimental trials from small laboratory devices to large
scale pilot units have been deployed. Tests have been done in
moderate (∼20-30%) to high (∼40-55%) oxygen concentrations in
combination with real recycled flue gas. Most importantly, the CIU-
DEN TDP for oxy-CFB (at 30 MWth ) has provided a platform to
validate and scale up this technology.
Operationally, the CFB configuration can also use external heat
exchangers to provide flexible options for adjusting the heat bal-
ance. The injection of O2 into an oxy-CFB boiler may be separated
from the addition of fluidising gases and is an additional operat-
ing parameter for tailoring the combustion, heat transfer and fluid
dynamics.
In moderate oxygen concentration, the devolatilization, char
burnout and gas phase reactions during oxyfuel combustion behave
principally in the same manner to the air-fired CFBs. Combustion
efficiency in CFB combustion is mainly dependent on unburned car-
bon in ash and to some extent of the CO emission. Results reported
in various test indicated that the combustion efficiency seems to
be similar or slightly better when compared to air combustion. As
a result, the design principles related to combustion behaviour and
heat release profiles can be based on the similar guidelines as in air
combustion.
Heat transfer in CFBs is mainly affected by fluid dynamics and
concentrations of solid bed materials. The fluid dynamics and flow
profile are mainly affected by the flow rate and the location where
fluidising gas are introduced into the boiler; and to some extent the
properties of the fluidising gas and the solid materials in the bed. In
oxy-CFB, having the option to modify the ratio of recycled flue gas
and oxygen in different feeding location could provide additional
flexibility to control the heat transfer at different loads and/or when
operating with varying fuels.
Properties of fluidising gases in oxyfuel combustion are differ-
ent as compared to the gas properties in air combustion. Higher
CO2 and H2 O content could affect the heat transfer profile of the
CFBs especially in the regions where solid concentration are lower
(i.e. upper levels of the furnace or during low loads). Similarly,
the higher heat capacity of CO2 and H2 O could also impact the
117
temperature in the hot loops (due to higher heat absorption by
the triatomic gas species). However, the flexibility to adjust the
ratio of recycled flue gas and oxygen should provide the capa-
bility to match the heat transfer profile of an air-fired CFBs –
typically this should correspond to an oxygen concentration in the
range of 22–24%. As a result, the thermal performance of oxy-fired
CFBs can be designed by using the same design rules used in air-
fired CFBs with the additional considerations for the differing gas
properties.
Specific to CFB’s is the in-bed capture of SO2 with limestone.
The SOx can be captured in the furnace by limestone to form CaSO4
based on two main mechanisms – (a) by direct sulphation mech-
anism – where SO2 is directly adsorb by CaCO3 ; or (b) by indirect
sulphation mechanism – where the CaCO3 is first calcined to CaO,
and the SO2 is adsorbed by CaO. The direct mechanism is favoured
at lower temperature whilst the indirect mechanism is favoured
at higher temperature (i.e. as shown in the calcination curve). The
concentrations of SO2 and SO3 in oxy-CFB are typically higher than
in air-fired CFBs due to missing nitrogen in gases, whereas emission
levels are reduced due to lower flue gas flow rates and more effi-
cient sulphur capture in the furnace. Based on the various pilot scale
tests, relatively good sulphur capture can be expected in oxy-CFB.
The sulphur capture efficiencies and SO2 emissions have been sim-
ilar or better in oxy-fired conditions as compared to air-fired cases.
Latest results from CIUDEN further validate the good performance
in terms of sulphur capture. In many cases, the high sulphur cap-
ture efficiency has been observed to occur at higher temperature
favourable to indirect sulphation mechanism. It could be surmised
that the optimum temperature in relation to sulphur capture is
higher in oxy-CFBs as compared to air-fired CFBs. As a result, this
may require some considerations when designing the furnace heat
transfer and temperature profiles.
Agglomeration of the bed materials in the external fluid bed
heat exchangers or in the loop seal of the CFBs is an issue that
needs to be considered in the design of the oxy-CFBs. Agglomer-
ation tends to be promoted by the recarbonation of the CaO to
CaCO3 especially if fluidization becomes disturbed. Some agglom-
eration has been recorded in many test facilities, but continuous
operation in the large scale pilot plants have not experienced any
agglomeration. The agglomeration tendency can be affected by
temperature and gas atmosphere. Higher CO2 concentration could
favour recarbonation when subjected to the right temperature con-
ditions (typical to the CFB hot loops and external heat exchangers).
To prevent and minimize any agglomeration, it is essential to avoid
the defluidization and stagnant regions in the loop. As a conse-
quence, recarbonation may affect the thermal design and operating
conditions of the boiler and lead to somewhat different design and
operation of the oxy-CFB as compared to air-fired CFBs. Detailed
criteria and understanding for the occurrence of agglomeration
promoted by recarbonation are still lacking and this is one of the
areas where more research is required.
In general, NOx and SOx emissions from the oxy-CFB are lower
as compared to oxy-PC. Typically, only about 10% of sulphur and
less than 5% of nitrogen contained in the fuel have been emitted in
the flue gases of oxy-CFBs. In this context, the need for additional
flue gas processing units (i.e. deSOx and deNOx) will now depend
on the allowable concentrations required by the CPU.
Higher SO2 and SO3 concentration in the flue gas during oxy-
CFB combustion should be expected and could increase the risk of
corrosion in the boiler and the different flue gas ducting. However,
corrosion issues has not been the focus of research in most existing
pilot tests. In similar note, assessing the possible impact of SO3 at
the cold end of the boiler is not yet well evaluated.
Typical conversion of fuel N to N2 O during oxy-CFB combustion
is about 1-2%. Generally, increasing the bed temperature reduces
N2 O concentration. Understanding the fate of N2 O during oxyfuel
118 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125
combustion is crucial given that N2 O could present some potential
issue to the cold box of the CPU.
Emission of trace elements during oxy-CFB combustion have
only been studied in the pilot tests of CanmetENERGY (Jia et al.,
2013). No other studies have been done in this area. Among the
different trace elements, mercury emission is an important con-
sideration to the design of the CPU. Due to the limited test results
reported, it is difficult to draw a conclusion on the fate of Hg during
oxy-CFB combustion. Further investigation is needed.
Oxy-CFB allows also use of high oxygen concentrations (40-50%)
by reducing the ratio of recycled flue gas leading to smaller furnaces
with increased local energy production. In CFB boilers the extensive
heat production can be balanced by the heat capacity of circulating
bed material and by many options to locate additional heat trans-
fer surfaces in the hot loop. Based on the pilot tests and process
modelling, it has been shown that CFB combustion process can be
controlled and operated also under higher oxygen concentrations.
At high oxygen concentrations the performance of the process is
mainly similar to combustion in moderate oxygen concentrations.
Combustion efficiency is expected to be slightly higher and heat
transfer to behave according to the same rules as in moderate oxy-
gen concentrations. There has not been presented clear differences
in SO2 and NOx emissions, but the research has not yet focussed
on the topic to justify more detailed conclusions. Proceeding with
large scale high oxygen CFB units will need design and develop-
ment of boiler configurations suitable for balancing the combustion
energy and heat recovery in smaller furnaces and for meeting the
requirements of the steam cycle.
Overall, the operational experience with large scale pilot oxy-
CFBs have reached similar scales to the oxy-PC. Although there are
still several areas where research are needed, the maturity of the
oxy-CFB could be at par with oxy-PC. It is essential to move this
technology to the next level (i.e. large scale demonstration) in order
to realize the potential of an alternative where fuel flexibility may
improve the economics.
7.3. Oxy-GT
In this paper, different cycles for oxyfuel combustion for gas
turbine applications are presented. The focus is on 4 cycles that use
internal combustion and recirculation of either water or CO2 for
controlling combustion and turbine inlet temperature. The consid-
ered cycles include the SCOC-CC, the CES cycle and the Graz cycle
which are extensively investigated in the literature. In contrast,
information about Allam cycle is scarce which is mainly due to
being a recent announcement of the cycle. However, some sim-
ilar processes have been proposed earlier. Additionally, a brief
overview is given for cycles that are based on advanced reactor
designs, e.g. membrane reactors.
The Allam cycle is claimed to have a net efficiency of 59% which
is the highest efficiency of the 4 considered processes. This is due
to a high amount of heat integration that significantly reduces the
penalty for the oxygen supply. However, no comparison with the
other considered cycles is available on the same basis. The Graz
cycle is considered to have the highest efficiency (49–53%) of the
other 3 cycles if similar conditions are assumed. It is followed by
the SCOC (46–49%) and the CES cycle (44–47%). This ranking is
confirmed by a comparative study by Kvamsdal et al. (2007). They
also show that higher efficiencies of over 50% can be achieved with
membrane based or CLC gas turbine systems. The operational chal-
lenges and the maturity of the cycles are ranked in the opposite
direction (Kvamsdal et al., 2006).
All cycles need several newly designed components to be real-
ized. The main component that is affected is the combustion
system. It has to enable stable combustion in a significantly differ-
ent working fluid than air. Depending on the chosen cycle different
types of turbomachinery are needed. The Allam cycle only needs
one turbine that has to combine the high pressures of modern steam
turbines and nearly as high temperatures of a gas turbine in a super-
critical working fluid. The CES cycle has three turbines in a working
fluid mainly consisting of steam. The HP and LP turbine are com-
parable to conventional steam turbines whereas the IP turbine is
supposed to have advanced gas turbine inlet parameters. The turbo-
machinery needed for the SCOC-CC turbomachinery is comparable
to a conventional NGCC power plant. While the steam turbines are
conventional equipment, the oxyfuel gas turbine needs to achieve
much higher pressure ratios as a comparable air-blown gas tur-
bine. The Graz cycle is characterized by a complex arrangement of
several turbines and compressors.
None of the considered cycles has yet been demonstrated in its
full cycle configuration. However, the most demonstration activi-
ties were done for the CES cycle in the Kimberlina test facility. It
was achieved to produce power to grid with the main combustion
system and an existing steam turbine. The IP turbine and the reheat
combustor have been developed from conventional gas turbine
equipment and were tested separately at the plant. Combustors
of the SCOC-CC and Allam cycle have been tested in test rigs.
Future demonstration work is planned for the SCOC-CC in
a small scale pilot gas turbine in Norway. Within the projects
regarding the CES cycle more goals for demonstration are given,
e.g. testing the reheat combustor with the IP turbine. Further
testing is put on hold because of budget limitations. The largest
project in the near future focusses on the Allam cycle with a
50 MWth demonstration plant that is planned for commissioning in
2016.
7.4. Concluding remarks
The last decade has seen significant R&D on oxyfuel combustion.
Large scale testing combined with targeted laboratory studies have
provided underpinning fundamental scientific knowledge and has
generated experience with the large individual and integrated unit
operations.
For oxy-PC and oxy-CFB, the next step is to demonstrate this
technology in near-commercial scale unit. As this is important
step to validate the underlying operating principles and to allow
equipment vendors to provide performance guarantees that could
underpins any financial investment decisions. Further develop-
ment could be stalled without such demonstration.
Oxy-GT combustion is also emerging as an option for capturing
emissions from natural gas combined cycles, with the technology
related to coal gasification. As with coal fired oxy-combustion, the
ASU and CPU are the main additional energy consuming compo-
nents. The higher efficiencies of the combined cycles are expected
to reduce the impact on sent out electricity giving an overall effi-
ciency of 44-59%. Oxygen must be supplied at high pressure and
different cycles are currently being assessed. The technology is cur-
rently in development at small pilot scale with only a few projects
on larger scale tests on-going (i.e. CES cycle) or to be commissioned
by 2016 (i.e. Allam cycle).
The coming decade is critical for oxyfuel technology to extend
this basis and prove its operation at commercial scale. Its success as
a viable CO2 mitigation technology will ultimately be determined
by a combination of technical readiness, economic incentives, polit-
ical will as well as public acceptance of CCS.
Second generation oxyfuel technologies after the next decade
may include: (a) higher integration, (b) alternative O2 supply, (c)
development of alternative oxyfuel combustion process such as
pressurized oxyfuel or CLC, and (d) incremental development of
options to increase overall efficiency and to reduce the cost and
risk of implementation.
 R. Stanger et al. / International Journal of Greenhouse Gas Control 40 (2015) 55–125 119

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