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Progress in Energy and Combustion Science 35 (2009) 385397

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Progress in Energy and Combustion Science


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

Emission control of nitrogen oxides in the oxy-fuel process


Fredrik Normann*, Klas Andersson, Bo Leckner, Filip Johnsson
teborg, Sweden
Department of Energy and Environment, Chalmers University of Technology, SE412 96 Go

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 29 December 2008
Accepted 10 April 2009
Available online 21 May 2009

The interest in oxy-combustion as a method to capture carbon dioxide has increased drastically during
recent years. The oxy-fuel process offers new process conditions and may take advantage of innovative
techniques as well as of new ways to apply conventional measures for emission control. The present
work reviews available techniques for controlling both the emission of nitrogen oxides (NOx) to the
atmosphere and the content of NOx in the captured carbon dioxide. The results indicate that for a rst
generation of oxy-fuel power plants, conventional primary NOx control should be sufcient to meet
todays emission regulations, if based on emission per unit of fuel supplied. However, there are several
opportunities for new methods of NOx control in oxy-fuel plants, depending on future emission and
storage legislation for carbon capture schemes. Improved understanding of the behaviour of nitric oxide
and nitrogen dioxide during compression and condensation of carbon dioxide is needed, as well as
improved knowledge on the inuence of the parameters of oxy-combustion on nitrogen chemistry.
2009 Elsevier Ltd. All rights reserved.

Keywords:
Oxy-fuel
O2/CO2
CO2 purication
NOx
Emissions
Boiler

Contents
1.
2.
3.
4.

5.

6.

7.
8.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
The oxy-fuel process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
3.1.
Limits for NOx in the oxy-fuel process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387
Nitrogen chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
4.1.
NOx in combustion processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
4.2.
Influence of oxy-fuel combustion on nitrogen chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
4.3.
Influence of CO2 conditioning on nitrogen chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
Primary measures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
5.1.
Fuel-staging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
5.2.
Air-staging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
5.3.
Low-NOx burner technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
5.4.
Flue-gas recirculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
5.5.
High-temperature NOx reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
Secondary measures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
6.1.
SCR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
6.2.
SNCR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
6.3.
Absorption of NOx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
6.4.
Phase separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
Summary and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
Future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396

* Corresponding author.
E-mail address: fredrik.normann@chalmers.se (F. Normann).
0360-1285/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pecs.2009.04.002

386

F. Normann et al. / Progress in Energy and Combustion Science 35 (2009) 385397

1. Introduction
The emission of carbon dioxide (CO2), as a cause of global
warming, is of current concern for the power industry. For
centralized power generation systems, where most of the fossil
fuels for electricity generation are consumed, capture and subsequent storage of CO2 is under consideration with signicant efforts
made in research and construction of pilot and demo-scale plants.
Oxy-fuel (O2/CO2) combustion is one of the technologies considered
as a promising and near-term option to capture CO2 from power
plants. In addition to reduction of CO2 emissions, an oxy-fuel power
plant offers new conditions for emission control of other pollutants
such as NOx, which is the subject of the present investigation.
The design of oxy-fuel power plants may be divided into two
generations. A rst generation uses technology that is proven in airred power plants as far as possible in order to gain a rapid and
secure introduction of the oxy-fuel technology. In the rst generation, the operational data of oxy-combustion are controlled to
imitate air combustion, and conventional ue-gas cleaning equipment is used. In a second generation, the acceptance for innovative
techniques is higher and new parameters available for optimization
of oxy-fuel combustion can be utilized to nd new optimal operational conditions. For example, the possibility to control the
concentration of oxygen (O2) in the oxidizer (not possible in
combustion with air) could lead to lower gas ows through the
boiler (other furnace dimensions) and higher ame temperatures
with inuence on ash behaviour and combustion efciency.
Furthermore, the second generation of oxy-fuel power plants will
be designed when capture and storage of CO2 is an established part
of the energy system and, thus, with legislation adapted for oxyfuel conditions.
The aim of this review is to evaluate and summarize the technology status of NOx-control systems for the oxy-fuel process,
including aspects relevant to a second generation of oxy-fuel power
plants. The areas investigated are.
1 Applicability of conventional NOx reduction measures to the
oxy-fuel process.
2 Chemistry and performance of new NOx reduction measures in
oxy-fuel combustion.
3 Need for research on NOx control for second-generation oxyfuel power plants.

briey described (more information in Refs. [13]) and aspects of


the process that are important for NOx control are introduced.
Furthermore, the basic principles of nitrogen chemistry are
summarized (more information in Refs. [4,5]), and it is discussed
how these are affected by the oxy-fuel process. Finally, solutions for
NOx reduction are presented and discussed.
The NOx-control technologies are divided into primary and
secondary measures. Primary measures are techniques applied
during combustion (A in Fig. 1), whereas secondary measures are
applied downstream of the combustion process (B through E in
Fig. 1). The techniques are conceptually described and evaluated
qualitatively with respect to present development, requirement of
additional equipment, critical design parameters, power
consumption, additives, catalysts, and by-products.
The reduction measures are evaluated by two approaches,
differing in their level of maturity. For conventional reduction
measures, the performance and design of todays power plants are
employed (more information on NOx control in air-red power
plants in Refs. [68]), and the possible impact of oxy-fuel
combustion is evaluated. For innovative reduction measures (not
feasible in air-red plants), the performance and design are
obtained from published simulations of the reduction measure
investigated. It is difcult to compare the operational performance
of existing techniques with the performance of innovative
processes, for which only theoretical data are available. Nevertheless, the published process calculations are well established and
with this background the possibilities of the new processes can be
illustrated.
As a complement to literature experience, modelling of gasphase nitrogen chemistry is carried out to illustrate the effect on
the reduction measures of oxy-fuel combustion. Gas-phase reactions are dominating nitrogen chemistry [9] and the modelling of
these reactions gives a good approximation on the behaviour of the
system with respect to NOx reduction. The reacting system is
modelled as a plug-ow reactor at atmospheric pressure and with
a predened temperature prole. The reaction calculations are
performed with the SENKIN [10] code of the CHEMKIN-II [11]
software, and the rate-of-production analysis is carried out with
the CHEMKIN-PRO [12] software. A detailed kinetic mechanism
developed for modelling of NOx reduction by staged combustion,
reburning and selective non-catalytic reduction (SNCR) is used for
the calculations. More information on the kinetic reaction mechanism and on the associated thermodynamic library used are given
in Ref. [13] and references therein.

2. Methodology
3. The oxy-fuel process
The main part of the work is based on a literature review, but
some theoretical evaluations are made on the behaviour of NOx in
combustion systems. As a background, the oxy-fuel process is

The oxy-fuel (O2/CO2) combustion process is outlined in Fig. 1


and a rough overview of property values of the ue gas throughout

Fig. 1. Principles of the oxy-fuel process with wet ue-gas recirculation. Letters indicate locations of possible emission control. Representative properties of the ue gas are given in
Table 1. FGC ue-gas condenser.

F. Normann et al. / Progress in Energy and Combustion Science 35 (2009) 385397


Table 1
Rough overview of properties of the ue gas in an oxy-fuel power plant (see Fig. 1 for
stream numbers).
Stream

Pressure (bar)
Temperature ( C)
Mass Flow
Volume Flow
Phase

1
300
1
1
Gas

1
300
1/3
1/3
Gas

1
20
1/3
1/7
Gas

30
20
1/3
1/200
Gas

30
30
1/4
1/900
Liquid

100
20
1/4
1/1000
Fluida

1
20
1/25
1/40
Gas

Supercritical uid.

this process is presented in Table 1. Pulverized coal is burned in


oxygen (>95% purity) mixed with recycled ue gas (RFG) in order to
moderate the ame temperature. Due to the absence of atmospheric nitrogen (N2), the ue gas mainly consists of carbon dioxide
and water vapour (H2O). The ow of recycled ue gas controls the
properties in the combustion process, such as temperature, burner
aerodynamics, and residence time. Particles are separated from the
ue gas before recycling, to limit enrichment in the furnace and
erosion. Water is separated from the ue gas in a ue-gas
condenser (FGC). Generally, it is suggested to extract the ue-gas
for recycle from a position upstream of the FGC, i.e. wet-recycle
(shown in Fig. 1). The wet-recycle is thermodynamically favourable
compared to a dry recycle of ue-gas, which is extracted downstream of the FGC (the temperature is determined by the temperature in the dust separator instead of the temperature in the FGC). A
dry recycle would be required if there are any restrictions on the
level of moisture or SO2 in the RFG. Before the CO2 in the ue-gas is
discharged from the power plant, it has to be condensed for costeffective transportation and storage. The condensation takes place
at a pressure between 15 and 40 bar and a temperature between
20  C and 55  C, depending on process conditions. After
condensation, the CO2 is compressed to supercritical conditions.
For typical design parameters (oxygen purity and combustion
operation), the exhaust ue gas consists of w95% CO2 on a dry
basis. The remaining part is mainly excess oxygen from combustion, nitrogen and argon (Ar) from impurities in the oxygen, and, to
less extent, pollutants, such as nitrogen oxides (NOx) and sulphur
oxides (SOx) (w0.10.2%). The purity of the oxygen supplied is
a question of energy consumption and investment in the airseparation unit. Besides purity of oxygen, the other important
source of impurities in the CO2 is air ingress. For safety reasons,
coal-red furnaces often operate at slight sub-atmospheric pressure and have to be made gas-tight to avoid air ingress. However,
even for a gas-tight or slightly pressurized oxy-fuel boiler there are
still possibilities for air ingress, e.g., in the particle separation, in the
recycle fan, and in the coal feeding system. Air ingress will decrease
the CO2 concentration below 95%. The requirement on the nal CO2
purity is not clearly dened in carbon capture and storage schemes,
and the need for emission control in the oxy-fuel process is,
therefore, uncertain. The CO2 condensation separates most of the
O2, N2 and the Ar, which are not condensed at the given conditions
but vented to the atmosphere. Control of impurities (i.e. NOx, SOx
and mercury) is required for emissions into the environment and
potentially for CO2 storage. The impurities can be controlled in
various parts of the process (as indicated in Fig. 1).
A In the furnace.
B In the ue-gas recycle loop, to limit the enrichment of impurities in the furnace.
C During the conditioning of the CO2, to limit the concentration
of impurities in the stored CO2 and/or in the ventilated gas.
D After the CO2 separation, to limit emissions in the ventilated
gas.
E After the CO2 separation, to limit impurities in the stored CO2.

387

In oxy-fuel combustion the once-through residence time of gas


in the furnace (sonce) must be distinguished from the effective
residence time (stot), which is the cumulative residence time
depending on the number of times the gas passes through the
furnace. For isomolar combustion, this can be calculated as the total
ow through the furnace divided by the fresh inlet ow of gas
(excluding the recycle), which is illustrated by the following
relationships,

sonce

stot

VC
FO2 FI FRFG

FO2 FI FRFG
VC
sonce
FO2 FI
FO2 FI

(1)

(2)

where FO2 is the volumetric ow of oxygen, FI the ow of other


gases introduced with the oxygen (mainly N2 and Ar), and FRFG the
ow of recirculated ue gas through the volume of the combustion
chamber (VC). For oxy-fuel combustion, FI approaches zero (from
being around four times FO2 in air combustion), and the total
residence time is signicantly increased under otherwise similar
conditions. The total residence time is most critical for the nitrogen
chemistry, and the once-through residence time (or volume) has
a subordinate impact on NOx reduction and could, therefore, be
reduced in the design of an oxy-red furnace. The combustion
process depends, however, on the once-through residence time,
which is also affected by the amount of RFG (or oxygen concentration), Eq. (1). Normally, in oxy-fuel combustion of the rst
generation, FRFG is set to obtain similar temperature and heattransfer conditions as in air combustion (30% O2 in the oxidizer),
which results in similar furnace volumes for air and oxy-fuel
combustion.
3.1. Limits for NOx in the oxy-fuel process
The oxy-fuel process has two outlet streams; the emitted vent
stream and the CO2-rich stream to be stored. The amount of NOx
allowed in the two streams should probably be limited, even
though there are no clear regulations at present. Such legislation
can be based on either environmental requirements or on best
available techniques (BAT) [14]. The BAT approach to emission
legislation is based on an assessment of the available techniques for
emission control. A denition of BAT is given in the EU directive for
integrated pollution prevention and control [15].
Emission of NOx to the atmosphere has been a major environmental concern since the beginning of the 1970s, and today there
are regulations on emission levels worldwide [14]. Emission limits
are usually dened as concentration limits (e.g. in Europe as mg/
Nm3 ue gas [16]). In oxy-ring, nitrogen is excluded from the
combustion and the ue-gas volume (Nm3) is decreased with
around 80% compared to air ring. Furthermore, the main part of
the ue gas is extracted for storage and only around 10% of the
generated ue gas is emitted to the atmosphere, see Table 1. The
same emission formation generates, thus, a higher concentration of
pollutants in oxy-fuel combustion, and emission limits based on
concentration in ue gas from air ring are not comparable to those
of oxy-ring without adjustments. Standards based on emission
per unit energy produced (e.g. mg/MJ electricity), which encourages emission reduction by efciency improvements, are incorporated in the USA. The energy penalty associated with O2 production
and CO2 compression and the efciency of the power process
inuence the emission per unit of energy produced. With state-ofthe-art efciencies, the emission must be reduced by around 20%
per unit of energy supplied in order to reach same emission per
unit of energy produced in an oxy-fuel power plant as in a

388

F. Normann et al. / Progress in Energy and Combustion Science 35 (2009) 385397

corresponding air-red unit. The emission per unit of fuel supplied


(e.g. mg/MJ fuel) is a similar unit, but it is not affected by the efciency of the power plant. Therefore, if a comparison between
processes is focused on the emissions only, the latter unit is
preferred.
The requirement for the purity of the gas to be stored is not an
emission limit in the same sense as that applied to a vented stream.
Storage of CO2 offshore was allowed in 2006 according to an
amendment to the London Convention Protocol (on dumping of
waste in the marine area) [17] and by a similar amendment to the
OSPAR Convention (on the protection of the North-East Atlantic) in
2007 [18]. Both conventions state that the gas to be stored should
consist overwhelmingly of CO2. No quantitative limits are dened.
The feasibility of co-storing NOx (and other pollutants) with the CO2
depends on the understanding of reservoir mechanics and
geochemistry as well as the public acceptance for dumping of NOx.
A review of on-going work on the determination of these limits is
given by Bachu [19].
4. Nitrogen chemistry
Nitrogen oxides or NOx include nitric oxide (NO) and nitrogen
dioxide (NO2). NO is the most important nitrogenoxygen product
of combustion, but it is further oxidized to NO2 at lower temperatures. Considerable formation of nitrous oxide (N2O) can take place
at lower combustion temperatures, as in uidized-bed combustion,
but it is not included in the present work. Nitrogen chemistry
during air ring has been thoroughly studied in several reviews, for
instance Refs. [4,5]. As indicated above, the conditions are changed
in the oxy-fuel process compared to an air-red power plant, both
with regard to the combustion process and the ue-gas train. The
principal changes, inuencing the NOx control, are summarized in
Table 2.
4.1. NOx in combustion processes
The nitrogen chemistry in combustion processes is summarized
in Fig. 2a. NOx are formed along three routes: thermal and prompt
formation from N2 and oxidation of fuel-bound nitrogen. Thermal
NO evolves from the recombination of N2 and O2, described by the
extended Zeldovich mechanism [20];

N2 O4NO N

(3)

N O2 4NO O

(4)

N OH4NO H

(5)

Reaction (3) has high activation energy, which controls the


reaction rate of thermal-NOx formation; temperatures above
1500  C are required to initiate the reaction. The Zeldovich

Table 2
Principal changes in the oxy-fuel process compared to an air-red power plant with
respect to NOx control (FGR ue-gas recirculation).
Relevant to primary measures

Relevant to secondary measures

Lowered concentration of N2
Recycling of ue gases (NOx)
Increased concentration of
combustion products
Changed residence time
(depending on FGR)
Changed temperature conditions
(depending on FGR)

Increased pressure
Decreased temperature
Increased concentration of combustion
products
Reduced mass ow

mechanism is reversible and reduces NO when the equilibrium


concentration of NO is low enough, given that the temperature is
sufciently high for the Zeldovich mechanism to be active. Prompt
NO [21] is initiated by the reaction between N2 and hydrocarbon
radicals forming a volatile-N (an intermediate gaseous compound)
species, which is oxidized to NO or reduced back to N2. Prompt NO
is of minor importance and occurs predominantly under fuel-rich
conditions. The conversion of fuel-bound nitrogen contributes to
most of the NO formed during combustion of coal. Fuel-N is split
into volatile- and char-N during the devolatilization. The volatile-N
transforms into either NO or N2, while char-N reacts through a set
of heterogeneous reactions along with the oxidation of char. The
split between volatile- and char-N varies with type of coal and
depends on qualities like nitrogen content, coal rank and volatility,
but it also depends on combustion conditions, such as heating rate
and temperature. The NO formed can also be reduced to N2. Similar
to the prompt formation, NO can be reduced by hydrocarbons to
volatile-N under fuel-rich conditions (known as reburning).
Furthermore, if present in sufcient quantities, char could be
important as a catalyst for the reduction of NO, either directly, or by
reaction with carbon monoxide (CO) or hydrogen (H2).
The volatile-N formed from fuel-N, N2 or from NO mostly
consists of hydrogen cyanide (HCN) and ammonia (NH3). These
species react in a series of reactions, but nally they end up as NH
and N, as shown in Fig. 2b. The subsequent reactions, which
determine if NO or N2 is formed, are highly dependent on the O/OH/
H radical pool, which is related to the ame conditions (e.g. stoichiometry, temperature and composition) [4].

4.2. Inuence of oxy-fuel combustion on nitrogen chemistry


The properties of the combustion process differ between air and
oxy-combustion. The new conditions of the oxy-combustion
process that may be of importance for nitrogen chemistry are listed
in Table 2. The external recycle of ue gas in the oxy-fuel process
affects nitrogen chemistry, since it increases the concentration of
combustion products and inuences the residence time and the
temperature prole in the furnace. In air-fuel combustion, N2 is
dominant in the combustion gas, whereas in the oxy-fuel case with
recirculation, CO2 plays that role. The higher thermal capacity of
CO2 (the ratio of molar heat capacity for CO2 and N2 is around 1.6)
tends to decrease the combustion temperature, which can be
compensated for by higher oxygen concentration (reduced CO2
mass ow). Besides the heat capacity difference, N2 is transparent
to thermal radiation, and the gas emissivity is higher in an atmosphere with elevated concentrations of CO2 and H2O. The importance of increased gas radiation in a coal-red ame is, however,
limited because of the dominance of particle radiation [22].
Chemically, the replacement of N2 with CO2 is, obviously, of
importance for the prompt and the thermal-NOx formation. Fig. 3
presents the inuence of N2 concentration on the equilibrium
concentration of NO and on the reduction of 1000 ppm NO during
a residence time of 5 s at two oxygen stoichiometries. At low
temperatures, the equilibrium concentration is always low and no
formation of NO occurs. At higher temperatures, both the equilibrium concentration and the reaction rate increases. When the
concentration of N2 and the stoichiometric oxygen/fuel ratio (l) are
high, as during air ring, NO is formed, but when the concentration
of N2 and l are low, NO is reduced. The optimal temperature with
respect to NOx reduction depends on the combustion conditions,
but it is higher in oxy-ring than in air ring. At temperatures
above 1600  C, reduction of NO is strongly dependent on the
nitrogen concentration (oxygen purity and air ingress). This
dependence is, however, lower at sub-stoichiometric conditions.

F. Normann et al. / Progress in Energy and Combustion Science 35 (2009) 385397

389

Fig. 2. (a) Overall mechanisms of NO formation and reduction. (b) Reaction-path diagram, illustrating the decisive steps in volatile-N conversion to NO or N2 (shaded area in Fig. 2a)
[4]. The dashed line indicates multiple reactions. Vol-N denotes intermediate gaseous compounds containing nitrogen, e.g., HCN or NH3.

The elevated concentration of CO2 in oxy-fuel combustion also


inuences the radical pool of the combustion process, primarily
through Reaction(6), [23,24];

to the increased CO concentration in oxy-fuel combustion, it is


small compared to the contribution of the homogeneous reactions.

CO2 H4CO OH

4.3. Inuence of CO2 conditioning on nitrogen chemistry

(6)

Glarborg and Bentzen [25] investigated the effect of increased


CO2 concentration in a small-scale methane ame and detected
signicantly increased concentrations of CO, see Fig. 4, caused by
Reaction (6) and, to some extent, by reactions of CO2 with hydrocarbons. They also concluded that Reaction (6) will raise the
concentration of hydroxyl radicals (OH), which could promote the
formation of NO from volatile-N (cf. Fig. 2b). It has been suggested
[26,27] that the concentration of CO in oxy-coal combustion could
also be affected by the heterogeneous Boudouard reaction;

CO2 CS42CO

(7)

This was further investigated by Mackrory [28] who concluded


that, even though the contribution of Reaction (7) is of signicance

The purpose of the ue-gas train in an oxy-fuel power plant is


different from an air-red plant. In an oxy-fuel power plant, the
focus is on the conditioning of CO2 rather than on the treatment of
the vented gas. Therefore, new conditions that may be of importance for the nitrogen chemistry are created; see Table 2. Representative physical properties of the CO2 conditioning are presented
in Table 1. The most important effect is that the reduced mass ow
(elimination of N2), high pressure and low temperature drastically
reduce the volume ow throughout the ue-gas train. As a consequence, the later in the ue-gas train the NOx reduction is performed, the smaller is the ue-gas volume that has to be treated,
and the size of the treatment equipment is reduced in a corresponding manner.
The elevated pressure and the low temperature required in the
CO2 condenser also affect the chemistry of importance for NOx
control. The oxidation rate of NO by the O2 present in the ue gas,
according to

2NO O2 42NO2

(8)

is favoured by low temperature and high pressure [29]. This is


a well known reaction, describing NO2 formation in the industrial
production of nitric acid (HNO3) by the Ostwald process [30] at
pressures around 10 bar. Fig. 5 illustrates the oxidation rate of NO to
NO2 in a ue-gas stream at representative pressures, calculated
with the reaction scheme of Skreiberg et al. [13]. Downstream of
the compressor (Stream 4 in Fig. 1 and Table 1), the pressure is

Fig. 3. Inuence of N2 concentration on the NOx reduction potential as obtained by


modelling of gas-phase chemistry. i 0% N2, ii 1% N2, iii 10% N2. Full lines
equilibrium concentration, dashed lines 5 s residence time. l stoichiometric ratio.
Initial concentration of NO 1000 ppm.

Fig. 4. Experimental data on outlet CO concentration from a ow reactor for oxidation


of CH4 under fuel-lean conditions with N2 (closed symbols) or CO2 (open symbols) as
bulk gas. Source: Ref. [25].

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F. Normann et al. / Progress in Energy and Combustion Science 35 (2009) 385397

Fig. 5. Inuence of pressure on the conversion of NO to NO2. Calculated by gas-phase


chemistry applied to a plug-ow reactor, NOinitial 400 ppm and, O2,initial 3%,
temperature 20  C.

sufcient (around 30 bar) for a large part of the NO to be converted


to NO2 within the ue-gas train, which is not feasible in an air-red
power plant. NO2 can be controlled by other techniques than those
available for NO, and new measures are enabled (further discussed
in Chapter 6). A complete oxidation to NO2 is feasible only at very
high pressures and long residence time, which is a limitation of the
technique.
5. Primary measures
Primary measures aim at adjusting the combustion parameters
in order to reduce the formation of NOx from fuel-bound nitrogen
and N2, or to reduce the NOx formed inside the furnace. Conventional primary measures for NOx control that could be applied in
oxy-fuel combustion are illustrated in Fig. 6. These are: fuel staging
(reburning), air-staging (staging), and low-NOx burner technology.
In addition, the ue-gas recirculation in oxy-fuel combustion offers
an opportunity for NOx reduction, and a technique using hightemperature oxy-fuel combustion to reduce NOx has been proposed
[31].
5.1. Fuel-staging
Fuel staging, or reburning, (Fig. 6a) is a way to reduce the formed
NOx to N2 by reaction with hydrocarbon radicals, according to
Fig. 2a. The reduction is carried out by introduction of fuel downstream of the primary combustion zone. No additional oxidizer is
added in the reburning zone, and the ame is partly sub-stoichiometric yielding hydrocarbon radicals, which reduce the NOx
formed in the primary combustion zone to volatile-N species.
Downstream of the reburning zone, additional oxidizer is

introduced into the furnace to ensure burnout of the fuel. The goal
is to convert the volatile-N to N2. In accordance with Fig. 2b, this is
achieved by creating a sub-stoichiometric zone when introducing
the reburning fuel. Often, natural gas is used as reburning fuel, but
any hydrocarbon fuel may sufce. Current development of fuel
staging under air-red conditions is focused on optimization of the
controlling parameters (i.e. stoichiometry, temperature and residence time), investigating fuels for reburning, and, developing
advanced reburning concepts with additives like ammonia to
enhance NOx reduction [32,33].
The formation of OH radicals by Reaction (6) at elevated
concentrations of CO2 could affect fuel staging negatively during
oxy-fuel combustion by promoting the formation of NO from the
volatile nitrogen species produced by the reburning mechanism
[25]. It is also discussed by Park et al. [34] that elevated CO2
concentration can suppress the reburning mechanism. Fuel staging
has not yet been applied in experimental NOx studies related to
oxy-fuel ring. There is, however, some related work where the
reburning mechanism has been studied for reduction of NOx in the
primary zone (further discussed in Section 5.4). Based on these
studies, the reduction potential can be expected to be similar to that
during air ring, despite the possible negative impacts mentioned.
5.2. Air-staging
In air-staged (or simply staged) combustion (Fig. 6b) the aim is
to inhibit the formation of NOx by dividing the furnace into two
zones. In the primary zone, only a part of the oxidizer is introduced
with the fuel to form an initial oxygen-lean combustion zone. The
remaining oxidizer is added as over-re air (over-re oxidizer) in
the secondary combustion zone to complete the fuel burnout. By
reducing the supply of oxygen in the primary zone, which is critical
to NOx formation, less NOx (and more N2) is formed from the fuelbound nitrogen (see Fig. 2). The peak temperature of combustion is
decreased by the sub-stoichiometric conditions. The major drawback of this procedure is the risk for low combustion efciency and
corrosion. The research on air-staging is mostly focused on developing further understanding of the process for optimization of
combustion parameters and ring strategies.
Staged combustion has been experimentally investigated for
pulverized-coal combustion in an O2/CO2 environment. Fig. 7
shows results of a staging experiment by Maier et al. [35] performed in a once-through (O2/CO2 combustion without ue-gas
recirculation) 20 kW electrically heated test unit. The results show
that staged combustion is as effective for NOx reduction in oxy-fuel
as in air combustion. Furthermore, Maier et al. detected increased
concentrations of CO in the oxygen-lean zone during oxy-fuel
conditions, which can be seen as a result of Reactions (6) and (7), as
discussed in Section 4.2. Possible consequences are increased
corrosion if the atmosphere at the furnace walls is reducing and
a requirement to redesign the burners to counteract this issue. Liu
et al. [36] investigated two levels where the secondary oxidant

Fig. 6. Sketches of conventional primary measures for NOx control: (a) fuel-staging (reburning), (b) air-staging in furnace (overre), and (c) air-staging in burner (low-NOx burner).
l is the stoichiometric ratio.

F. Normann et al. / Progress in Energy and Combustion Science 35 (2009) 385397

391

oxy-fuel processes. In contrast, Becher et al. [38] and Hohenwarter


and Giendl [39] have investigated burners operating with high O2
concentration (up to 50% O2), where the combustion temperature is
controlled by lowering the stoichiometric oxygen/fuel ratio. The
inuence on NOx formation during the employment of these
burner concepts was, however, not investigated. Tan et al. [40]
studied the performance of burners for NOx reduction using
a combination of experiments and CFD modelling. They concluded
that burners should be specically designed for oxy-fuel combustion and take advantage of the pure O2 stream to minimize NOx
formation.

5.4. Flue-gas recirculation

Fig. 7. Measured axial emission prole during staged combustion with 27% O2/CO2
(once-through) and air combustion at a burner stoichiometry of 0.75, overall stoichiometry of 1.15 and a residence time in the reduction zone of 3 s. Filled symbols:
unstaged combustion [35].

could be introduced in a 20 kW test unit and came to similar


conclusions: staging of the oxidizer is an efcient method for
controlling emissions of NOx, and the conventional design of OFA
(over-re air) ports should work well also in oxy-fuel combustion.
5.3. Low-NOx burner technology
Low-NOx burners (Fig. 6c) are a well proven technology for NOx
control in pulverized-coal combustion. Staging of the oxidizer is the
central technique applied in low-NOx burners. The combustion
zones are created by dividing the oxidizer ow into secondary and
tertiary streams surrounding the main combustion zone where the
fuel is converted. New boilers in countries with strict NO-regulations all employ low-NOx burners. Low-NOx burners are easily
combined with air-staging, fuel staging, or secondary measures to
achieve further reduction of NOx. The development of low-NOx
burners is an on-going process with the following common
objectives [37]:

Recirculation of ue gases is used in air-red power plants to


lower the emission of NOx by decreasing the concentration of O2 in
the combustion zone and to lower the combustion temperature to
suppress the formation of fuel-NOx as well as thermal-NOx. It was
concluded by Andersson et al. [41], Mackrory [28] and Okazaki and
Ando [42] that a more important effect of the ue-gas recirculation
in oxy-fuel combustion is reduction of NOx that is reintroduced to
the ame. Nozaki et al. [43] came to a similar conclusion after
detecting elevated concentrations of HCN and NH3 in the early
stages of the ame, which indicates that NOx is reduced via
reburning reduction when recycled as illustrated by Fig. 2. The
effect of the increased reduction is seen in several experimental
investigations (in test furnaces of a fuel power between 0.1 and
2.5 MW) [40,41,4448] on the differences in NOx emissions
between oxy-fuel combustion with recycle and air combustion.
Fig. 8 presents data from previous work, showing the maximum
reduction in NOx emission when switching from air to oxy-fuel
combustion. The emission of NOx from oxy-fuel combustion related
to unit of fuel supplied is typically reduced to around 30% of the
emission during air ring, mainly due to the reduction by reburning
in the fuel-rich regions generated in the ame during recirculation
of ue gas. It should be noted that these experiments were performed in a temperature range where the inuence of the thermal

- maximizing the rate of volatile evolution and total volatile


yield from the fuel in the early reducing part of the ame,
- creating an initial oxygen-lean zone to minimize the conversion of fuel-N to NOx,
- optimizing the residence time and temperature in the reducing
zone with respect to fuel-N to NOx conversion,
- maximizing the residence time of char in fuel-rich regions to
minimize conversion of char-N to NOx, and,
- avoiding high-temperature peaks to minimize formation of
thermal NOx.
In connection with the design of oxy-fuel burners it has been
commonly suggested that the oxygen concentration in the recirculation gas should be around 30% to achieve stable combustion
with conventional burners, see review by Buhre et al. [1]. Also,
burners specically designed for oxy-fuel combustion have been
proposed: Toporov et al. [27] designed a burner to sustain
combustion at O2 concentrations below 21% for membrane-based

Fig. 8. Experimental data on NOx emissions under air-fuel and oxy-fuel conditions
(maximum reduction achieved). Full line: NOx emission during oxy-fuel combustion is
34% of the emission during air ring. The dashed line denotes equal emission.

392

F. Normann et al. / Progress in Energy and Combustion Science 35 (2009) 385397

mechanism (Reaction (35)) is low for both NOx formation and


destruction.
The importance of ue-gas recycling is emphasized by
comparison with once-through oxy-fuel experiments [35,36,49]
(>0.1 MW), which do not show any substantial difference in the
emission of NOx between oxy-fuel and air-red cases. Instead,
once-through experiments show increasing conversion of fuel-N to
NOx with increasing concentration of oxygen and combustion
temperature. In order to decrease the concentration of O2 in the
oxidizer without reducing the combustion efciency, Liu and
Okazaki [50] proposed an oxy-fuel combustion process with heat
recirculation. By heating the ue gas before recycling it to the
furnace, the concentration of O2 required in the oxidizer for stable
combustion was lowered from 30% to 15% and, thereby, the
conversion of fuel-N to NO was lowered from 0.08 to 0.04 (it was
0.3 for air combustion).
5.5. High-temperature NOx reduction
In a second-generation oxy-fuel power plant, new concepts of
combustion chambers can be considered. In this context, Normann
et al. [31] have proposed a combustion process that uses high
combustion temperatures to reduce nitrogen oxides in oxy-fuel
combustion, taking advantage of the reversed Zeldovich mechanism. The furnace is designed for an oxidizer with high concentration of oxygen (low ue-gas recirculation) and with burners
promoting rapid mixing to achieve high combustion temperature;
18002000  C is required. This design would achieve more intense
combustion and lower volume ows through the furnace, which
increase combustion efciency and result in a more compact and
cost-effective boiler. In the proposed process, the concentration of
nitrogen should be kept low in the combustion atmosphere (w1%)
through high purity oxygen and low levels of air ingress to decrease
the equilibrium concentration of NO (cf. Fig. 3). The major feature of
the technique is melting of the ashes, which has to be handled by
the furnace design. Boilers (air red) with wet ash drainage exist
and a similar design should be applicable. The high-temperature
NOx reduction is proven in principle by modelling, employing
detailed reaction mechanisms with NOx reduction efciencies up to
95%, but experimental validation remains to be done.
Fig. 9 presents a comparison between NOx emissions in hightemperature combustion and conventional combustion (the reference case, 1500  C) calculated with a detailed kinetic mechanism
[31]. The inlet concentration of NO (marked with a circle in Fig. 9) is
calculated from the outlet concentration of the furnace adjusted for
the addition of oxygen to the RFG. The difference between the inlet
and maximum concentrations of NO arises from the conversion of
volatile-N to NO, which is fast at the time scale of the diagram. The
diagram shows that the reduction during the high-temperature
combustion is improved compared to the reduction at conventional
temperature [31]. Staging of the oxidizer reduces the emission
further. Fig. 10 shows the major reaction paths obtained by a rateof-production analysis, integrated for a time scale of 0.1 ms to 2.5 s.
The calculations are based on the cases in Fig. 9. The rst 0.1 ms is
left out as it is dominated by the oxidation of fuel-N. It is shown
that the reaction route NO to N2 via N and NO to N2 dominates
the reduction of NO, which is caused by the reverse Zeldovich
mechanism (Reactions (13)), as opposed to air-red conditions
where this mechanism forms NOx from air-borne nitrogen.

Fig. 9. Performance of high-temperature NOx reduction. Calculation of CH4O2/RFG


combustion in a plug-ow reactor with a mixture of HCN (60%) and NH3 to represent
fuel-N (0.6 wt% d.a.f.). The circles indicate the inlet concentration of NO and the arrows
a temperature drop of 100  C. Maximum temperature is 1500  C and 2000  C in the
reference and high temperature cases, respectively. The stoichiometric ratio is 1.1,
except during the rst 2 s in the staged combustion case when it is 0.8. Source:
Ref. [31].

6. Secondary measures
Secondary measures aim at converting or capturing NOx in the
ue-gas downstream of the combustion process. Generally,
secondary measures have the disadvantage of requiring additional

Fig. 10. Normalized net production of major species during the reduction of NO in
Fig. 9.

F. Normann et al. / Progress in Energy and Combustion Science 35 (2009) 385397

393

equipment and additives to control the emissions. On the other


hand, secondary measures do not interfere with the combustion
process and usually perform better in terms of NOx reduction than
primary measures. The two most common secondary measures are
selective catalytic reduction (SCR) and SNCR, Fig. 11. The oxy-fuel
process also has the possibility to remove NOx as NO2. NO2
formation is favoured by high pressure, and the NO2 removal
processes must be located in the high-pressure part of the ue-gas
train (Streams 46 in Fig. 1). In addition to SCR and SNCR, three
options to capture NO2 are presented, Fig. 12: absorption in water,
co-storage with CO2, and distillation.
6.1. SCR
Selective catalytic reduction is based on reduction of NOx by
ammonia (or urea) to form nitrogen and water according to Reaction (9),

4NO 4NH3 O2 44N2 6H2 O

(9)

The reduction occurs over a catalyst, usually at 300400  C, but


the temperature window can be expanded depending on the
catalyst used, see [51]. The ammonia is injected into the ue-gas
upstream of the catalyst. Catalyst technology is important for the
process, and much of the on-going research is focused on
improving the catalyst [51]. There is, however, no work presented
on the inuence on the catalyst activity from the changed ue-gas
composition during oxy-fuel combustion. The selectivity of the
process is high, allowing for an NH3NOx stoichiometry near unity.
Even distribution of the NH3 and efcient reactions are important
to avoid ammonia slip (unreacted ammonia in ue-gas after the
NOx reduction unit) with possible downstream effects, such as
build-up of ammonium salts on heat-transfer surfaces or emission
of ammonium chloride and gaseous ammonia.
The ue-gas train of an oxy-fuel power plant offers new
conditions to consider when deciding where to locate the SCR unit.
The cost of an SCR unit depends on the ue-gas volume [52], and
a location in the latter part of the oxy-fuel ue-gas train is, therefore, benecial, as seen by the ue-gas conditions in Table 1: the
treated volume decreases throughout the ue-gas train and is
smaller than in an air-red power plant. The reduction of NO by
Reaction (9) is not thermodynamically favoured by an increased
pressure and, the SCR unit should not be placed in the pressurized
part of the ue-gas train. Fig. 11 shows the four basic locations for
the SCR reactor in the ue-gas treatment train: High-dust, lowdust, tail-end and tail-end vent. The high-dust option is the most
common technique in air-red power plants. In the oxy-fuel
process, a high-dust unit would be placed in the recycle loop where
the ue-gas ow is larger but the total residence time (stot) is
increased by the recycle (cf. Eq. (2)), which decreases the required
volume of the SCR unit. The gas recycle will also have the consequence that the N2 formed from the ammonia added and from the
NOx reduced may be converted to NOx when returned to the

Fig. 12. Sketches of NO2 processes, located downstream of the rst compression in
Fig. 1. (a) Absorption in water, (b) co-storage with CO2, (c) distillation.

furnace. The low-dust SCR is placed outside the recycle loop and
has lower catalyst degradation compared to a high-dust option. The
low-dust option is normally not used in air-red power plants due
to the high cost of installing a high-temperature dust separation.
However, in oxy-fuel combustion ue-gas recycle at higher
temperature gives an incentive to install a high-temperature dust
separator. The ue gas of an oxy-fuel power plant will have higher
concentration of sulphur dioxide (SO2), which could be oxidized to
sulphur trioxide (SO3) in the SCR. To prevent SO3 formation, a uegas desulphurization unit (FGD) prior to the SCR might be required,
which would necessitate a tail-end SCR. The tail-end option differs
from the low-dust option in that it is placed downstream of an FGD
where the ue gas is cooled and must be re-heated before entering
the SCR, and this has a negative impact on plant efciency. In the
tail-end (vent), option the SCR unit is placed downstream of the
CO2 condenser and only a fraction of the initial volume is processed.
In this case the NOx following the CO2 stream is not reduced. The
NO part of the NOx leaves the CO2 condenser with the vent gas,
while NO2 stays with the CO2, and, consequently, it may be of

Fig. 11. Positions for SNCR and SCR (high-dust, low-dust and, tail-end) in the oxy-fuel process. FGD ue-gas desulphurization.

394

F. Normann et al. / Progress in Energy and Combustion Science 35 (2009) 385397

Fig. 13. Comparison between NO reduction by SNCR during air and oxy-fuel conditions. Calculated by gas-phase chemistry applied to a plug-ow reactor, residence time
0.1 s, NOinitial 400 ppm, O2,initial 3% and, NH3:NO 2:1. Based on modelling of gas-phase
chemistry.

importance to control the oxidation of NO (see Fig. 5). The tail-end


(vent) option also requires re-heating of the ue gas to attain the
desired temperature for reaction, but the ue-gas ow is small and
heating to some extent is probably required anyway before the
stack.
6.2. SNCR
Selective non-catalytic reduction operates by the same overall
reaction as SCR (Reaction (9)), but the SNCR arrangement does not
include a catalyst. Instead, the temperature must be higher for the
reactions to be active (>800  C). At too high temperatures
(>1100  C), the ammonia tends to oxidize to form NOx instead of
reducing it. Thus, the reduction takes place in the temperature
window between 800 and 1100  C, which is normally found
somewhere along the gas path of a pulverized coal-red boiler. The
SNCR principle is, therefore, simply applied by injection and thorough mixing of the reducing agent (ammonia) in the ue-gas
stream within this temperature window. The SNCR is not as
selective towards reduction of NOx as the SCR system, and the NH3
to NOx molar ratio should be above unity. The efciency of the
reduction tends to increase with the NH3 to NOx ratio up to
a certain level depending on operational condition: the optimum

performance is often found at a molar ratio between 1.5 and 2.5.


The SNCR system is more difcult to control during load variation
than the SCR, and the risk for ammonia slip is higher. The slip of
ammonia is mainly caused by insufcient mixing or if applied with
inappropriate temperature or concentration proles in the ue gas.
It is known that the NH3NOx reaction is sensitive to changes in
the radical pool, and the effect of the ue-gas composition and
additives has been thoroughly investigated; see review by Javed
et al. [53]. For example, water slightly increases the optimum
temperature [54], whereas presence of hydrogen could reduce the
optimum to as low as 700  C [55]. The inuence of oxy-fuel
combustion on the NH3NOx reaction mechanism has not been
investigated. However, as previously mentioned, an increased CO2
concentration will inuence the radical pool and this will affect the
temperature window. To illustrate the effect of CO2, the reduction
of NO by SNCR is calculated for both air and oxy-fuel conditions
with the detailed kinetic mechanism from Ref. [31]. In the latter
case, N2 in the ue gas simply is replaced by CO2. The result is
shown in Fig. 13. The efciency of SNCR is similar in oxy-fuel and air
combustion, but the optimum temperature is shifted to higher
temperatures and the temperature window is increased.
An SNCR arrangement must be placed inside the recycle loop to
nd the required temperature of the process. Similar to the case
with a high-dust SCR unit, the total residence time is increased by
the recycle of ue gas (cf. Eq. (2)), and a large part of the N2 formed
from both NOx and NH3 will be reintroduced to the ame with
a chance of reforming NOx, but in SNCR even more NH3 is added
due the lower selectivity. The inuence of this excess of NH3 on the
emission depends on the combustion conditions and on the
performance of the SNCR in reducing NOx.
6.3. Absorption of NOx
Absorption of NOx in water has been thoroughly studied due to
its importance for industrial production of nitric acid; see [30] and
references therein. The mechanism of NOx absorption presented by
Counce and Perona [56] is shown in Fig. 14. NO is oxidized in the gas
phase before it is absorbed and nally bound in the liquid as HNO3.
The oxidation of NO to NO2 is the critical step for the absorption. As
discussed in connection with Fig. 5, the low temperature and high
pressure in the CO2 condensation step of the oxy-fuel process
favour NO2 formation. Furthermore, these conditions increase the
concentration of nitrogen tetroxide (N2O4) at the expense of NO2,
which is known to enhance the absorption [57]. The initial
concentration of NOx in the gas and the concentration of HNO3 in
the absorbing liquid are important design parameters. The acid
strength is of great importance for the equilibrium between the gas
and the liquid phase, and thus for the outlet concentration
(achievable reduction) of NOx, while the concentration of NOx
mainly inuences the absorption rate. The concentration of NOx in

Fig. 14. Mechanism for absorption of NOx in water [56].

F. Normann et al. / Progress in Energy and Combustion Science 35 (2009) 385397

the ue gas is lower than in an acid production plant, but the


requirement on concentration of HNO3 is not necessarily high for
ue-gas cleaning. Absorption in water has been proposed for
secondary NOx control in air-red power plants [58]. The
requirement of a strong oxidizer (e.g. ozone or hydrogen peroxide)
or an efcient catalyst to oxidize NO to NO2 at atmospheric
pressure has, however, prevented these processes from commercial breakthrough.
Absorption of NOx in the oxy-fuel process (Fig. 12a) has been
studied by Allam et al. [59], White et al. [60,61], and Kuhnemuth
et al. [62,63]. They conclude that absorption of NOx in water at
around 30 bar and 30  C is a feasible technology, achieving reduction efciencies of up to 90%. Fig. 15 shows the absorption of NOx
from an oxy-fuel ue-gas [63]. The oxidation of NO to NO2 is
strongly dependent on pressure and this is a condition for the
absorption of NOx (cf. Fig. 5). The absorption is limited by equilibrium, and in the calculated case the reduction limit is just below
200 ppm (at 30 bar). The performance of the downstream CO2
condenser is negatively affected by pressures above 30 bar where
the purity of the nal CO2 decreases [64], and it is, therefore, not
practical to further increase the pressure solely for the NOx
absorption.
Common for the processes investigated is that they include
simultaneous removal of SO2 based on the Lead-chamber process
[65] for sulphuric acid (H2SO4) production. In this process, the NO2
formed works as a catalyst for the rapid oxidation of SO2 to SO3. SO3
is highly soluble in water and is transformed to sulphuric acid in
a separate absorption column upstream of the absorption of NOx. In
the case of simultaneous SO2 removal, NO2 is required in relatively
high concentration, and, therefore, the formation of NOx in the
preceding system must be sufcient [63]. Initial small-scale
experiments have been performed on the SO2 absorption with
promising results [61]. However, the technique cannot be considered mature, as can the absorption of NO2.
6.4. Phase separation
Phase-separation is a common industrial method for separating
the components of a mixture. The separation is based on the
difference in composition between the liquid and the gas phase of
the mixture. In practice, there are two principal methods: singlestage partial vaporization without reux (ash distillation), and
multi-stage distillation with reux (distillation). Flash distillation is
used for separating components that boil at widely different

Fig. 15. Absorption of NOx from an oxy-fuel ue-gas at different pressures (20  C).
Source: Ref. [63].

395

temperatures, while the more rigorous distillation column is


needed for separating components of comparable volatility. In the
oxy-fuel process, phase separation is performed in connection with
the CO2 condenser to separate gaseous O2, N2 and Ar. The boiling
point of NO2 (Tb,30bar z100  C) is higher than the boiling point of
CO2 (Tb,30bar z0  C) and NO2 is, thus, condensed in the CO2
condenser. In contrast, NO has a lower boiling point than CO2
(Tb,30bar z100  C) and is emitted with the vented gases from the
CO2 condenser. An option to control the atmospheric emission of
NOx, which is not available for air-red power plants, is to co-store
the NO2 with the captured CO2 (Fig. 12b). To avoid emission of NO it
is important that the residence time of the ue-gas at elevated
pressure is sufcient for the oxidation of NO to NO2 to go to
completion (see Fig. 5). This option is achieved without extra
equipment as the CO2 condenser is required anyway, but the CO2 to
be stored is polluted by NO2, which might not be acceptable.
To prevent pollution of the CO2 stream, Allam et al. [66,67] have
suggested a process with a distillation column operating at a higher
temperature downstream of the CO2 condenser (Fig. 12c) to separate NO2 from the CO2 stream. In this column, NO2 remains in the
liquid phase while CO2 is separated as a gas. The CO2 is then
condensed again and compressed to the transportation pressure.
This process has also been studied by Kuhnemuth et al. [63] and
Gonshorek [68], of which the latter indicates on-going construction
of a pilot plant. Common for all studies is that also the CO2
condenser consists of a distillation column, instead of a ash tank.
The separation of CO2 and NO2 is efcient and a high reduction of
the NOx emission is achieved (up to 97%) [63], but compression
work in addition to that needed for the condensation of CO2 is
required. SO2 has a boiling point in between CO2 and NO2 (Tb,30bar
z100  C) and can be separated with the NO2 in the second column
at the cost of even further increased compression work.
7. Summary and discussion
The performance of the NOx-control measures reviewed in the
present work is summarized in Table 3 as independent processes
(combinations are not considered). Overall, the conditions for
controlling NOx emission in the oxy-fuel process are better and the
number of parameters available for process optimization is higher
than in an air-red power plant, both in terms of primary and
secondary measures. Primary measures have proven a reduction of
around 65% of the emission (per unit of fuel supplied) during oxycombustion compared to air-combustion, utilizing technology
designed for air ring (see Fig. 8). High-temperature NOx reduction
is an example of how the combustion and emission levels could be
further improved if the features of oxy-fuel combustion are optimized. Secondary measures normally require additional equipment, but the volume ow of ue gas throughout the oxy-fuel
process is heavily decreased compared to an air-red power plant
(see Table 1), which directly reduces the investment cost of the
additional equipment. Furthermore, in the high-pressure part of
the ue-gas train, the oxidation rate of NO to NO2 increases and
a new set of secondary measures applicable to NO2 is enabled.
Primary and secondary measures can be used separately or in
series. For a rst generation of oxy-fuel power plants, conventional
primary measures should be enough to achieve the present emission limits if based on unit of fuel supplied. The secondary
measures are favoured by a combination with primary reduction of
NOx, with one exception; the lead-chamber process requires NOx to
capture SO2. Even co-storage of NOx with CO2, which is basically
free of cost, benets from primary measures in terms of improved
public acceptance and less need for safety measures during transport and storage. Based on this, it is probable that the combustion
process will be designed for NOx reduction also in a second

396

F. Normann et al. / Progress in Energy and Combustion Science 35 (2009) 385397

Table 3
Summary of the performance of measures for NOx control when applied to the oxy-fuel process. The achievable reduction is for the measure concerned and not for addition or
multiplication of measures. The achievable reduction for High temperature is in combination with staging as described in Section 5.5.
Advantages

Disadvantages/tendencies

Achievable reduction

Primary Measures
Reburning

Conventional technology

(Natural gas consumption)


High-temperature corrosion

60%a

Staging

Conventional technology

Reduced combustion efciency


High-temperature corrosion

40%a

Low-NOx burner

Conventional technology

Reduced combustion efciency


High-temperature corrosion

60%a

Flue-gas recirculation

Included in the oxy-fuel process

High temperature

Improved combustion efciency


Small and compact furnace

Melting of ashes
Requires low N2 concentration
High-temperature corrosion

90%c

Secondary Measures
SCR

Conventional technology

Requires catalysts
Ammonia consumption
Extra units
Ammonia slip

95%a

SNCR

Conventional technology

Ammonia consumption
Ammonia slip

50%a

Absorption

Simultaneous removal of SOx


Placed in high-pressure part

Extra units
Waste (weak nitric acid)

90%c

Co-storage

Included in the oxy-fuel process

Pollution of the CO2

95%c

Distillation

Simultaneous removal of SOx


Placed in high-pressure part

Power consumption
Extra units
Waste (liquid NOx)

95%c

a
b
c

65%b

Based on practical experience under air-red conditions [52].


Based on experiments under oxy-fuel conditions (Fig. 8).
Based on modelling of the oxy-fuel process [31,63].

generation of the oxy-fuel process. However, the optimization may


be different from that of present pulverized fuel plants and could
focus more on combustion efciency. The constraints on fueloxidizer mixing to lower the combustion temperature in order to
control thermal-NOx formation are not as important. With low N2
concentration in the furnace, high combustion temperatures could
even be promoted to reduce NOx by the thermal mechanism.
Furthermore, if any of the secondary measures prove to be efcient
and cost-effective for NOx control in the oxy-fuel process, the
demand on primary reduction could be lowered, i.e., during the
design of the combustion process less consideration is required on
NOx emission.
As the design of oxy-fuel power plants matures, secondary NOx
control in connection with the compression and the CO2 condenser
are of interest, due to the benet from the lower volume ow. The
tail-end (vent) SCR unit is a favourable option to control NOx in the
vent stream; the concentration of NO is high and the treated ow is
small. If required, distillation and absorption of NO2 are promising
techniques to control NOx in the CO2 stream, although both have
the disadvantage of creating a by-product that must be disposed.
The most advantageous alternative to control emissions of NOx in
the oxy-fuel process is co-storage with the captured CO2. It is,
however, uncertain to what extent co-storage of NO2 will be
allowed, although the concentration in the storage gas is small. This
may also depend on the type of storage employed.

8. Future work
The present study has demonstrated several methods to reduce
NOx emission in the oxy-fuel process. However, an economical
evaluation or a system study to nd out the optimum organisation

of NOx capture still remains to be done. The survey has lead to the
conclusion that more knowledge is required in three key areas to
optimize NOx control in future oxy-fuel power plants.
- Legislation. NOx control is driven by emission legislation.
Regulations adapted to CO2 removal processes are, therefore,
required both with respect to emissions to the atmosphere and
for the storage gas in order to nd appropriate design solutions
for the oxy-fuelCO2 capture system.
- Oxidation of NO to NO2. The differences in behaviour of NO and
NO2 makes it essential to further investigate the oxidation of
NO under the conditions of the CO2 conditioning. The performance of the CO2 condenser in separating NO and NO2 is also
crucial.
- The combustion process. NOx control has constrained the design
of air combustion for a long time. It is, therefore, of importance
not to imitate air combustion in future developments but to
utilize the opportunities given by oxy-fuel combustion to nd
the optimal performance, both with respect to emissions and
combustion efciency.
Acknowledgements
This work is nanced by Vattenfall AB. Our colleague, Mr Daniel
Kuhnemuth, is acknowledged for his valuable input on the removal
of NO2.
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