Proy. Eneroy Combust. Sci., Vol. 6, pp. 287 302. 0360 1285/80/0901 0287505.

00/0
© Pergamon Press Ltd., 1980. Printed in Great Britain.

POST COMBUSTION METHODS FOR

CONTROL OF NOx EMISSIONS

H. S. ROSENBERG, L. M. CURRAN, A. V. SLACK, J. ANDO a n d J. H. OXLEY

Battelle Columbus Laboratories, 505 Kin 9 Avenue, Columbus, Ohio 43201, U.S.A.

Abstract--This paper is a reviewof stack gas treatment methods for the control of NO~ emissions.Particular
emphasis is placed on status of developmentand factors affectingthe performance of the processes. Catalytic,
noncatalytic, and scrubbing processes are compared on a uniform engineering basis. Most of the active
process development work is taking place in Japan. The three leadingstack gas treatment techniquesfor NO~
control are catalytic reduction with ammonia, noncatalytic reduction with ammonia, and direct scrubbing of
NO with simultaneous absorption of SO2. The wet processes are much less developedthan the dry processes.

1. I N T R O D U C T I O N reduction is required, treating the combustion gas to

Nitric oxide (NO) and nitrogen dioxide (NO2) are
important links in the chain of photochemical reac-
tions leading to the formation of smog. Six other
nitrogen oxides are known to exist but they seldom
occur in the atmosphere in measurable quantities, and
then only under special conditions.
The major component of worldwide atmospheric
NO x (NO + NO2) is biologically produced NO.
Natural sources produce about 500 x 106 tons of NO
per year while man-made sources emit 50 x 106 tons
of NOx. However, NO~ concentrations in urban areas
are 10-100 times higher than those in nonurban
areas, 1 thus reflecting the importance of technological
sources over natural sources.
Much of the man-made NOx emission is from
mobile sources such as automobiles. Because the
mobile source emission regulations have been relaxed,
stationary source NOx control has become more
important for maintaining air quality. 2 The emission
from stationary sources such as industrial boilers is
unique in that, unlike SO 2 and particulate matter, not
all of it comes from the fuel. Although coal in
particular contains nitrogen compounds, much of the
NOx formation is from the air introduced into the
burners; 3 nitrogen and oxygen react at the high
temperature and the gas is cooled before the resulting
NO can fully decompose. The nitrogen compounds in
the coal also oxidize, thus increasing the total emission.
The degree to which air nitrogen, and to a lesser
extent fuel-bound nitrogen, reacts with oxygen can be
reduced by "combustion modification"--i.e, various
adjustments that lower the flame temperature and thus
reduce oxidation. Techniques for doing this include:
(1) use of a boiler type that produces a relatively "cool"
flame, (2) staged combustion (feeding only part of the
air to the burner followed by injection of the remainder
into the gas after the burner), and (3) recirculation of
combustion gas to cool the flame. Reducing the
amount of excess air fed to the burners is also effective.
Although all these techniques reduce NOx form-
ation, there is a limit to the reduction that can be
accomplished by combustion modification. If further
decompose the NO~ or passing the gas through some
material that will absorb it selectively may be necess-
ary. Currently, Japan has the most stringent ambient
and emission standards for NOx in the world and, as a
result, most of the active process development work on
removing NOx from stack gas is taking place there.
2. C L A S S I F I C A T I O N O F STACK G A S C L E A N I N G
TECHNOLOGY FOR NO X
The various technologies being developed for NOx
removal from stack gas are summarized in Fig. 1. One
of the major divisions in the technologies is between
removal of NOx alone and simultaneous removal of
NOx and SO2. Although both methods can be carried
out in either dry or wet systems, the leading tech-
nologies involve dry removal of NOx alone or wet
simultaneous removal of NOx and SO z. Wet processes
are "add-on" types which can be installed at a point
where the gas has passed through all the equipment
and is about to enter the stack. Most dry processes
require higher temperatures and would be inserted
ahead of the air preheater on new boilers. Retrofit
application of these dry processes would require
expensive reheating of the flue gas or rebuilding with a
bypass duct between the economizer and air preheater.
The dry methods for removal of NO x alone include
homogeneous (noncatalytic) reduction, catalytic re-
duction, sorption by solids (physical adsorption or
chemical absorption), and catalytic decomposition.
However, process development efforts have concen-
trated on selective reduction of NO x with NH3, either
with or without a catalyst.
Wet methods for removal of NOx alone are limited
by the relatively inert nature of NO. This difficulty can
be overcome by oxidation of NO to the more reactive
NO2 in the gaseous phase using ozone or C102 prior to
absorption (oxidation absorption) or by the use of a
strong oxidizing agent such as K M n O a or NaC102 in
the liquid phase (absorption oxidation). However,
these methods usually convert the NO x to nitrites and
nitrates which present water pollution problems.

287
288 H.S. ROSENBERG,L. M. CURRAN,A. V. SLACK,J. ANDOand J. H. OXLEY

Absorption of NOx and

SO2 by Liquids with
Liquid Phase Reduction
of NOx to N2 by SO~

Absorption of NOx
and SO2 by Liquids
with Liqu,d-Phase
)xldat,on to NO3 and SO~ Liquid.Phase J
Reduction of
GasPhase Oxidation
l N o T ~ so~
of NO or Recycle ~f
NO2 Followed by
Absorption of NOx
Simultaneous and SO~ by Liquids
Removal of L Liquid-Phase
Oxidation of l
NOx and SO2 NOx to NO:~
Sorptlon of
NOx and SO2
by Solids
f Reaction
SO2 withof I
Copper Oxide
Selective Catalytic
Reduction of NOx by
NH3 with Simulta-
neous Sorptlon of SO2
Adsorption I
of SO2 by
Activated Carbon
Electron
Beam
Radiation

J Absorptionof NOx I
by Liquids with
Liquid-Phase Reduction
to NH~

Absorption of NOx
by Liquids with
Liquid-PhaseOxidation
to NO~2/NO~ I Liquid-Phase
Reduction
to N2
'" Gas PhaseOxidation
of NO or
NO2 Followed by
Removal of
Absorption by Liquids I Liquid-Phase
NOx Alone Oxidation
to NO2/NO3
Catalyhc
Decomposition
of NOx

Sorption
by Solids
Selectwe

J Catalytic
Reduction
to N2
[ w~th NH3

Nonselective
with Reducmg
Gases
L Homogeneous
Reduction
to N2 with NH3

FIG. l. Technologiesfor the removalof NO~ from stack gas.

 Post combustion methods for control of NOv emissions
There are specialized cases where NO2 can be reduced
to nitrogen by urea scrubbing (oxidation absorption-
reduction) or where NO can be reduced to NH~- by
scrubbing with a chromous salt solution (absorption
reduction); however, these methods are not under
active development for stack gas treatment. Wet
processes usually involve simultaneous removal of
NO~ and S O 2 because when S O 2 is present in the gas it
is difficult to avoid SO2 absorption. Furthermore, SO2
absorbed from flue gas can assist in NOx absorption.
There are a few dry methods under development for
the simultaneous removal of NOx and SO2 from stack
gas. These include electron beam radiation, absorption
by alkalized alumina, and.selective catalytic reduction
of NO~ by NH 3 with simultaneous reaction of SO2
with copper oxide or adsorption of SO 2 by activated
carbon. The former two methods are "add-on" types,
while the latter method requires temperatures higher
than the air preheater exit temperature.
The wet methods for simultaneous removal of SO2
and NO~ are more developed than the dry simul-
taneous removal methods. The wet methods for simul-
taneous removal fall into the same categories as the
wet methods for NOx removal alone; i.e. oxidation
absorption, absorption oxidation, and absorption
reduction. However, in the case of simultaneous
removal, the presence of SO 2 offers the possibility of
reducing the NO~ to usable products such as NH 3 and
fertilizer, or to nitrogen with the methods of oxidation
absorption-reduction and absorption reduction. The
methods of oxidation absorption-oxidation and ab-
sorption oxidation convert the NO x to nitrates and the
SO2 to sulfates which create either waste disposal or
marketing problems.
3. GENERAL CONSIDERATIONS
The technology of NO~ emission control is quite
complicated, with many interlocking considerations.
Technical considerations of importance are as follows :
(1) When NOx removal from a coal-fired boiler is
required, there is a choice among: (1) equipping the
boiler with combustion modification equipment, (2)
using a conventional boiler and designing the gas
cleaning system to take care of the resulting inlet NO x
concentration, or (3) combustion modification fol-
lowed by gas cleaning.
(2) The NO~ can either be destroyed by reduction to
elemental nitrogen or converted to nitrate or ammonia
(or an ammoniacal compound). Numerous consider-
ations affect the choice between the two routes.
(3) The gas cleaning process can be wet or dry. If
dry, the equipment is usually, but not necessarily,
located between the economizer and air heater, where
the temperature is on the order of 400°C (750°F). If wet,
it is placed after the air heater, and the wet scrubber
reduces the temperature from the air heater or precipi-
tator outlet temperature--i.e, from about 300°F, down
to 130°F.
(4) In practically all dry systems, the NOx is de-
stroyed by reduction. A selective reducing agent is
289
needed since if it were nonselective much of the agent
would be wasted by reaction with oxygen. Ammonia,
when used with care, appears to be the best selective
reductant. It can he used either with or without a
catalyst. Not well known, however, is the fact that
ammonia can form explosive mixtures with air within
the lower and upper limits of 15.5. and 27.0 volume
percent NH3, respectively.'*
(5) Most of the NOx, about 90-95%, is in the NO
form. In wet systems, much better absorption is
obtained if the NO is first oxidized to NO2. If this is not
done, it is necessary to carry a homogeneous catalyst in
the scrubber solution to promote absorption of NO.
(6) In wet scrubbing, SOz is absorbed along with the
NO x. Actually this is helpful, both because overall cost
may be lower than for separate removal and also
because the sulfite resulting from SO2 absorption
serves as a reducing agent for the absorbed NOx. These
processes require a minimum SO2 : NOx mole ratio of
about 2.5 : 1.
(7) In dry processes, the presence of SO2 is generally
undesirable for various reasons. Chief among these is
reaction of SOx with the catalyst substrate.
Alternatives considered have been : (1) wet scrubbing
to remove SO2, followed by reheating the gas and
using a dry process (reduction to nitrogen) for NOx, (2)
a dry process in which a solid material both absorbs
SO2 and serves as a catalyst for NO~ reduction, and (3)
a dry process that minimizes interference from the SO2
and allows it to pass on downstream where it can be
removed or not as required.
(8) Particulate matter is normally removed before
the scrubber in wet processes. For dry methods,
particulate matter does not interfere if noncatalytic
reduction is used. For catalytic reduction, however,
catalyst plugging and inactivation by flyash are major
problems. Since removal before the catalyst is expens-
ive because of the high temperature, the main emphasis
has been on development of catalysts that resist
plugging.
These considerations suggest a variety of system
design and equipment arrangements. A chart of the
various combinations of stack gas treatment tech-
niques for NOx removal that have been used or
proposed is shown in Fig. 2. Currently the three most
important techniques are as follows :
(1) Catalytic reduction with ammonia is the method
most favored in Japan. It is relatively efficient for NO~
removal (refer to Fig. 2b).
(2) Noncatalytic reduction is also being field tested
in Japan. Although relatively inefficient in regard to
degree of NO~ removal, the capital cost is relatively
low (refer to Fig. 2a).
(3) Direct scrubbin 9 of NO (no prior oxidation to
NO2) with simultaneous SO2 absorption may be the
best combination among the wet processes. Oxidation
before absorption is highly expensive as are ap-
proaches such as SO2 removal before NO~ scrubbing.
However, all the wet processes are complicated and
therefore it is difficult to say which type of process is the
best (refer to Fig. 2e).
290 H.S. ROSENBERG,L. M. CURRAN, A. V. SLACK, J. ANDO and J. H. OXLEY

NH 3

750 F l---I 3~o, I-'-5"1 3~oF F ..... l ,,or F---I ,,~

~--~ AH ~ EP ~ WDS l---------a=,-! H I- . . . .
I I I I i o / o
I I I I L ..... J ~.... J

T
F--L-1
I CM I
I I
L___J a. Noncatalytic Reduction

_1
t
750 F I 750 F
"J EP DDN ~--- WDS |
-I I
L____-I L__-J D ..J
I .... F1140 F
I
i" m E "-I
I I
i CM I
L__/ I.... ]
b. Catalytic Reduction

750 F ~ ] DDN
DDS
,~0~ ~ I 320 F

r-a-1
I
'
I CM I
L.... J
I NH3
l
c. Catalytic Reduction with Dry Simultaneous Removal of SO2

285 F - - ! WDS
J -I
r-.-l-- ~
I '
I CM I
L___J
I t I
DDN
~__ 750 F
I~
i~j ~ 555 F

NH 3

d. Catalytic Reduction Preceded by Wet Removal of SO2

FIG. 2. Stack gas treatment techniques for HOx removal

 Post combustion methods for control of NO, emissions 291

I 03 or
I CiO2

285 F
750 F ~ 1 ~ _ as ox ;
-[ WDN
WDS
125 F _ [ - - ~ 1 7 5

-I I
F

I
I I
I
r-L-I I
I I I
I TM I r "1
L__J I I
- ~ t - - . - - ~ CV I
N - Containing L . - _ J
e. Wet Simultaneous Removal of NO x and SO 2 Compounds

750 F "~-I~ 285 F

--I--I EP 1285F _I WDS
L__J -I -I I -
I
r--L--i
I I
I CM I
L__J

f. Wet Removal of NO x Preceded by Wet Removal of SO 2

Legend
AH = Air Heater
B = Boiler
CM = Combustion Modification
CV = Converter for Nitrogen Compounds
DDN = Dry Flue Gas Denitrification
DDS = Dry Flue Gas Desulfurization
EP = Electrostatic Precipitator
H = Heater
HE = Heat Exchanger
OX = Oxidizer
WDN = Wet Flue Gas Denitrification
WDS = Wet Flue Gas Desulfurization

NOTE: Dashed Lines Refer to Optional

Process Steps.

FIG. 2. ( c o n t i n u e d ) .

The main emphasis in this paper is on these three
categories. Numerous other approaches in addition to
the ones shown in Fig. 2 have been proposed and some
tested, but none have attained any great significance.
4. N O N C A T A L Y T 1 C REDUCTION WITH AMMONIA
4.1. Background
The simplest way to remove NO~ from combustion
gas is to inject a gaseous reducing agent and reduce the
NOx to elemental nitrogen. The amount of reductant
required should not be unduly high if it is selective for
NOx because the actual weight of the NOx is relatively
low (about 17.5 lbs NO per ton of coal or on the order
of 45 tons per day for a 500 MW boiler at full load).
J.P.}.( S 6 3 I
Most of the oxidizable gases such as CH 4, CO, and
NH 3 will reduce NOx, but some also react with the
oxygen in the gas. Ammonia is a selective reductant for
NOx and if proper conditions are used it is relatively
resistant to oxidation. Although NH3 in certain pro-
portions with air can also form explosive mixtures, this
has apparently never been a problem in boiler appli-
cations to date.
The use ofNH 3 as an NO= reductant in combustion
gas to meet current standards was investigated by
Wendt. 5 Both Exxon Research and Engineering
Company and KVB, Inc., have done work in the area,
part of which has been sponsored by the Electric
Power Research Institute (EPRI). Exxon started work
on the process in August 1972,6 and has obtained a
patent. 7 Independent development has also been
292 H.S. ROS~Na~RG,L. M. CURRAN,A. V. SLACK,J. ANDOand J. H. OXLEY
carried out in Japan. s Nippon Kokan filed a patent
application in 1970 and the Central Research Institute
of the Electric Power Industry (CRIEPI) has carried
out studies on the process chemistry.
The method involves injection of ammonia into the
boiler at high temperatures (about 1800°F). Reactions
of NH 3 with NOx are usually represented as
4NH 3 + 6NO---, 5N 2 + 6H20
8NH 3 + 6 N O 2 ~ 7N2 + 12HzO.
Since the presence of oxygen has a significant positive
effect on the reaction of NH 3 with NOx, the actual
reactions are probably better expressed as
4NH 3 + 4NO + 02 ~ 4N2 + 6H20
4NH 3 + 2NO 2 + 02--* 3N 2 + 6H20.
In addition, the following undesirable side reactions
between NH 3 and oxygen can take place
4NH 3 + 5 0 2 - * 4NO + 6H20
4NH 3 + 302 ~ 2N 2 + 6HzO
4NH 3 + 402 ~ 2N20 + 6HzO.
In a typical boiler situation, the NO reduction by
Reaction 3 dominates at temperatures of 1700-
1800°F. At higher temperatures, NO formation by
Reaction 5 becomes significant, and above 2000°F
injection of NH 3 becomes counterproductive, causing
increased NO. 9 AS temperatures are reduced below
1600°F, the rate of both reactions becomes extremely
low, the NO reduction falls off drastically, and the
NH 3 flows through unreacted.
The net situation is shown in Fig. 3.6 The tempera-
ture must be at least 1800°F to minimize the amount of
unreacted ammonia, but if raised much higher the NO
increases rapidly because of Reactions 5, 6, and 7.
\ c
÷
L200 1500 1400 1500 1600 1700
Temperoture, g
FIG. 3. Effectof temperature on NO~ reduction by NH~.
The critical temperature level can be reduced by
adding hydrogen along with the ammonia. 6
Other reactions can produce undesirable side
products.
(1) N20. From 1 to 2 moles of N20 are said to be
produced per 100 moles of NO reduced. 6 Exxon points
out that NzO appears to be harmless and is present in
the atmosphere at a concentration of about 0.3 ppm.
(1)
(2) HCN is produced if there are hydrocarbons
(2) present in the reaction zone, which usually is not the
case.
(3) CO is not formed in the reaction but oxidation of
the CO is inhibited. For oil- and gas-fired boilers, the
CO should be already oxidized at 1800°F. No data
(3) appear to be available for coal firing.
(4) SO3 formation is not affected.
(4)
4.2. Factors Affecting Performance
(5) 4.2.1. Temperature control
(6) Since the process is so sensitive to temperature, it is
quite important to locate the injector at the proper
(7)
point in the boiler. The main problem, however, is that
in an operating boiler the temperature at a given point
changes with load. Thus, if the injection point were
selected to give the optimum temperature at full load,
the temperature would drop at reduced load and the
exit ammonia concentration would become excessive.
The ammonia feed could be reduced to avoid this but
then NO x removal would drop off.
Exxon has proposed use of hydrogen along with the
ammonia as a means of keeping the temperature
optimum at all times. As the temperature drops with
load reduction, the hydrogen feed is adjusted to keep
the temperature optimum. Although this probably
would be effective, purchasing hydrogen or installing a
hydrogen production unit would be quite expensive.
The use of hydrogen also represents an additional
safety hazard.
Multiple injection points have also been proposed
+ NO pprn
o NH 3 ppm and have been tested on a large oil-fired boiler in
Japan. In such an arrangement, the point of injection is
shifted upstream in the boiler as the load drops. If
enough injection points were provided and the system
could be controlled adequately, this also should
provide optimum temperature. However, the injection
points must be in the upper part of the boiler in an area
where heat exchangers interfere.
One of the problems in temperature control is that
boiler temperature at a given point changes with time.
As heat transfer surfaces become blocked with slag or
hard deposits, the temperature increases until the
deposits are removed. It is not clear how this would
affect the efficiency of noncatalytic reduction.
4.2.2. Ammonia feed rate
The NO~ removal efficiency can be increased con-
1800 1900 ?000
siderably by feeding more ammonia. The use of excess
ammonia is no1 practicable, however, because of the
residual ammonia carried on downstream. As in-
 Post combustion methods for control of NO ~emissions
dicated by the Japanese tests, an excess of 20~o or so
above the stoichiometric amount seems to be the limit.
However, some plants are operating with higher levels
of excess ammonia and exhibiting significant NH 3
emissions.
4.2.3. Ammonium bisulfate formation
As the gas cools in the boiler train, the temperature
decreases to the level at which ammonia and SO 3 (plus
H20) react to form ammonium bisulfate (NH4HSO4);
the exact temperature depends on the concentrations.
For the concentrations normally encountered (10-50
ppm SO3 and 10-20 ppm NH3), the condensation
temperature is on the order of 410-435°F, which
means that the condensation takes place in the air
heater.
Ammonium bisulfate at high temperatures is an
extremely corrosive material, so much so that the mild
steel normally employed in air heaters probably would
not be usable. In addition to corrosion, bisulfate
condensation can also produce fouling and plugging of
the air heater. There has not been enough noncatalytic
reduction work carried out yet to fully evaluate the
problem. The subject is discussed more fully in the
section on catalytic reduction, where the same prob-
lem is encountered and a much larger data base has
been accumulated.
4.2.4. Pollution by ammonia
Any residual ammonia not deposited as NH4HSO4
goes on with the gas and either is caught in the SO/
scrubber (if there is one) or escapes from the stack. In
either case there is a pollution problem, either water
pollution in the scrubber case or air pollution if the
ammonia escapes from the stack. The ammonia
pollution problem has also been explored more fully in
the catalytic reduction area and will be covered in
more depth in the next section.
4.3. Commercial Status
Noncatalytic reduction with ammonia has been
tested on at least four boilers in Japan, three of the
industrial type and one at a utility.
MW (or
Company Site Equivalent)
Tonen Petrochemical Kawasaki
Mitsubishi Chemical Industries Mizushima
Mitsui Petrochemical Chiba
Chubu Electric Chita
The 375 MW No. 2 boiler at Chita. Station of Chubu
Electric was retrofitted for noncatalytic reduction by
Mitsubishi Heavy Industries (MHI). The boiler is
fueled with 0.2~o sulfur, heavy residual oil. Two
locations are used for NH 3 injection because tempera-
ture is very important. The forward injection nozzles
293
are used at low boiler loads. The nozzle manifolds have
to be cooled with high quality water. The inlet NOx
concentration is 130-160 ppm and the removal
efficiency is 40~o at a feed ratio of 1.5 mole NHa/mole
NOx. The NH 3 emission is 10-20 ppm. After 4 months
of operation, the air preheater pressure drop increases
by about 35~o because of plugging by NH4HSO4. Soot
blowing and a water wash is applied on the high-
temperature side of the preheater. Corrosion is not a
serious problem with the air preheater which is
constructed of Cot-Ten steel.
An industrial boiler equivalent to about 40 MW
was retrofitted for noncatalytic reduction by
Ishikawajima-Harima Heavy Industries (IHI) at the
Chiba plant of Mitsui Petrochemical. Three locations
were provided for NH 3 and hydrogen injection at
1240-1450°F. Hydrogen is used because no space was
available to inject the NH 3 at higher temperatures. For
an inlet NO~ concentration of 130 ppm, the average
removal efficiency is 35~o at feed ratios of 2.0 mole
NH3/mole NO~ and 4.0 mole H2/mole NO~. The
ammonia emission is 10-15 ppm.
Noncatalytic reduction of NOx with ammonia is
falling into disfavor in Japan because of the relatively
large NH 3 requirement and the relatively high NH3
emission. Also, about one-half of existing boilers do
not have suitable locations for NH 3 injection ports.
Nevertheless, the relatively low investment for non-
catalytic reduction is a major advantage. For existing
boilers, where retrofit with some other system would
be excessively expensive, the process can play an
important role in meeting regulations that cannot be
met by combustion modification. It has been reported s
that in Japan two systems were installed in 1978, at the
Isogo and Takasago Stations of the Electric Power
Development Corporation (EPDC). The installation
at Isogo is on two 265 MW boilers and at Takasago on
two 250 MW units (all coal-fired).
A combination of noncatalytic reduction and select-
ive catalytic reduction (SCR) is being used to minimize
NH 3 emission and obtain a moderate amount (50-
60Vo) of NOx removal in several retrofit installations
by placing a minimum amount of catalyst in the
ductwork after the economizer. Minimizing the pres-
sure drop allows the use of the existing fan. The main
purpose of the catalyst is to reduce the NH3 emission.
Fuel Start-up
160 Fuel gas and heavy oil 1975
138 Fuel oil 1975
40 Fuel gas and cracked naphtha oil 1976
375 Heavy oil and crude oil 1977
IHI has installed the combination process on two
utility boilers fired with low sulfur oil. At an inlet NO x
concentration of 150 ppm, 50-60~o removal is ob-
tained at a feed ratio of 1.5 mole NH3/mole NOx. The
NH 3 emission is 10-20 ppm. A honeycomb catalyst
with a pressure drop of 1-2 in. H 2 0 was placed in the
294 H.S. ROSENBERG,L. M. CURRAN,A. V. SLACK,J'. ANDOand J. H. OXLEY
duct. The catalyst does more of the removal job at low
load when the space velocity is lower and when the
temperature is below the optimum for noncatalytic
reduction. The amount of catalyst required in this case
is about 20~o of the amount required to achieve 80-
90~o NOx removal with SCR only. Catalytic reduction
is discussed more fully in the next section.
5. CATALYTICREDUCTION WITH AMMONIA
5.1. Background
Since NOx reduction with ammonia requires a very
high temperature to get an adequate reaction rate, and
as a result part of the ammonia is consumed in
undesirable reactions, the logical course is to use a
catalyst. By this means the operating temperature can
be reduced to the 650-850°F range, the reaction
becomes much less sensitive to operating temperature,
more complete NOx decomposition (90~o or better) is
attained, and very little of the ammonia is used in
undesired reactions. Offsetting drawbacks are higher
capital cost, more difficulty in retrofitting, and adverse
effects of SO 3 and dust on the catalyst.
Some experimental work on catalytic reduction
(generally called SCR or "selective catalytic reduc-
tion") has been done in this country but most of the
effort has been in Japan.
The chemistry of the process is the same as for
noncatalytic reduction except that the side reactions
are not significant at the lower temperature. The
problems of air heater corrosion/plugging and
downstream pollution with ammonia are also the
same but probably somewhat less severe, since residual
ammonia seems to be generally higher in noncatalytic
operation.
The main additional problems introduced by use of
a catalyst are poisoning of the catalyst surface and
plugging of the catalyst bed. Since the poisoning is
mainly caused by SO3 in the gas and the plugging by
dust generated from the fuel, catalytic reduction works
much better with "clean" fuels such as gas and low
sulfur light oils than with dirtier fuels such as residual
oil and coal. In fact, this has led to three categories of
application in Japan :
(1) Clean gas. Most of the early work, particularly
that of Sumitomo Chemical Industries, was on very
clean gas containing no SO 3 or dust. The Sumitomo
installation that started up in May 1974 (in a methanol
plant, 65 MW gas-flow equivalent) appears to be the
first commercial NOx removal operation in the world.
The packed-bed catalyst used has given very good
performance. Another application of the clean gas
technique is a combination process in which the gas is
first treated to remove SO2, SO3, and dust by scrub-
bing (or a combination of electrostatic precipitator
and scrubber) and is then reheated to a temperature
suitable for catalytic NOx reduction. One such plant
has been built in Japan but the approach is cumber-
some and expensive.
(2) Semi-clean gas. When "ordinary" low sulfur oil is
burned, the amounts of SO3 and dust in the combus-
tion gas are small but still large enough to plug a fixed
bed catalyst fairly rapidly. To counter this, companies
such as Kurabo and MHI in Japan have developed
systems in which the catalyst is removed from the gas
stream for cleaning and reactivation. The removal can
be either continuous, by use of a moving bed, or
periodic.
The "regeneration" approach adds considerably to
both capital and operating costs. Moreover, recent test
results in Japan indicate that the dust concentration
must be quite low to make the system practical. In one
case, an inlet dust concentration of 0.0044).008
grain/scf plugged a moving bed reactor in 10 days to
the extent that the entire catalyst had to be removed
for cleaning.
(3) Dirty gas. For coal and high sulfur oil, especially
the residual type, the high dust loading precludes use of
the usual type of catalyst, either fixed or moving bed.
The dust can be removed ahead of the catalyst, of
course, by use of a hot precipitator, but this makes dust
removal unduly expensive for high sulfur fuel. The SO3
produced in burning such fuel makes the dust conduct-
ive enough for good performance with a medium-sized
cold precipitator. A hot precipitator must be much
larger and therefore is more expensive.
The major current development effort is on develop-
ing "parallel flow" catalysts. The catalyst is shaped in
such a way that the assembly provides open spaces
through which the gas can flow with little resistance
and which cannot be easily plugged by dust accumu-
lation. The catalytic effect is obtained by the NOx and
NH 3 diffusing sidewise to the catalyst surface. The dust
particles tend to be carried along with the gas, with
minimum adherence to the surface.
Such an arrangement obviously is not as efficient as
a closely-packed granular catalyst and the shaped
catalyst is more expensive to fabricate. Nevertheless,
these problems appear to be relatively minor as
compared to the advantage of being able to operate a
catalytic system without prior removal of dust.
While the parallel flow may solve the dust problem
in burning high sulfur fuels, it does not solve the
catalyst poisoning problem that results from the
relatively high concentration of SO3 in the gas. This
problem has been attacked in Japan by altering the
catalyst composition. The alumina normally used
reacts with the SO 3, with the net result that the catalyst
loses activity; the exact mechanism for the poisoning
does not appear to be well understood. By using other
materials for the base, the problem seems to have been
resolved, although not enough testing has been done
yet to establish catalyst life very well.
For the U.S., the parallel-flow catalyst seems to be
the only practical approach. The packed-bed type
would be applicable only to boilers burning natural
gas or a very light oil. No new boilers of this type are
likely to be built and retrofitting catalytic reduction on
old boilers would be a major and expensive operation.
If it came to the point that retrofitting were required,
which seems unlikely, it might be better to "add-on"
 Post combustion methods for control of NO ~emissions 295

the catalyst system and reheat the gas by heat
exchange.
5.2. Factors Affecting Performance
5.2.1. Catalyst composition
Since catalyst composition is usually a proprietary
item, little is known about the actual compositions
used in Japan. The Japanese work has been mainly
with base metals such as iron, vanadium, chromium,
manganese, cobalt, nickel, copper, and barium, a'l°
Experimental results and vendor claims vary widely
for these.
The metals are normally deposited on a carrier
which, as noted earlier, was alumina in the earlier
stages of development. More recently, oxides of ti-
tanium and silicon have been used to increase resist-
ance to SO 3. MHI has reported resistivity to SO3 as
follows :
TiO 2 = SiO 2 > GtA1203 > r/A1203 > TA1203.
For some catalysts a carrier is not used. For
example, one company has developed a catalyst made
of solid goethite (Fe203 - n 2 0 ) , said to be active and
resistant to SO3. Others use an all metal construction,
apparently with an active metal impregnated into the
surface. Very few data on this have been released.
One of the important problems associated with SCR
therefore the pressure drop is relatively high. Also, it is
possible that appreciable erosion can occur at this high
gas velocity when treating flue gas from a coal-fired
boiler without prior particulate removal. The
honeycomb catalysts avoid some of these problems by
operating at a velocity of 3-16 ft/sec because of the
larger surface area per unit volume. A ceramic
honeycomb may be preferable to a metal honeycomb
for two reasons. With metal, the catalyst is deposited
or etched on the surface in a thin layer that may be
removed by flyash erosion. Also, the catalyst com-
position is limited. With ceramic, the catalyst exists
throughout the substrate and any catalyst compo-
sition can be used. However, in a metal honeycomb,
the catalyst is deposited in a layer of about 0.154).3
mm on each side of a 0.4 mm wall. In a ceramic
honeycomb, about 2 mm is the thinnest wall that can
be produced. Therefore, a metal honeycomb can
provide more reactive surface in a given volume than a
ceramic honeycomb.
IA/\/\/\/\/\, t 'H
//~/\/\/\1\I\,
A/~/~/\/\,
/\/~/\A/\/\,
a Meto~ Honeycomb

catalysts is the tendency to oxidize some of the SO2 in

the flue gas to SO3. An increased concentration of SO3
can exacerbate the ammonium bisulfate problem as
well as cause secondary environmental pollution.
Generally speaking, SCR catalysts are oxidation cata-
lysts in nature and it is likely that they can cause
b ParoHef Plate
oxidation of SO 2. This is especially true in the case of
V205 and further studies are needed on SO2 oxidation ~Omm IOmm
2 mm
and its prevention.
Catalyst composition appears to be still in a state of
development. More data are needed especially on
catalyst life under varying conditions.
I
5.2.2. Catalyst shape C Ceramic Honeycomb

The parallel-flow catalysts are made in various

shapes, including rings, tubes, plates, and
"honeycomb". There is also an arrangement in which
granular catalyst is carried in thin "envelopes" and
held in place by metal gauze. The envelopes are
suspended in the gas stream in such a way that the gas
flows parallel to the surfaces. Five types of parallel-
flow catalysts that have been used in Japan for SCR are
shown in Fig. 4. These are: (a) metal honeycomb, (b)
©©
d. Tubular
parallel plate, (c) ceramic honeycomb, (d) tubular, and
(e) parallel passage. Reactors using catalyst types b, d,
and e have a fairly wide passage for gas flow, as shown
in Fig. 5, and have little tendency for dust plugging.
However, the wide passage requires a relatively high
gas velocity of 16-32 ft/sec in order to produce
turbulent flow to yield a high NOx removal efficiency.
e Parallel Passaqe
Because of the high gas velocity, a tall reactor is
required to give the necessary space velocity and FIG. 4. Types of parallel-flowSCR catalysts.
296 H.S. ROSENBERG,L. M. CURRAN,A. V. SLACK,J. A~oo and J. H. OXLEY
tor~
R'eoc
FIG. 5. Tubular catalyst cells arranged in a reactor.
5.2.3. Operatin9 temperature
The temperature range for catalytic reduction is
usually 570-750°F. The process is not sensitive to
temperature change in this range because the side
reactions that make temperature so important in
noncatalytic reduction do not take place to any
significant extent.
In some cases, designers have feared that tempera-
ture reduction during turndown would aggravate the
bisulfate deposition problem and therefore have in-
stalled an auxiliary heater to maintain a fairly uniform
operating temperature. If this were necessary for large
industrial boilers, it would be so expensive as to be
almost unacceptable. The recent test experience in
Japan indicates that auxiliary heat may be
unnecessary.
5.2.4. Space velocity
The catalyst volume required is a very important
factor in cost. If the space velocity (volume of
gas/hr/volume of catalyst) were as low as, say, 2000/hr
or less, the reactor would be relatively large and a
major plant component in regard to size and cost. The
Japanese experience does not provide very complete
information on space velocity but the upper limit
seems to be in the 5000-10,000/hr range. The catalyst
requirement is often given in terms of"area velocity" or
gas volume/hr/unit of catalyst surface area (m3/hr/mZ).
The parallel-flow catalysts would be expected to
require a larger volume than the granular type, but this
is not clear from the Japanese data available so far.
5.2.5. Turndown
Operation at reduced load is no problem in catalytic
reduction. MHI pilot plant data show that the de-
crease in efficiency caused by lower temperature in
Ceils
going from full load to 25~o load is more than offset by
the lower space velocity. For 10,000/hr space velocity
(SV) and 660°F at full load, SV was 3500/hr and
temperature 520°F at 25~ load in pilot plant tests.
NOx decomposition increased from 92 to 98~o
(NH3:NO mole ratio of 1.0) and residual NH 3
dropped from 12 to 5 ppm. However, depending upon
the SO2 concentration in the flue gas and the amount
of SO2 oxidation caused by the catalyst, the reactor
temperature may have to be kept above 625°F to
prevent NHaHSO 4 condensation on the catalyst.
Some companies suggest bypass of part of the flue gas
around the economizer as a method of maintaining a
reactor temperature of 625°F at reduced boiler load.
5.2.6. Ammonium bisulfateformation
The problem of NH4HSO 4 condensation in the air
heater varies widely in severity with conditions, and
there is not enough information available yet for
adequate evaluation. It has been pointed out that
ammonia has been injected in conventional boiler
operation to reduce air heater corrosion by H2SO4. 6
Some of the Japanese test work indicates significant
corrosion and plugging and other tests do not. There is
some experimental evidence that coal-fired operation
may give less trouble because the dust scours out
deposits that form on air heater surfaces. ~1
Hitachi Zosen made corrosion tests using the com-
mercial Ljungstrom-type heat exchanger at the
Yokkaichi SCR installation at Shindaikyowa
Petrochemical. Five materials were tested : (1) carbon
steel similar to AISI 1020, (2) carbon steel similar to
AISI 1020 coated with polyimide resin, (3) carbon steel
similar to AISI 1010, (4) Type 316 stainless steel, and
(5) Type 316L stainless steel. Test coupons of the
materials, 120 × 50 × 3 mm in size, were placed in six
different locations in the heat exchanger and exposed
 Post combustion methods for control of NO~ emissions 297

to the flue gas for 95 days. Since a considerable deposit
formed on the coupons, they were washed with an
acidic solution prior to weighing. The corrosion rate
was higher for the samples placed in the colder
positions. The stainless steels were fairly resistant to
corrosion but it may be very expensive to manufacture
Ljungstrom units from these materials. The resin-
coated steel had a relatively low corrosion rate at 136-
138°F but the rate was much higher above 212°F.
The experience in Japan with the bisulfate problem
is varied and the situation is not yet clear. Much
depends on the extensive test program of EPDC on
coal-fired boilers, which is the Japanese experience
most applicable to the U.S. situation.
5.2.7. Pollution by residual ammonia
The problem of residual ammonia pollution has
been evaluated even less than bisulfate deposition. The
situation in japan is somewhat different from the U.S.
in that in Japan the high degree of dewatering required
NOx catalyst. This was tested by Sumitomo and MHI
in early work and found to be effective, although the
method has not been adopted in Japan. The tradeoffs
are a larger and more expensive reactor against the
problem of ai~ preheater corrosion and plugging, the
severity of which has not yet been determined.
5.3. Commercial Experience and Status
The widespread testing of catalytic reduction in
Japan indicates the commercial interest in the process.
Because of the growing pressure to reduce NO x
emission, most of the new boilers may be required to
have gas treating facilities for NOx removal, in which
case catalytic reduction will likely be the most econ-
omical process for Japanese conditions. However, only
four large installations are installed or definitely
planned by utilities, two on boilers fired with liquid
natural gas and which therefore do not require a
catalyst resistant to dust and SO3. The utility SCR
installations planned or installed are as follows :

Company Site MW Fuel Start-up

Tokyo Electric Yokosuka 13 Low sulfur heavy oil 1977

Chubu Electric Taketoyo 6 Crude oil 1977
Kansai Electric Kainan 112 Crude oil 1977
Chubu Electric Chita 700 x 2 LNG 1978
Kyushu Electric Kokura 600 x 2 LNG 1978
Chugoku Electric Kudamatsu 675 Low sulfur heavy oil 1979

in making marketable gypsum in SO2 scrubbing Catalytic reduction has been installed on several
makes it necessary to purge a waste stream of scrubber industrial plants. The major ones are as follows :

MW
Company Site Gas source (equivalent) Start-up

Higashi Nihon Methanol Sodegaura Furnace 60 1974

Nihon Ammonia Sodegaura Furnace 75 1975
Sumitomo Anegasaki Boiler (gas fired) 30 1975
Sumitomo Anegasaki Boiler (gas fired) 60 1975
Sumitomo Niihama Furnace 60 1975
Sumitomo Sodegaura Boiler (oil fired) 75 1976
Sumitomo Sodegaura Boiler (oil fired) 90 1976
Idemitsu Kosan Chiba Boiler (CO fired) 105 1975
Shindaikyowa Petrochemical Yokkaichi Boiler (oil fired) 130 1975
Mitsubishi Petrochemical Yokkaichi Boiler (oil fired) 45 1975
Kawasaki Steel Chiba Coke oven 105 1976
Kawasaki Steel Chiba Sintering furnace 240 1976
Mitsui Petrochemical Chiba Boiler (oil fired) 60 1975
Ukishima Petrochemical Chiba Boiler (oil fired) 72 1977
Mitsui Toatsu Takaishi Furnace 55 1976
Fuji Oil Chiba Boiler (oil fired) 62 1978

liquor to keep soluble impurities purged out of the
system. Since discharge of oxidizable materials is
subject to stringent control, any ammonia collected in
the SO2 scrubber becomes a serious problem. At the
Isogo station of EPDC, where catalytic decomposition
in a parallel-flow catalyst is being tested, a reverse
osmosis process is being studied as a means of
removing ammonia from the scrubber liquor.
One solution to the residual NH 3 problem is to
install an ammonia decomposition catalyst after the
All of these are on clean or semiclean gas, either from
burning gas or low sulfur oil or, in the case of
Shindaikyowa, from removing dust and SO3 before
the catalytic converter.
It is difficult to discuss the technology under "pro-
cesses" because only one "process" is involved. All the
installations, both test and commercial, are much the
same, the main difference being the type of catalytic
converter--either fixed bed, moving bed, or parallel
flow. Many of the engineering companies have worked
298 H.S. ROSENBERG,L. M. CURRAN,A. V. SLACK,J. ANDOand J. H. OXLEY
with all three, moving from packed to moving bed to
parallel flow as heavier fuels were used and more dust
encountered. There are a few differences in layout but
most of the "processes" are essentially the same.
Hitachi Ltd. installed SCR systems on two new 700-
MW LNG-fired boilers at Chita Station of Chubu
Electric. Each system uses four parallel fixed beds of
pellet catalyst. Each bed is 4 in. deep and the pressure
drop is 6 in. H20. The inlet NO x concentration is 35
ppm and the removal efficiency is 79% at a feed ratio of
0.8 mole NH3/mole NOx. The NH 3 emission is 5 ppm.
Since there is no SOx in the flue gas, there is no
NH4HSO4 deposition.
Hitachi Ltd. also installed an SCR system as a
retrofit to treat one-quarter of the flue gas from a 450
MW boiler fired with 0.1% sulfur crude oil at Kainan
Station of Kansai Electric. The Raschig ring-type
catalyst is in two parallel fixed beds each 1 ft deep. One
bed has a low cost catalyst and the other bed has a
better catalyst. The overall feed ratio is 1.07 mole
NH3/mole NOx and the removal efficiency is 80% for
an inlet NO x concentration of 150 ppm. The NH 3
emission is 20 ppm. The inlet dust loading to the
reactor is less than 0.008 grains/scf. The pressure drop
in the reactor increased from 1.8 in. H20 to 6.4 in. H20
after 1 yr. The catalyst was cleaned and reused. There
are no problems with NH4HSO 4 deposition because
low sulfur oil is used and the treated gas is diluted by
three-quarters of the flue gas which is untreated. The
installation time for the SCR unit was 3 months.
Mitsui Petrochemical installed an SCR system
utilizing tubular catalyst at their Chiba plant on an
industrial boiler fueled with 1% sulfur oil. For 100-150
ppm NO~, 95% removal is obtained at a feed ratio of
0.95 mole NH3/mole NO~ and an NH 3 emission of 5
ppm. The space velocity is 4000/hr. With 3 '~,,sulfur oil
and 15-20 ppm of NH 3 emission, the air preheater
plugged after 1 week. Sootblowing and reduction of
the NH 3 emission to 5 ppm allows 3 months of
continuous operation with high sulfur oil. The air
preheater is washed with water only during the annual
boiler maintenance period.
EPDC will install a 250 MW SCR demonstration
unit at Takehara Station on a coal-fired boiler. The
system will use a hot electrostatic precipitator ahead of
the SCR reactor, but particulate removal ahead of the
reactor may not be necessary. The boiler already has
an FGD system so that biological treatment for
nitrogen removal from the wastewater will be used.
The same SCR system will be used on a new 700 MW
coal-fired boiler.
In the U.S., the EPA has awarded two contracts for
pilot scale (about 0.5 MW) investigations of two NOx
removal processes by catalytic reduction with am-
monia. One contract was awarded to Hitachi Zosen of
Tokyo, Japan, to evaluate their SCR process which
utilizes a metal honeycomb catalyst. Hitachi Zosen has
subcontracted to Chemico Air Pollution Control
Corporation to build and operate the pilot-scale unit.
It will be connected to Georgia Power Company's
Unit No. 3 at Plant Mitchell near Albany, Georgia.
Application of the process, which is expected to
remove 90% of the NOx from the flue gas, will be the
first test of the technology on a coal-fired boiler in the
U.S.
The other contract, for a simultaneous NOx/SOx
removal unit, was awarded to UOP Inc. to evaluate the
Shell Flue Gas Treating process. In this process, SO 2
reacts in a bed of copper oxide to form copper sulfate.
The copper sulfate and, to a lesser extent, the copper
oxide act as catalysts in the reduction of NOx with
ammonia. When the bed is saturated with copper
sulfate, flue gas is switched to a second bed for
pollutant removal, and the spent bed is regenerated. In
the regenerating cycle, hydrogen is used to reduce the
copper sulfate to copper, yielding a concentrated SO2
stream which can be used to generate a salable
byproduct. The copper in the bed is oxidized, and the
unit is ready for acceptance of flue gas again.
UOP will operate the test unit which will be
connected to coal-fired boilers at Tampa Electric
Company's Big Bend Station in North Ruskin,
Florida. The Shell process is expected to remove 90%
of both the NOx and SOx from the flue gas. The project
will be the first test of this technology on a coal-fired
source anywhere in the world. The process utilizes a
parallel passage reactor in which the copper oxide is
contained in a series of cells arranged in a parallel
configuration (refer to Fig. 4e). The copper oxide is
contained between layers of wire gauze with spaces
between the cells for flue gas flow so that there is no
restriction of particulates in the passages.
EPRI has contracted with Kawasaki Heavy
Industries, Japan, to evaluate an SCR process de-
veloped by Kawasaki and EPDC. This jointly funded,
$1.5 m project will design, construct, and operate a 2.5
MW pilot plant for NOx removal. The pilot plant will
be installed at the EPRI Emissions Control and Test
Facility at the coal-fired Arapahoe Station of Public
Service Company of Colorado. EPRI tests, which are
scheduled from November 1979 to June 1980, will
provide information on the performance, cost, and
operational and environmental implications of SCR
technology.
6. WET SCRUBBING OF NO
6.1. Backyround
There has been a large amount of research activity
aimed at developing wet scrubbing processes for NOx.
Much of the earlier work was concerned with gases
containing NOx only, such as the tail gas from nitric
acid plants. This has little applicability to power plant
flue gas unless a sulfur-free fuel such as natural gas is
used or the gas is first scrubbed to remove SO2. There
have been a few "NOx-only" scrubbing processes
developed in Japan for flue gas treatment but it is
unlikely that they will attain any significance.
Thus, the main emphasis is on simultaneous scrub-
bing of NO x and SO2, because with SO2 in the gas it
would be difficult to avoid SO2 absorption. The main
 Post combustion methods for control of NOx emissions
problem is getting NO into solution; because of its
inert nature and low solubility, getting an adequate
rate of mass transfer is extremely difficult. Three
approaches to improving mass transfer have been
used :
(1) Oxidize the NO to NO 2 in the gas phase before
absorption. NO2 is much more reactive than NO.
(2) Oxidize the NO partially to give an equimolar
mixture of NO and NO 2. This also is relatively easy to
absorb because of nitrite formation.
(3) Use a dissolved catalyst to promote absorption
of NO and conversion to nitrogen-sulfur compounds.
Of the three approaches, the first two are so
expensive that their future is in doubt. The third may
have some chance, although it also has some major
drawbacks.
The catalyst normally used is ethylenediamine tet-
raacetic acid (EDTA) plus ferrous ion. The SO2 is
absorbed by either Na2SO 3 or NH4OH, and these
compounds enter into the complex series of reactions
that take place after the NO is absorbed. Although the
chemistry is not entirely clear, it appears that the
EDTA and iron form a complex with the NO :
Fe +2 - EDTA + NO--} Fe +2 - E D T A . N O (8)
and that this reacts with bisulfite
Fe +2 -- E D T A ' N O + 3NaHSO 3__} Fe + 3 - EDTA
+ NH(SO3Na)2 + 1/2Na2S206 + H20. (9)
The NH(SO3Na)2 is an imidodisulfonate and the
Na2S20 6 a dithionate. These are reacted in various
ways to give end products such as ammonia, nitrogen,
sodium sulfate, and gypsum.
A major feature of the process is that several moles of
SO2, probably above three to get high NOx removal
efficiency, are required per mole of NO absorbed.
Therefore, in order to absorb 400ppm of NOx from
coal-fired boilers, it would be necessary to absorb
about 1200ppm of SO:. Thus, the method probably
would not be applicable to low sulfur coal. The
processes under development vary too much to allow
a general treatment of operating variables. There-
l TOSTACK
AFTER-
h I ....
I-!rT
FLUEGAS
FIG. 6. Block diagram of Chisso engineeringprocess for the simultaneous removal of NOx and SO2.8
299
fore, two representative processes will be described
below. None of these processes has been carried
beyond the pilot plant stage. The prospects for com-
mercialization of a wet simultaneous removal process
for SO2 and NOx are not good in Japan because there
are no new boilers using high sulfur oil and the dry
NO x reduction systems are much more developed.
6.2. Process Development
6.2.1. Chisso
Chisso Engineering has developed a wet simul-
taneous removal process for NO~ and SO 2 based on
scrubbing with an ammoniacal solution containing
EDTA and ferrous ion. a A pilot plant with a capacity
for treating 190 scfm of flue gas from an oil-fired boiler
has been in operation since 1974. NOx in the flue gas is
converted to NH 3 by the reducing effect of SO2 to
produce (NH4)2SO 4. The reactions are complex, but
the overall reaction can be simply expressed as follows :
2NO + 5SO 2 + 8NH 3 + 8H20 ~ 5(NH4)2SO 4. (10)
A block diagram of the process is shown in Fig. 6.
The flue gas is first subjected to water scrubbing for
cooling and removal of particulates and chlorides, and
then treated in a scrubber by an ammoniacal solution
at a pH of 6. The main reactions are as follows :
S O 2 + H 2 0 + (NH4)2SO3--~ 2NH4HSO 3 (11)
NO + 3NH4HSO 3 ~ NH(SOaNH4) 2
+ 1/2(NH4)2S206 (12)
2NH4HSO 3 + 1/202--~(NH4)2S206 + H 2 0 (13)
(NH4)2SO 3 + 1/2 02 ~ (NH4)2SO 4. (14)
To obtain a high NOx removal efficiency, more than
3 moles of SO 2 are needed per mole of NO. Normally,
70-85% of the NOx is removed along with more than
90% of the SO2 in a scrubber with about 20 stages of
perforated plates. A portion of the scrubber liquor is
q
300 H.S. ROSENBERG,L. M. CURRAN,A. V. SLACK,J. ANDOand J. H. OXLEY
subjected to air bubbling to oxidize ammonium sulfite
and bisulfite to sulfate and dithionate. Dithionate is
produced as a result of the catalyst being present.
Sulfuric acid is added to the oxidized liquor to lower
the pH to 0.5 prior to cooling to 23-32"F using
ammonia as a refrigerant. The cooling operation
crystallizes about 90~o of the EDTA, which is sep-
arated by centrifugation and returned to the scrubber.
The mother liquor from the centrifuge is heated to
250-265°F under a pressure of 3 atm to decompose
ammonium imidodisulfonate and dithionate. The de-
composition reactions for the acidic liquor are :
NH(SO3NH4)2 + H20--~ NHzSO3NH 4
+ NH4HSO4 (15)
NH2SO3NH 4 + H 2 0 ~ (NH4)2SO 4 (16)
(NH4)2S206---, (NH4)2SO4 + SO2. (17)
The liberated SO 2 is returned to the scrubber. The
liquor obtained from the decomposition step contains
ammonium sulfate and bisulfate with small amounts of
dithionate, EDTA, and ferric ion. The liquor is neutra-
lized with ammonia and concentrated in a flash
evaporator after separating ferric hydroxide. The
crystallized ammonium sulfate is separated by centri-
fuging, and the mother liquor is returned to the
catalyst recovery step. A considerable portion of the
EDTA is lost in the decomposition step.
About 70~ of the sulfur and 10-20~o of the nitrogen
in the byproduct ammonium sulfate are derived from
SO2 and NOx in the flue gas, with the remainder
supplied by sulfuric acid and ammonia added to the
system. The process advantages include the simul-
taneous removal of NOx and SO 2 without the need for
a costly oxidizing agent such as ozone, and the
production of ammonium sulfate as an end product,
which has potential use as a fertilizer. The dis-
advantages include the requirement of many stages of
perforated plates in the scrubber and the consumption
of considerable amounts of ammonia and sulfuric acid.
Chisso plans to prevent ammonium fume formation by
control of scrubber conditions.
If the market for ammonium sulfate is limited, the
process can be modifed to produce gypsum by lime
addition or to produce sulfur by the Institut Franqais
du P6trole (IFP) method. The reaction between am-
monium sulfate and slaked lime is
(NH4)2SO 4 + Ca(OH)2---~CaSO4
+ 2NH 3 + 2H20. (18)
The ammonia would be recycled to the scrubber
and/or neutralizer. The I F P method involves reduc-
tion of ammonium sulfate by submerged combustion
of a fuel gas. The reactions are as follows :
(NH4)2SO4 ~ NH4HSO4 + NH3 (19)
2NH4HSO 4 + S--* 3SO2 + 2NH3 + 2H20. (20)
The vapors from the sulfate reducer are fed to an HzS
generator where H 2S is made by catalytic reduction of
SO 2 with producer gas. The vapors are then fed to a
wet Claus reactor, where H2S and S O 2 react to form
elemental sulfur. Ammonia is recovered from the off-
gas for recycle. The production of elemental sulfur
would significantly increase the process cost.
Catalytic Inc. has licensed the Chisso Engineering
process and combined it with the former's technology
for fumeless ammonia scrubbing and IFP's technology
for sulfur recovery (also licensed by Catalytic) into an
integrated process for potential application to coal-
fired boilers. However, the integrated process has not
yet been tested, and the simultaneous removal of NOx
and SO2 has not been tried on flue gas from a coal-fired
boiler. The process developers suggest that, since this is
a wet process, the increased particulate and chloride
loadings associated with coal combustion will not
present significant problems in adapting their process
to treat flue gas from a coal-fired boiler. The only
modifications envisioned by Chisso to prevent the
buildup of these particulates in the circulating solution
is the addition of a prescrubber and associated process
equipment to remove most of the ash before the flue
gas reaches the absorber, and also a small purge
stream to remove some of the ash-contaminated
Fe(OH)2 sludge from the circulating solution. The
chlorides will be removed primarily in the prescrubber
with a minor amount purged as an NH4C1 contamin-
ant in the (NH4)2SO 4 byproduct stream.
6.2.2. Asahi
Asahi Chemical has developed a wet simultaneous
removal process for NO x and SO2 based on scrubbing
with a sodium sulfite solution containing EDTA and
ferrous ion. Asahi Chemical has obtained a United
States patent on their process. 12 A small pilot plant
with a capacity for treating 25-38 scfm of flue gas from
an oil-fired boiler has been in operation since 1975. In
addition, a 320 scfm scrubber has been operated for the
absorption step only.
A flow sheet for the process is shown in Fig. 7. Flue
gas is first scrubbed with water for cooling and
removal of particulates and chlorides. The flue gas is
then introduced into the absorber, where 80-90~o of
the NOx and more than 99~0 of the SO 2 are removed.
The reactions occurring in the absorber and the
reduction tank (holding tank) are as follows :
Na2SO3 + SO 2 + H20--~ 2NaHSO 3 (21)
Fe +2 _ _ EDTA + NO ~ Fe + 2 _ _ EDTA. NO (8)
2NaHSO3 + 1/202 ~ Na2S206 + H 2 0 (22)
Fe +2 - EDTA + 1/402 + H +
Fe + 3 - E D T A + 1/2H20 (23)
Na2SO 3 + 1/2 O2---, Na2SO4 (24)
Fe +2 -- E D T A - N O + Na2SO3--~ Fe +2 -- EDTA
+ 1/2N 2 + NazSO4 (25)
2Fe +2 -- E D T A - N O + 4NaHSO3 + NazSO 3
--, 2NHISO3Na)2 + Na2SO4 + 2Fe +2 -- EDTA
+ H 2 0 (26)
 Post combustion methods for control of NO~ emissions 301

Cleon ceheoted
stock gas

t H20

LlLimestone
n
slurry

Oouble
conver tel
~:om position
reactor

Hot flue Qo~s !

Ash HzO prqc~

thlcken~

Recycle
tank
Limestone

slurry ~'~--Bleedneutrohzing I H20

2

(CoSO a - I / 2 H~O)
CoSO 3
Separator
~sh CaSO` • 2HzO
CoCIz
CoSO`"2H20
so,
luct PrOdUCt( gypsum )
waste slurryto 0isposol

FIG. 7. Schematicflow diagram for Asahi NO,/SO~ removal process for coal-fired boilers.~3

Fe +3 - EDTA + l/2NazSO 3 + 1/2HzO
--> Fe +2 - EDTA + 1/2NazSO4 + H +.
The sodium dithionate formed is separated by
evaporation and cooling and calcined to produce
concentrated SO 2 and sodium sulfate.
Na2S206 • 2H20---, Na2SzO 6 + 2H/O
Na2S206 --~ NaESO4 + SOz.
Sodium imidodisulfonate in the liquor is treated
with potassium sulfate to precipitate potassium imi-
dodisulfonate, which is separated and calcined to
produce potassium sulfate and SO2.
NH(SO3Na)2 + K2804----> NH(SOsK)2 + Na2SO,,
(30)
2NH(SO3K)z-~ Nz + 2SOz
+ K 2 S O 4 + K 2 S O 3 + H20.
Sodium sulfate is treated with SO/ and calcium
sulfite to regenerate sodium sulfite and produce
gypsum.
CaSO3 + 802 -}- H20----~Ca(HSO3)/
Ca(HSO3)2 + Na2SO4 + 2HzO
--+ 2NaHSO 3 + CaSO4"2H20
2NaHSO 3 + CaCO3--* NazSO 3
+ CaSOs' 1/2 HzO + 1/2 HzO + CO/.
The Asahi Chemical process requires about 2.5
moles of SO z for each mole of NO~ in the flue gas. The
oxygen content of the flue gas should be kept below
5%. NO~ is converted to nitrogen and SO 2 to gypsum.
A sodium sulfate purge stream may be required. The
(27) process chemistry is very complex and many proces-
sing steps are required.
7. CONCLUSIONS
(28)
Currently, Japan has the most stringent ambient
(29) and emission standards for NOx in the world. As a
result, most of the active process development work on
removing NOx from stack gas is taking place there.
About 50 individual processes for removing NOx from
stack gas have been identified. Catalytic reduction
with ammonia is the method most favored in Japan.
Noncatalytic reduction with ammonia is also being
field-tested there. However, the removal efficiency is
not as high as for catalytic reduction. Direct scrubbing
of NO with simultaneous SO 2 absorption may be the
(31)
best combination among the wet processes. Oxidation
before absorption is highly expensive, as are ap-
proaches such as SO2 removal before NOx scrubbing.
However, all the wet processes are complicated and
therefore it is difficult to say which type of process is the
(32)
best. Dry simultaneous removal processes for NO~
and SO 2, with the possible exception of the Shell-UO P
(33) process, are generally less developed and more difficult
to apply than other types of processes.
The dry systems for NOx removal (catalytic or
(34)
noncatalytic reduction with ammonia) do not require
stack gas reheat as opposed to wet systems. However, if
flue gas desulfurization is required, stack gas reheat
may be needed downstream anyway. Corrosion and
plugging problems usually encountered in wet scrub-
302 H.S. ROSENBERG,L. M. CURRAN,A. V. SLACK,J. ANDOand J. H. OXLEY
bing processes are avoided and the relative simplicity
of the dry methods is likely to make them less
expensive than the wet types. Another consideration is
that the main NOx wet scrubbing processes under
development in Japan require at least 3 moles of
SO2/mole of NOx to make the scrubbing chemistry
work. Thus, fuels low in sulfur content may not be
applicable. The main drawback to dry operation is
the particulates in the gas, especially, for coal-fired
boilers. If a catalyst is used, the flyash must either be
removed beforehand or a catalyst type must be used
that resists plugging. The latter approach is by far the
more desirable one.
One of the reasons that the dry processes are the
only types reported being installed on large boilers in
Japan is the fact that flue gas desulfurization (FGD) is
now less attractive there because the market for
byproduct gypsum is becoming saturated. The current
practice is to use low sulfur fuel so that wet scrubbing
of NOx is not considered appropriate. However, the
situation in the U.S. is quite different. Since the 1977
Clean Air Act Amendments require F G D on most new
coal-fired boilers, SO2 scrubbing will be used more and
more and thus would provide the opportunity for
simultaneous NOx removal. Dry methods may still be
preferred for western coal, however, because the SO2
content in the flue gas would probably not be high
enough for good NOx removal in wet scrubbing.
Acknowledgements--The authors want to express their
gratitude to the Electric Power Research Institute for
supporting the research project upon which this paper
is based. Special thanks are due to Donald P. Teixeira
and Navin D. Shah, the EPRI Project Monitors for
this program.
(Manuscript received 12 M a y 1980)
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