Design of Scrubber PDF

PERGAMON
Progress in Energy and Combustion Science 25 (1999) 305337

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Design of scrubbers for condensing boilers

F. Haase*, H. Koehne
Lehr- und Forschungsgebiet fur Energie- und Stofftransport, RWTH Aachen, Kopernikusstr. 16, 52056 Aachen, Germany
Received 16 April 1997; received in revised form 15 January 1999; accepted 15 January 1999
Abstract
Many fuels (oil, wood or process gases) contain components which can be found as acid-forming compounds in the flue gas
after combustion and which are absorbed to a small degree in the condensate when the dew point is reached. This acid, and
therefore highly corrosive condensate, increases the demands on the materials used for the areas affected by condensation in
condensing boilers. The concepts described in the article Design of Scrubbers for Condensing Boilers are based upon use of
the condensate for washing the flue gas. To achieve this, the flue gas is cooled below the dew point in contact with the already
neutralized condensate. This process step allows the wet separation of noxious matter and avoids acid corrosion of the materials
in the area of condensation, raising the choice of possible materials decisively. The review article also exemplifies the state-ofthe-art for condensing boiler technology, as it gives a view of the fundamental principles of two-phase flows, of absorption of
acid-forming gases and their neutralization. Using the examples of sulfuric oxides SOx and nitrous oxides NOx, the effects of
different characteristic features of the gases on the reaction steps are described and possible process steps of the wet separation
in the condensate are discussed. To achieve as high a separation degree as possible between the flue gas and the condensate,
good heat and mass transfer conditions must be guaranteed between the two phasesflue gas and condensate. Dispersing one
of the two phases leads to a strong increase of the interphase. Generally, fluid vaporizers (flue gas as coherent phase) and gas
bubble washers (condensate as coherent phase) can be taken into consideration. Advantages and disadvantages of these
absorbers are worked out for use as washers in combination with condensing boiler technology and the fluid-mechanical
principles necessary for the design of a gas bubble washer. The sometimes contrary influences of constructive parameters
on pressure changes in the flue gas, as pressure loss and mass transfer conditions between flue gas and condensate, are
discussed. q 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Condensing boiler; Scrubber; Desulfurization; NOx absorption; Neutralization
Contents
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2. State of science and technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Condensing boiler technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.1. Dew point and combustion efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.2. Integration of condensing boiler technology in the heating system . . . . . . . . . . . . . . . .
2.1.3. Concepts for condensing boiler technology for sulfurous fuels . . . . . . . . . . . . . . . . . . .
2.2. Deposition of sulfur oxides from flue gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1. Phase equilibria and oxidation at the absorption of SO2 . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2. Mass transfer at SO2 absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
306
308
308
308
308
311
312
314
315
316
* Corresponding author. Address for correspondence: Shell Research and Technology Centre, Hamburg, Deutsche Shell AG, PAE Labor,
OGMPT/4, Hoh-Schaar-Str. 36, 21107 Hamburg, Germany. Tel.: 1 49-40-7565-4739; fax: 1 49-40-7565-4581.
E-mail address: frank.f.haase@ope.shell.com (F. Haase)
0360-1285/99/$ - see front matter q 1999 Elsevier Science Ltd. All rights reserved.
PII: S0360-128 5(99)00002-7
306
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337
2.2.3. Neutralization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3. Wet separation of nitrogen oxides from flue gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.1. Solution of NO and NO2 in water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.2. Oxidation of NO in aqueous solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.3. Absorption and reduction of NO in aqueous solution . . . . . . . . . . . . . . . . . . . . . . . . . .
3. Experimental apparatus and measuring techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. Design of the test boiler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Measuring techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.1. Gas analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.2. Water analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4. Fluid-mechanical layout of a gas bubble washer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. Gas flow through the complete perforated bottom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2. Drag reduction of the flue gas flowing through the water bath . . . . . . . . . . . . . . . . . . . . . . . . .
4.3. Mass transfer between dispersed gas and liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5. Experiments on the absorption and neutralization of SO2 and NOx in the water bath . . . . . . . . . . . . .
5.1. Neutralization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.1. Formation of Mg(OH)2 via hydration of MgO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.2. Carbonate formation by CO2 absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2. SO2 absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.1. Influence of pH on the SO2 absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.2. Sulfite oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3. Wet absorption of nitrogen oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.1. Oxidation and absorption of NO in the water bath . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.2. Absorption of NO2 in water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nomenclature
Physical symbols
A
area (m 2)
a
volume specific interphase (m 21)
b
weir height (m)
c
concentration (mg/l, mol/m 3)
c
specific heat capacity (J/kg K)
d
diameter (m)
dS
Sauter diameter (m)
E
specific emission (mg/MJ)
F
force (N)
f
power ratio of a radiator
Fr*
modified Froude number
g
gravitation constant (m/s 2)
H
enthalpy (J)
h
height of water column above perforated
bottom (m)
H
Henry constant (N m/mol)
h
specific enthalpy (J/kg)
hfg
latent heat of vaporization (J/kg)
HHV
higher heating value (J/kg)
K
equilibrium constant (mg/l) 21
k
velocity constant (s 21)
l
length (m)
LHV
lower heating value (J/kg)
m
mass (kg)
m_
M
n_ 00
318
319
319
320
321
322
322
323
323
323
323
324
327
327
329
329
330
330
332
332
332
334
334
335
335
336
v_d
V_
mass flux (kg/s)

molar mass (kg/kmol)
transferred mole number per time and area
(mol/s m 2)
mole number (mol)
power (W)
pressure (Pa)
pH
heat (J)
heat flow density (J/m 2 s)
heat flow (J/s)
standard heat demand (J/s)
gas constant (J/mol K)
reaction velocity (mol/m 3 s)
specific vaporization enthalpy (J/kg)
jet length (m)
temperature (K)
time (s)
time until 90% of the stationary value is
reached (s)
average velocity in tube (m/s)
volume flow (m 3/s)
Symbols
w
We
average gas velocity (m/s)

Weber number
N
P
p
pH
Q
q_ 00
Q_
Q_ std
R
r
r
s
T
t
t90
x
y
z
a
b
D
1i
1
h
l
q
Dq ln
r
s
j
c
mole fraction
height of perforated bottom above boiler
bottom (m)
number of holes
absorption degree
mass transfer coefficient (mol/N s, m/s)
difference
Henry activity coefficient
volume fraction
efficiency degree
airfuel ratio
temperature (8C)
logarithmic average temperature (K)
density (kg/m 3)
interfacial tension (N/m)
mass fraction
mole fraction
Chemical symbols
Ag
silver
AgCl
silver chloride
Al
aluminum
Ca
calcium
Ca(OH)2
calcium hydroxide
CaCO3
calcium carbonate
CaO
calcium oxide
CaSO3
calcium sulfite
CaSO4
calcium sulfate
methane
CH4
ClO42
perchlorate ion
CO2
carbon dioxide
carbonate ion
CO322
e
electron
EDTA
ethylene diamine tetra-acetate
Fe
iron
H1
hydrogen ion
H2CO3
carbonic acid
H2O
water
H2O2
hydrogen peroxide
H2SO3
sulfurous acid
H2SO4
sulfuric acid
HN(SO3)222 imido disulfonate
HNO2
nitrous acid
HNO3
nitric acid
HO22
hydrogen dioxide ion
HON(SO3)222 hydroxylamine disulfonate
H3PO4
phosphoric acid
hydrogen sulfite ion
HSO32
K
potassium
KClO4
potassium perchlorate
potassium permanganate
KMnO4
M1
metal cation
M2SO3
metal sulfite
Mg
magnesium
Mg(OH)2
magnesium hydroxide
MgNO3
magnesium nitrate
MgO
MgO2
MgSO3
MgSO4
Mn
MnO2
MOH
N(SO3)332
N2
N2O
N2O4
Na2O2
Na2C2O6
Na2SO3
Na2SO4
NaOH
NH3
(NH4)2SO4
NO
NO2
NO22
NO32
NOx
NTA
O2
O3
OH 2
PbO2
Pt
Rh
S2O422
S2O622
SiO2
SO2
SO3
SO322
SO422
magnesium oxide
magnesium peroxide
magnesium sulfite
magnesium sulfate
manganese
manganese dioxide
metal hydroxide
nitrilo trisulfonate
nitrogen
dinitrogen monoxide
dinitrogen tetroxide
sodium peroxide
sodium peroxocarbonate
sodium sulfite
sodium sulfate
sodium hydroxide
ammonia
ammonia sulfate
nitrogen monoxide
nitrogen dioxide
nitrite ion
nitrate ion
nitrogen oxide
nitrilotriacetate
oxygen (molecular)
ozone
hydroxide ion
lead dioxide
platinum
rhodium
dithionite ion
dithionate ion
silicon dioxide
sulfur dioxide
sulfur trioxide
sulfite ion
sulfate ion
Index
*
0
aq
b
bu
c
c
crit
d
dp
fg
fp
g
g
gran
h
i
state of saturation
standard conditions
dissolved
base
gas bubble
combustion
continuously
critical
dispersed
dew point
flue gas
flow pipe
gas side
gaseous
granulated
heating medium
component
307
308
in
kin
l
l
lim
max
min
out
p
r
s
std
wb
entering
kinetic
lifting force
liquid side
limit
maximum value
minimum value
leaving
pressure
return
interfacial tension
standard state
water bath
1. Introduction
Burning fossil energy sources, the acid-forming components sulfur dioxide (SO2) and nitrogen oxides (NOx)
are formed, as well as others, and are emitted into the atmosphere. Following the mass flow of the nitrogenous and
sulfurous compounds after their emission, it is necessary to
differentiate between their effects on the air and on plants,
earth and water.
As the average retention times of the trace gases SO2 and
NOx are only very short (hours up to several days), their
influence on air quality is regionally limited. SO2 and NOx
are toxic to human beings at a certain concentration. The
current discussion about anthropogene influences on the
climate considers SO2 and NOx not in the first place. The
major climate influencing gases in the atmosphere are steam
(H2O), carbon dioxide (CO2), ozone (O3), dinitrogen oxide
(N2O) and methane (CH4). These gases cause the so-called
greenhouse effect of the atmosphere. But SO2, NOx (and
ammonia NH3) lead to the formation of aerosols which are
solid or liquid parts in the air outside of clouds with a
diameter between 0.001 and 100 mm. They scatter and
absorb solar irradiation and emit thermal radiation so they
behave contrary to the anthropogene heating of the earth [1].
The largest part of the emission is chemically converted
in the air before it is deposited via rain. At the chemical
conversion of sulfur dioxide, sulfuric acid (H2SO4) is
formed; its salts are called sulfates (SO422). Finally, gypsum
or Na2SO4 is formed. Nitrogen monoxide is oxidized to
nitrogen dioxide, which forms nitric acid; its salts are called
nitrates (NO32).
Before the acids formed by SO2 and NOx get into the
ground, the protective wax coating on tree leaves and
needles can be damaged. Nutritive substances are washed
out. Also, the supply of nutritive substances of the ground
decreases. With increasing acidity of the ground, first
calcium magnesium and potassium, and in later stages,
manganese and aluminum are dissolved out of the ground
particles. They are washed out and lost to the ecosystem [2].
Together with the washed out alkali sulfates and nitrates
combine with drained rainfall into surface waters or via

the sewage system into a sewage treatment plant.
Fig. 1 shows the effects of sulfurous and nitrogenous
compounds in the air, on plants, earth and water for the
emissions of SO2 and NOx.
This mass flow proves that the wet deposition of SO2 and
NOx in condensing boilers under the formation of sulfate
and nitrates and the necessary neutralization correspond to
the processes in nature.
The wet deposition of SO2 and NOx, immediately after
their formation in the combustion chamber of the washer for
condensing boilers, is described here. The specialty of these
washers is that the condensate formed by falling short of the
steam dew point is used as washing water.
Thus, an almost complete absorption of the sulfur dioxides is possible in the condensate if the flue gas contacts
immediately neutralized condensate under good heat and
mass transfer conditions. Meeting these requirements results
in washing the flue gas and preventing the boiler parts in the
condensation area from corrosion.
Combining the condensing boiler technology (CBT) with
flue gas washing increases the choice of usable materials for
fuels with a very aggressive condensate and the operative
expense is kept low at the same time. As a result of low
energy prices, condensing boiler technology is difficult to
realize economically for the fuels mentioned and a small
power output. But the additional flue gas washing provides
a motivation which should be encouraged by means of
legislation.
2. State of science and technology

2.1. Condensing boiler technology
According to their energy content, fuels are described by
the lower heating value (LHV) and the higher heating value
(HHV). The LHV of a substance is the amount of heat set
free at complete combustion when reactants and products
show the same temperature and water formed at combustion
exists as steam. The difference to the gross caloric value of
the fuel is that it considers the water as liquid, so the gross
caloric value is, by the condensation heat of the water,
greater than the net caloric value (HHV=LHV
hfg jh =LHV with j h mass fraction of hydrogen in the
fuel). Condensing boilers are those which make the latent
heat contained in the flue gas usable by condensation.
2.1.1. Dew point and combustion efficiency
The condensation of water begins when the state of
saturation for the steam in the flue gas is reached while
cooling the flue gas. This point is called the dew point,
and its temperature is the dew point temperature q dp. At the
dew point the steam pressure equals the saturation steam
pressure of water, which isas an approximationfor
309
Fig. 1. Deposition of SO2 and NOx in the condensate of the flue gas as an alternative to their emission.
a total pressure below 10 bar, only dependent on the

temperature.
For the combustion of fuels, the partial pressure of steam
in the flue gas depends on fuel composition (hydrogen
content), airfuel ratio l and the humidity of the combustion air. Disregarding the air humidity, the dependence
between the dew point temperature q dp and airfuel ratio
l is obtained, as shown in Fig. 2 for the standard heating oil
in Germany called EL (extra light). With an increase in
airfuel ratio l , the flue gas must be cooled to achieve
steam condensation.
By burning sulfurous fuels, the hydrophile sulfur trioxide
(SO3) in the flue gas acts as a condensation nucleus resulting

in an increase of the dew point temperature. For an exact
determination of the so-called acid dew point, knowledge
of the conversion of sulfur dioxide (SO2) to sulfur trioxide
(SO3) is necessary. As an approximation, it is assumed that
the volume concentration of SO3 is about 1% of the concentration of SO2 [3]. It can be seen in Fig. 3 that the dew point
increases under these conditions for a sulfur content in the
flue gas of j S 0.2 % by 72 K and lies for an airfuel ratio
l 1.1 at q dp 1208C.
As a measure against acid corrosion or sooting, conventional heating technology avoids falling short of a flue gas
310
Fig. 2. Dew point temperature q dp of the flue gas from the combustion of heating oil EL versus airfuel ratio l .
temperature q fg 1508C before leaving the flue gas system.

By introducing condensing boiler technology into an existing heating system, a large fraction of the sensible heat
connected to the high flue gas temperature of conventional
heating systems can be used.
To evaluate a heat generator, the combustion efficiency
supplied energy 2 energy at flue gas outlet
1
hc
supplied energy
can be used (the so called boiler efficiency takes into
account in addition heat losses through the jacket).
Determining the delivery energy by the HHV, one
obtains:

P
ji hi qfg 2 hi q0 1 jH2 O hfg
2
hc 1 2 i
Hg q0
where hi is the specific enthalpy of the gaseous component i,
j i the mass fraction of the gaseous component i in kg/kgfuel,

q 0 the flue gas temperature and hfg the latent heat of vaporization of water at standard temperature.
Here we assume that fuel and dry air are supplied at a
standard temperature q 0, which usually is the thermodynamic standard temperature q 0 258C. The enthalpy of
the condensed water is disregarded here. For heating oil
EL, the result is dependence between combustion efficiency
h c, flue gas temperature q fg and airfuel ratio l shown in
Fig. 4.
When falling short of the dew point temperature, a strong
increase of the combustion efficiency h c can be observed,
which is attributed to the addition of condensation heat to
the sensible heat.
The concept of flue gas washing, used with condensing
boiler technology, dealt with here, aims at complete
absorption of the sulfur oxides in the condensate of the
Fig. 3. Increase of the dew point caused by sulfuric acid in the flue gas (calculated data) [3].
311
Fig. 4. Combustion efficiency h c specific to HHV.
flue gas. Good mass transfer conditions between flue gas and
necessary condensate result in complete saturation of the
flue gas with steam, so that for only a slight increase of
the temperature above the dew point, condensate will vaporize and combustion efficiency decreases compared to a dry
flue gas system. This phenomenon is shown in dashed
curves in Fig. 4 and provides the necessity of avoiding
flue gas temperature above the dew point by appropriate
control systems.
2.1.2. Integration of condensing boiler technology in the
heating system
For the layout of a heating system, the so-called standard
heat demand of a building, Q_ std is used; it describes the heat
power supplied to heat the rooms to comfortable temperatures at a low outdoor temperature [4]. Using the standard
heat demand for the layout of the boiler (provided that the
piping losses are negligible), the boiler has to supply the
power

3
Q_ h Q_ std m_ h ch qfp 2 qr
to the heating circuit. In the aforementioned equation, mh
represents mass flux of the heating medium, ch the specific
heat capacity of the heating medium, q fp the flow-pipe
temperature of the heating medium and q r the return
temperature of the heating medium.
The values of the process parameters mh, q fp, q r and their
combinations can only be chosen within certain limits. If the
flue gas is cooled below its steam dew point by the heating
medium, the maximum return temperature is then determined according to Fig. 2 depending on the airfuel ratio
l chosen.
Fig. 5. Influence of flow-pipe and return temperature on the power ratio f of a radiator.
312
Fig. 6. Condensing boiler technology with flue gas desulfurization;

concept I [13].

concept II [14].
The value of the flow-pipe and the return temperature of

the heating medium has a decisive influence on the heat
supply of a radiator; its heat flux Q_ can be described by

Q_ , A Dqln n
4
The following rules can be summed up for the integration

of condensing boilers into heating systems [710]:
with the radiator surface A and the logarithmic average

temperature
Dqln
qfp 2 qr

ln qfp 2 qroom =qr 2 qroom
The value of the exponent n lies within the limits 1.1 to 1.5;
for radiators, n < 1.3 is obtainted [5], for floor radiators, n <
1.1 [6]. Making the heat flux from Eq. (4) specific to standard conditions (q fp,std 908C, q r,std 708C, q room,std
208C) [5], the so called power ratio of a radiator for equalsized radiator surfaces
!n

Q_
q_
Dqln
Dqln
f _
6
q_std
Dqln;std
59:44 K
Qstd
This relation is valid for m_ H =m_ H;N $ 0:2 and can be used to
determine the heat a radiator supplies for various pairs of
flow-pipe and return temperature. Fig. 5 shows the power
ratio f dependent on the return temperature q r for different
flow-pipe temperatures q VL. It can be seen from Fig. 5 that
the supplied heat flux of a radiator decreases
if the temperature difference (q fp 2 q r) is increased
when the return temperature is lowered by reducing the
heat medium mass flux and keeping the flow-pipe
temperature constant (line A),
if the temperature difference is decreased by lowering
the flow-pipe temperature, keeping the return temperature constant (line B),
if the temperature level is decreased, keeping the
temperature difference constant (line C).
If the same heat flux is to be obtained as in the standard
case, the radiator surface must be increased according to
A
1
A :
f std
The temperature of the heating medium must be as low

as possible, with a considerable difference between flowpipe and return temperature. In new buildings, condensing boilers are often connected to floor radiators, or
heating systems with low temperature radiators. Even
in old buildings, there must be no limitations for appropriate integration of the condensing boiler technology.
Heat demands of the building are less than during
construction as a result of subsequent thermal insulation;
and because the existing heating systemdesigned for
temperatures q fp 908C and q r 708Cis overdimensioned because of formerly common security
factors, lowering the heating medium temperatures is
possible.
In contrast to humidity-sensitive boilers (standard or low
temperature boilers), measures leading to a raised return
temperature (mixing valves) must be avoided generally
when using condensing boilers.
An over-dimensioned installed boiler power does not
reduce the annual efficiency degree, in contrast to
conventional boilers, because the boiler walls are cooled
down intermittently so that lower flue gas temperatures
are reached at the beginning of each phase of burner
operation.
To adapt to a lower heat demand (part load), not the
heating medium flux, but the flow-pipe temperature
should be reduced. A high heating medium flux is
related to higher requirements on the thermostat
valves [11].
The use of liquid layer reservoirs with a separate
heat exchanger has proved to be efficient in combination with the condensing boiler technology. The
war water reservoir is connected via a prioritycontrolled three-way valve to the flow-pipe. The
heat exchange takes place in counter-flow with
the cold water for domestic use from the bottom
of the reservoir, so condensing boiler technology is
possible even for warm water temperatures of
608C.

concept III [15].
2.1.3. Concepts for condensing boiler technology for

sulfurous fuels
Condensing boilers have been offered for sulfurous fuel
for ten years. While the use of condensing boiler technology
is state-of-the-art today for the nearly sulfur-free energy
source gas, it has not found acceptance from planners,
installers and users because of the higher standards on the
boiler construction and the discharge of condensate into the
public sewage system connected to the condensing boiler
technology.
The boilers offered on the market offer the following
constructive principles. The combustion chamber is cooled
first by a heat exchanger, so the flue gas produces a temperature between 150 and 1808C. A lower flue gas temperature is
avoided because condensation forming sulfuric and sulfurous acids would then require the use of non-corrosive materials. Nevertheless, a low temperature is targeted so as
little energy as possible must be coupled out at a lower
temperature level in a second heat exchanger. This second
heat exchanger is constructed of non-corrosive material
because the condensation of the steam contained in the
flue gas takes place here, and sulfuric acid is formed. Gener-
313
ally, non-corrosive steels are used, but ceramics, glass or

graphite can be used as well.
The heating medium either flows continuously through
the heat exchangers, or as part of two separate heating
circuits operating at different temperature levels. Pre-heating the combustion air with the second heat exchanger is a
further variant.
The condensation of the steam which takes place, forming
sulfuric and sulfurous acid, leads to an acid condensate with
a pH value of about 2. Under these acid conditions, only a
small part of the sulfur oxides contained in the flue gas
remains in the condensate, so we cannot speak of a flue
gas desulfurization [12]. Together with condensate from
the flue gas system, the condensate is led to a neutralization
unit and is finally discharged into the public sewage system.
To achieve neutralization, either calcium or magnesium
granulate or ion exchangers are used. The granulates loose
their efficiency if the condensate contains metal ions which
may arise from low temperature corrosion. In this case,
metallic compounds settle down on the active surface of
the granulate because of the low flow velocity and do not
allow its further disassociation. To avoid this problem, ion
exchangers are often used before the granulate.
Following are four concepts for the condensing boiler
technology, which aim for desulfurization of the flue gas.
The common points of these concepts is that the flue gas is
brought in contact with the neutralized condensate when the
temperature falls short of the dew point.
The condensate from the combustion chamber of the first
boiler is drawn off via a drawing wheel and is dispersed in a
neutralized water bath (Fig. 6). A good mixing of water and
flue gas guarantees a complete heat transfer and the absorption of sulfur oxides. To achieve cooling of the flue gas,
three heat exchangers are used. The return flow of the heating medium flows continuously through a heat exchanger in
the cleaned flue gas, a coiled pipe which is arranged in the
Fig. 9. Condensing boiler technology with flue gas desulfurization; concept IV [16].
314
water bath and at last through the heat exchanger in the

combustion chamber. The electric motor used to power
the drawing wheel has a power demand of 600 W [13].
For a nominal power of 17 kW, efficiency decreases by
3.5% without considering the low efficiency for the
generation of electricity.
In the second concept for condensing boiler technology
with flue gas desulfurization, the condensate is led through a
neutralization cartridge via a circulation pump, is dispersed
via nozzles in a gas-washing tower and is returned to the
condensation heat exchanger (Fig. 7). In the gas-washing
tower the condensate absorbs the sulfur oxides from the flue
gas. In Fig. 7 are shown two heat exchangers, the first one for
preheating the returned heating medium, the other one for
heating the water for domestic use. The heat exchangers are
arranged in a reservoir of neutralized condensate. Thus excellent heat exchange makes a compact apparatus possible.
The third concept for condensing boiler technology with
flue gas desulfurization is a very compact burner/boiler
setup. A vertically-arranged combustion chamber is cooled
by surrounding water bath (Fig. 8). The flue gas leaves the
combustion chamber at its open bottom end and rises in the
water bath in the form of bubbles. Also in this concept, the
contact of flue gas and water realizes a complete heat transfer
and allows the absorption of sulfur oxides. The possibility of
producing boilers of plastic materials is seen as a central
advantage of this concept [15]. The complete combustion
heat is transferred by one heat exchanger from the water
bath to the heating medium. Preparing high flow-pipe temperatures and cooling the flue gas below its dew point at the same
time is not possible, so this boiler is to be regarded only as a
low-temperature heating system. As the combustion chamber
is completely submerged in the water bath, a water column as
high as the length of the combustion chamber must be overcome by a fan. The electric power demand is also connected to
a decrease of efficiency.
The fourth concept for the condensing boiler technology,
developed by the authors, is also based on a gas bubble
washer. Fig. 9 shows a module which can be used in
combination with a standard boiler or integrated in a
condensing boiler. The heat changes by two temperatures,
so the flow-pipe temperature above the dew point and
condensation is possible simultaneously.
For raising efficiency of condensing boiler different
measures are described. Variants on concept II [14] and
concept IV [17] use the heat transfer and mass transfer
(water steam) between flue gas and combustion air for
reducing flue gas temperature.
2.2. Deposition of sulfur oxides from flue gas
Sulfur contained in the flue gas is burned together with
oxygen to sulfur dioxide (SO2). Sulfur dioxide reacts with
oxygen to sulfur trioxide (SO3) according to the following
equilibrium:
2SO2 1 O2 N 2SO3
For gas temperatures higher than 12008C, no relevant oxidation takes place because of the state of the equilibrium.
Also, no relevant oxidation can be observed when cooling
the flue gas in the boiler, because the velocity of reaction (8)
is low [18]. SO3 shows a very good solubility in water and
reacts under the presence of steam to form sulfuric acid.
Thus, the technology used for a deposition of SO2 generally
also achieves good results for SO3, therefore in the following, the deposition of SO2 will be seen as the central point of
the investigations. In the USA and in Japan, flue gas desulfurization units have been used in power plants for over 30
years; in Germany, their use began about 20 years ago [19].
The long development time has led to a number of process
variants which generally can be divided into washing, spray
absorption and drying processes.
Washing processes
Washing processes usually work with suspensions of
calcium oxide (CaO, caustic lime), calcium hydroxide
(Ca(OH)2, slaked lime) or calcium carbonate (CaCO3, limestone). The primary product of the lime washing process is
calcium sulfite (CaSO3). In Germany, gypsum CaSO42H2O
is usually gained via oxidation, which is either dumped or
made usable by subsequent processes [20]. Alternatively,
the Walther Company uses an ammonia solution for washing and acquires ammonium sulfate ((NH4)2SO4) as a
product which can be used as synthetic fertilizer [21]. As
a result of the good solubility of the ammonia salts, no
fouling problems occur. MontanWerke Brixlegg, in
Austria, uses a washer which is operated with an
Mg(OH)2 suspension which is produced from MgO by
adding water [22].
Spray absorption processes
During spray absorption processes (also called mixed methods), calcium hydroxide suspensions with a high solid fraction are sprayed into the hot flue gas stream [23]. The water
vaporizes and the salts formed are drawn off, together with
the excess lime and some fine dust, by textile or electric
filters positioned further downstream. A disadvantage is
the over-stoichiometric consumption of lime and the lower
deposition degree of SO2 as compared with wet processes.
Dry processes
During dry processes, we differentiate between lime absorption (dry additive process) and the absorption via activated
coke (mining technology). During dry additive processes,
small-grained lime is blown into the hot flue gas. As an
alternative, lime may be added to the fuel. The calcium
sulfite, calcium sulfate and the remaining lime which are
formed are drawn off a dust filter. Low quality coal and
brown coal naturally contain lime. In pulverized coal
furnaces, which are common in boilers of large dimensions,
lime reaches the combustion chamber as fine dust and
absorbs part of SO2 in the ash. A complete desulfurization
seems possible with the fuel-own lime if a low combustion
315
Fig. 10. Course of concentration and partial pressure of SO2 according to the two-film theory [27].
temperature avoids burning the lime to death and realizes

low flue gas temperatures [24].
The mining-technological process [25] binds SO2 adsorptively to activated coke and converts it to sulfuric acid.
Sulfuric acid is stored in the pores of the activated coke.
The activated coke is then thermally regenerated so it can be
used again. The gas mixture set free contains 2030 vol.%
SO2, which is converted in further steps to sulfuric acid or
elementary sulfur. This process can also be used for similar
removal of sulfur and nitrogen oxides from flue gas, if
ammonia is also used.
Both sorption processes used for flue gas desulfurization,
adsorption and absorption, selectively take over one or more
components from a gaseous mixture into a condensed phase,
as happens during the simultaneous deposition of sulfur and
nitrogen oxides. In the following, the solution of a gaseous
phase in a liquid by absorption is examined because in the
concept of flue gas washing with condensing boiler technology described here, the deposition of sulfur oxides and nitrogen oxides takes place in the liquid condensate of the flue
gas.
2.2.1. Phase equilibria and oxidation at the absorption of
SO2
When dissolving a gas in a liquid, the physical and the
chemical absorption are differentiated. In physical absorption, the absorbed gas molecules are surrounded by a
hydrate cover, but no reaction takes place, so the gas molecules can leave the liquid very easily. In contrast, we speak
of chemical absorption or chemisorption if the gas is
engaged in a chemical reaction in the liquid.
To observe maximum load of the absorbent and the
composition of the gaseous mixture after the cleaning,
knowledge about the solubility of a gas in a liquid is
necessary. Such knowledge is dependent upon temperature,
pressure and composition of the gaseous and the liquid
mixture. According to the classification of physical and
chemical absorption, phase equilibria are described in

different ways.
For physical absorbents, the phase equilibrium of a single
component can be expressed by the Raoults law. For ideal
mixtures of gases and liquids, it reads
pi xi pi *
where pi is the partial pressure of the component i, xi the

mole fraction of the component i in the liquid and p*i the
saturation partial pressure of the component i as function of
temperature.
Raoults law states that the partial pressure of the component i in the gaseous phase is proportional to the mole fraction of the component i in the liquid for a constant
temperature. As the absorption of SO2 takes place exothermically, the solubility decreases with increased temperature.
Solubilities determined with Raoults law can be taken as
approximate values but they do not consider the type of
solvent. The law assumes that a certain gas has the same
solubilities in all solvents for the same temperature and
partial pressure [26].
To take into account the difference between the ideal
behavior of the gas and the liquid mixture, Raoults law
can be extended by the Henry activity coefficient 1 i:
pi 1i xi pi * and 1i 1i xi ; p; T
10
where 1 i is the Henry activity coefficient, p the total pressure

and T the temperature.
If the concentration of the absorbed component in the
liquid is low, 1 i is constant and one obtains the Henry law
found for dilute solutions:
pi 1i xi pi *
11
where 1i 1i p; T. For a given temperature, the partial

pressure of a component is connected via the Henry activity
coefficient in a linear path to the mole fraction of the component in the liquid. If the determination must be even more
316
exact than the Henry law, the dependence of the Henry

activity coefficient on the mole fraction of the component
in the liquid must be taken into account.
For the absorption of SO2 in water, the hydration
SO2 g 1 H2 O N SO2 aq 1 H2 O
12
is described by the physical absorption.

The following hydrolysis of the sulfur dioxide SO2(aq)
corresponds to the chemical absorption. The chemical
absorption of sulfur dioxide in water takes place as follows:
SO2 aq 1 H2 O N H2 SO3
13
The law of mass action states that a chemical reaction

stops at a given temperature (equilibrium), if the quotient
from the product of the concentrations of the reaction
products, and the product of the concentrations of the reactants, reaches a certain value K, which is characteristic for
the reaction. The characteristic value K, is called
equilibrium constant and can be determined for the
hydrolysis of SO2 according to Eq. (13) as follows:
cH2 SO3
K
14
cSO2 aq cH2 O
Sulfurous acid (H2SO3) formed here dissociates in two steps.
In the first step, hydrogen sulfite (HSO32) and hydrogen ions
(H 1) are formed, in the second steps, free sulfite ions (SO322)
and H 1 are formed:
H2 SO3 N HSO3 2 1 H1 N SO3 22 1 2H1
15
The hydrogen ions set free by the dissociation results in an

acid reaction of the solution. Adding a hydroxide MOH to
the absorbent which reacts with the hydrogen ions to
achieve a neutralization
H1 1 MOH N H2 O 1 M1
16
the concentration of the hydrogen ions decreases, and the

reactions described in the Eqs. (12)(14) react towards their
right side in order to re-establish the equilibrium, so as a
conclusion, SO2(g) can further be absorbed.
If the absorption of SO2 and the neutralization are continued, the total concentration of the dissolved SO2 (SO2(aq),
H2SO3, HSO32, SO322) increases until the state of saturation
of the salt M2SO3 formed out of sulfite SO322 and the cation
M 1 in the solution is reached. Exceeding the state of saturation results in precipitation of the formerly dissociated salt
as a solid.
Among the precipitation as a sulfite salt, it is possible that
the dissolved sulfite reacts with dissolved oxygen to sulfate
(SO422):
SO22
3 1
1
O aq N SO22
4
2 2
17
While the direction of the equilibrium reactions (11), (12)

and (14) can be influenced easily by temperature changes,
redox reactions show a strong dependence on the pH of the
solution. The equilibrium of the oxidation reaction (17) lies
in bothin acid and in alkaline solutionand for the

temperature range in which condensing boiler technology
is used on the side of the product.
The oxidation of a reductive (e.g. SO322) and the reduction
of an oxidizer (here SO422) takes place according to the
following equilibrium:
reductive
reduction
N oxidizer 1 electron
oxidation
18
A system which donates and accepts electrons according

to this equation is called redox system or redox pair.
As free electrons do not exist under normal chemical
conditions, the donation of electrons only takes place in
the presence of an appropriate reductant. The donated electrons are accepted by the reductant while it changes to the
corresponding oxidant. Thus, a redox reaction always
consists of two corresponding part reactions. The total reaction shown in Eq. (17) consists of the following part
reactions:
2
22
2
SO22
3 1 2OH N SO4 1 H2 O 1 2e
1
O 1 2e2 1 2H1 N H2 O
2 2
SO22
3 1
1
O 1 2OH2 1 2H1 N SO22
4 1 2H2 O
2 2
19
20
21
2.2.2. Mass transfer at SO2 absorption

At existing flue gas washers, gas mixture and washing
liquid are in contact repeatedly with a limited contact area
and for a limited contact time, so an almost complete mass
transfer of SO2 from the gas phase to the liquid phase takes
place. The mass transfer model presented here is greatly
simplified and will not be used for predicting the SO2
concentration in the gas mixture but will permit a clear
discussion of the influencing parameters.
The concentration differences between phase and interphase act as the moving force for the mass transfer. The twofilm theory can be used to describe the mass transfer from
fluid to fluid [27]. According to the two-film theory (Fig.
10), a laminar interphase is formed between the gas boundary layer and the liquid boundary. The boundary layers
represent the main resistance for mass transfer. The interphase does not show a resistance if the boundary layers are
in steady state.
Within the boundary layers, mass transfer takes place by
diffusion. Turbulences which are based on the penetration
model [28] result in a certain decrease of the boundary layer
thickness, so an acceleration of the mass transfer is the
result. The boundary layer that shows the highest resistance
against diffusion determines the velocity of the mass transfer. If one of the resistances is dominant, the other can often
be neglected. Gases which are easy to dissolvesuch as
SO2 diffuse faster through the liquid boundary layer than
through the gas boundary layer. Thus, the resistance of the
gas boundary layer becomes dominant and can be regarded

as the main resistance [28].
Generally, three kinds of phase distribution must be
considered for the absorption:
(a) Both phases exist coherently (film absorber).
(b) The gaseous phase is dispersed in the coherent liquid
phase (bubble column).
(c) The liquid phase is distributed dispersely in the coherent gaseous phase (spray washer).
A disperse distribution of a phase can achieve a larger
contact surface per volume unit than a continuous
distribution.
For the following model of a disperse distribution of the
gas phase in the coherent liquid phase, several assumptions
are made:
1. The SO2 concentration in the coherent phase is homogeneous.
2. An equilibrium exists at the interphase.
3. Pressure variations are negligible.
4. The mass transfer is dominated by the resistance of the
gaseous phase.
Regarding a single gas bubble, we can write for the
amount of SO2 transferred through the interphase:
n_ 00SO2 ;g bg pSO2 2 pSO2 ;int
22
n_ 00SO2 ;l bl cSO2 ;int 2 cSO2
23
n_ 00SO2 n_ 00SO2 ;g n_ 00SO2 ;l
24
n_ 00SO2
where
is the mole number per area and time of the
transferred SO2 b g, b l mass transfer coefficient for the gas
side in mol/Ns, for the liquid side in m/s.
Further
n_ 00SO2
dn 00SO2
dpSO2 1 Nbu
2
dt
dt pg Abu
25
where Nbu is the mole number in the gas bubble, Abu the
surface of the gas bubble and pgtotal pressure of the gas in
the bubble.
Substituting Eq. (22) in Eq. (25) and integrating over time
within the limits of entering the liquid and leaving the
liquid, we obtain:
pSO2 2 pSO2 ;int uttout

26
A
pSO2 2 pSO2 ;int uttin exp 2bg pg bu tout 2 tin
Nbu
The partial pressure of SO2 at the interphase pSO2 ;int cannot

be determined by experiments. Neglecting the resistance
from the liquid side and assuming a homogeneous concentration of SO2 in the liquid phase, as mentioned above, the
following equations are valid:
cSO2 ;gr cSO2 cSO2 t tout cSO2 t tin :
27
317
As an equilibrium exists at the interphase, according to the

two-film theory (assumption 2), the partial pressure pSO2 ;int
is connected via the Henry law to the SO2 concentration in
the liquid:
pSO2 ;gr H SO2 cSO2
28
Substituting this in Eq. (26), one obtains:

h
i
pSO2 t tout HSO2 cSO2 1 pSO2 t tin 2 H SO2 cSO2

A
exp 2bG pG bu tout 2 tin
Nbu
29
The SO2 partial pressure after leaving one stage of the
washer, pSO2 (t tout) is determined by
1. the concentration of SO2 in the liquid cSO2 ,
2. the SO2 partial pressure before entering the liquid pSO2
(t tin) as a function of the sulfur content of the used fuel
and
3. the parameters b G, (tout 2 tin), Abu =Nbu , pg which can be
influenced by design and operation modus of the washer.
The concentration cSO2 of the physically absorbed
SO2(aq) is dependent on the state of the reaction equilibria
according to Eqs. (13), (15) and (16). Assuming an ideal
neutralization which guarantees a constant pH, a constant
distribution of the various forms of sulfite (SO2(aq), H2SO3,
HSO32, SO322) is expected. In Section 2.2.3, the different
possible neutralizers and their effects on the mentioned
equilibrium chain are described.
Next to the equilibrium reactions, oxidation from sulfite
to sulfate, according to Eq. (17) also takes place in the
presence of dissolved oxygen. The reaction velocity is determined by the sulfite concentration, but not by the oxygen
concentration, as long as enough dissolved oxygen is
present [29]:
r kcSO22
1:5 c0O2 :
3
30
If gas is led stationary and under constant boundary

conditions through the liquid, a quasi-stationary concentration of the total sulfite will ensue. Its experimental determination using the law of mass action (Section 3.2.2) allows
conclusions to be drawn regarding the concentration
cSO2 (aq) of the physically absorbed SO2.
The parameters b g, (tout 2 tin),, pg, which are influenced
by design and operation modus of the washer, will be
discussed in Section 4.3 for an ideally chosen dispersion
unit. The choice of a long contact time (tout 2 tin) between
gas mixture and liquid has, according to Eq. (29), the same
influence as an increased contact area specific to the gas
amount Abu/Nbu or a large mass transfer coefficient b g caused
by turbulences in the gaseous phase. These variables determine the mass transfer from the gaseous phase to the liquid
phase and have an exponential influence on the SO2 partial
pressure pSO2 (t tout) after leaving the liquid.
318
Table 1
Solubility of the compounds at 20 and 508C in 100 g water
Cation
Reactants
Hydroxide (g)
Products
Carbonate (g)
Sulfite (g)
Sulfate (g)
Na
208C
508C
Mg 21
208C
508C
Ca 21
208C
508C
a
b
52.2 [30]
59.2 [30]
18.1 [30]
32.2 [30]
27.1 [30]
34.7 [30]
19.1 [30] as Na2SO4

46.4 [30] as Na2SO4 rhombic
0.000017 a [30]
0.000015 b [30]
0.000072 a [31]
0.6 [30] as MgSO4(H2O)3

0.844 [30] as MgSO3(H2O)3
25.2 [30] as MgSO4(H2O)7

33.4 [30] as MgSO4(H2O)6
0.126 [18]
0.0917 [30]
0.0065 [30]
0.0038 [30]
0.0043 a [30]
0.0057 [30]
0.2 [32] as CaSO4(H2O)2

0.21 [32] as CaSO4(H2O)2
At 188C.
At 458C.
Eq. (29) makes clear that even under ideal mass transfer
conditions, the SO2 partial pressure after the washer is not
zero; so the conversion of the sulfite in the liquid is of a
particular importance.
2.2.3. Neutralization
By absorption of sulfur dioxide or other acid gases, the
pH decreases and the adsorbent will be quickly saturated
with SO2. Raising the pH to a neutral area (neutralization)
will change the equilibria described in Section 2.2.2, so SO2
can be further dissolved. The neutralizer must either be
added continuously during the absorption of SO2, or it
must be in excess in the absorbent.
During neutralization, an acid reacts with a base under the
formation of a salt and water. The main reaction is the
synthesis of hydrogen ions and hydroxide ions:
H1 1 OH2 N H2 O
31
Substances used as neutralizers must either contain

hydroxide ions or form hydroxide ions in an aqueous solution. In choosing a neutralizer we must consider the following criteria:
1. affiliation of educates or products to a certain class of
hazardous materials,
2. availability and price,
3. aperitif expense of the neutralizer dosage.
Considering these criteria, a large number of possible
substances are reduced to oxides, hydroxides and carbonates
of sodium, magnesium and calcium. While hydroxides and
carbonates dissociate partly or (because of their high
solubility), completely in an aqueous solution while tending
toward a steady state, oxides are hydrated in an aqueous
solution.
The characteristic features of magnesium oxide (MgO)
and calcium oxide (CaO) depend on their preparation and
their preparatory treatment. Magnesium and calcium oxides
which were prepared at high temperatures are less reactive
and do not dissolve as well in water as those prepared at

lower temperatures. MgO and CaO can be gained by dehydration of hydroxides or, as it is technically usual for large
amounts, by heating (burning) the carbonates to temperatures between 800 and 10008C [18].
If MgO is added to water, magnesium hydroxide is
formed:
MgO 1 H2 O ! MgOH2
32
This hydration does not continue until the complete

conversion of MgO because the active surface of the
oxide decreases, pores are filled for compact material and
magnesium hydroxide forms a protective coating.
Calcium oxide reacts with water in high temperatures,
heat development and forms calcium hydroxide (slaked
lime) [18]:
CaO 1 H2 O ! CaOH2
33
Magnesium hydroxide (Mg(OH)2) is a compound which

is difficult to dissolve. Ca(OH)2 shows greater solubility
compared to Mg(OH)2 (Table 1), so dissolving this
compound results in a higher pH.
Sodium hydroxide (NaOH) is achieved by the chlor-alkali
electrolysis. Easily dissolved in water, its solution is caustic
soda and is a strongly etching substance and therefore a
hazardous material.
If carbon dioxide added to into an aqueous hydroxide
solution, it forms dissolved CO2, carbonic anhydride
H2CO3, hydrogen carbonate HCO32 and carbonate CO322
dependent on pH. With the absorption, the pH of the solution decreases until finally no carbon dioxide can dissolve
any longer (equilibrium reactions). Adding a stronger acid
(H2SO3, H2SO4), carbon dioxide exhales (replacement)
while the pH remains constant; so the carbonates act as
buffers:
M2 CO3 1 H2 SO4 ! CO2 1 H2 O 1 M2 SO4
34
The carbonates of magnesium and calcium are hardly
319
Fig. 11. Methods of absorbing nitrogen oxides in an aqueous solution.
soluble in water. Sodium carbonate dissolves in water with

an alkaline reaction and shows greater solubility as the
carbonates of magnesium and calcium. Handling sodium
carbonate is much less dangerous than handling sodium
hydroxide.
The different solubilities of the mentioned neutralizers
shown in Table 1 require different dosage concepts:
Na compounds
Sodium hydroxide and sodium carbonate must be administered doses in corresponding to the absorbed amount of SO2
to prevent the solution from becoming alkaline. If these
compounds are added in excess, discharging the absorbent
into the sewage system means a heavy loss of neutralizer.
For such a dosage, a continuous pH measurement, a dosage
valve or a dosage pump, a storage tank and a control system,
is necessary.
Mg compounds
As a result of the low solubility of Mg(OH)2, a dosage is not
necessary when using MgO (which hydrates to Mg(OH)2) or
Mg(OH)2 and the neutralizer can be added in excess to the
neutralization solution. In the slightly alkaline solution, the
equilibrium (MgOH2 ! Mg21 1 OH2 ) is disturbed with
the initial absorption of acid gases and a fast dissociation of
Mg(OH)2 begins, so the solution does not become acid. The
reaction velocity decreases when approaching the
equilibrium.
Ca compounds
Using calcium oxide and hydroxide in excess like the
magnesium compounds, a higher pH in the solution will
result because the slightly greater solubility of the calcium
compounds. Calcium sulfite and sulfate show very low solubility in comparison to the sodium and magnesium salts.
Therefore, the use of calcium compounds requires that the
salts formed at the absorption of SO2 be drawn off as solids

to be used as productsas they are used in the power plant
sectoror that they be dumped. To discharge the formed
salts into the public sewage system, sodium and magnesium
compounds are appropriate neutralizers.
The compounds described here are available in a very
wide price range, depending on their method of preparation
and their purity. Generally, calcium hydroxide is known as
the least expensive industrially used neutralizer. As a result
of its various applications in soap production, in dyes, in the
preparation of cellulose and as a cleaner, caustic soda is very
inexpensive.
2.3. Wet separation of nitrogen oxides from flue gases
In burning fossil energy sources, the noxious matter NO
and NOx are formed which together are spoken of as NOx.
As the Bodenstein reaction of NO
2NO 1 O2 N 2NO2
35
is exothermic, NO does not react with oxygen at temperatures above 6508C [18]. Nitrogen oxides emitted from
furnaces primarily exist as NO.
2.3.1. Solution of NO and NO2 in water
Gas is well absorbed in liquid, especially if the gas and
the liquid show about the same polarity. The polarity of a
molecule is determined by its structure and the difference
between the electronegativity of the atoms in the molecule.
As a result of its angular structure, water shows a large
dipole moment and therefore can easily dissolve molecules
with a high polarity.
Nitrogen monoxide (NO) has a low solubility in water as
a result of its low polarity. The linear structure of the molecule and the relatively small differences between the electronegativity of oxygen and nitrogen result in NO, which
320
Fig. 12. Reaction scheme of absorption and reduction of NO using Fe(II)EDTA.
can only partially be absorbed under the formation of gas

hydratessimilar to oxygen and nitrogen in water. The
solubility of NO in water decreases greatly with increasing
temperature until its minimum is reached at 818C. Afterwards, it slowly increases. The solubility decrease is proportional to the concentration decreased of a certain kind of
water molecule (probably (H2O)6) which reacts with NO
under the formation of a gas hydrate [33].
Nitrogen dioxide (NO2) shows a better solubility in water
than NO because the additional oxygen atom leads to an
angular structure similar to water and so increases the polarity of the molecule. Also, NO2 is the anhydride of nitrous
acid and nitric acid, whereas anhydrides generally show a
good solubility in water.
Nitrogen dioxide is in equilibrium with dinitrogen
tetroxide (N2O4):
2NO2 N N2 O4
36
As a result of the exothermic dimerization reaction, the

equilibrium moves to its left side with increasing temperature. Thus 20% of NO2 at 278C, 40% at 508C and nearly
100% at 1408C [18]. NO2 (1/2 N2O4) reacts with water,
transferring the nitrogen of a valence 4 to one part to a
lower oxidation number of valence 3 (nitrous acid HNO2)
and to another part to a higher oxidation number with a
valence 5 (nitric acid HNO3):
N2 O4 1 H2 O N HNO2 1 HNO3
37
Here the formed nitrous acid (HNO2) reacts with a part of

NO:
HNO2 N
1
2
1
HNO3 1 NO 1 H2 O
3
3
3
38
Under the presence of oxygen, NO2 reacts with H2O

according to the following total reaction to nitric acid:
2N2 O4 1 2H2 O 1 O2 N 4HNO3
39
Here, N2O4 is not oxidized with H2O to HNO3. First, N2O4
reacts with water according to Eqs. (37) and (38):

3N2 O4 1 3H2 O N 3HNO2 1 3HNO3
40
3HNO2 N HNO3 1 2NO 1 H2 O
41
Eqs. (40) and (41) result in following total reaction:

3N2 O4 1 2H2 O N 4HNO3 1 2NO
42
Not before now, the reaction of oxygen begins by oxidizing

the formed NO to NO2
2NO 1 O2 N 2NO2 N N2 O4
43
which now serves as reactant for the reaction in Eq. (40).

The reaction in Eq. (43) is for gases with a small NO2 fractionthe technical velocity determining reaction for the
total reaction in Eq. (39).
Fig. 11 shows the selected methods for the absorption of
nitrogen oxides which seem appropriate in combination
with the concept of flue gas washing in the condensing boiler
technique described here. The left branch shows the oxidation of NO to NO2 in the gaseous phase and the subsequent absorption of the NO2. In the middle, the method of
NO absorption via NO oxidation in the water is shown. On
the right side, we see methods of dissolving NO in water and
finally reducing them. All methods neutralize the water
necessary to convert the nitric and sulfuric acids produced
to nitrate and sulfate. The methods, which are shadowed in
gray represent the results gained experimentally and
described in this paper, so the following explanations will
deal with the principles of each process.
2.3.2. Oxidation of NO in aqueous solutions
The oxidation of gaseous NO flowing through water can
be achieved by adding various substances to the water. NO2
formed then will dissolve immediately according to Eq.
(39). Using potassium permanganate (KMnO4) as a strong
oxidizer, brownstone (MnO2) and dissolved manganate ions
are formed. Thus, potassium permanganate only can be used
321
Fig. 13. Basic layout of the test boiler with water bath [37].
in closed systems, therefore using it in the condensate of the

flue gas which serves as absorbent is not appropriate.
Perchlorates such as potassium perchlorate (KClO4) are
chemically unstable and tend to decompose explosively if
kept in larger concentrations. As a result of the danger arising from incorrect handling, use in domestic situations is
recommended only with special care.
The formation of ozone O3 at a light bow or with help of
an UV lamp requires electric energy. The costs of the
apparatus and the electricity do not favor this technique in
small plants. Additionally, ozone is toxic even in small
concentrations so its use can only take place with corresponding safety systems. The use of peroxides is appropriate
because neither they themselves nor the products formed are
dangeroususing hydrogen peroxide produces water and
oxygen. Magnesium peroxide (MgO2) can also be used
instead of H2O2.
The oxidation number of oxygen is 21 for peroxides, and
lies in between that in O2 (0) and H2O (22). Thus it is
expected that aqueous solutions of peroxides show a spontaneous dismutation (the change of an elementary
compound to a higher and a lower oxidation number). But
H2O2 decomposes very slowly without catalyzers. Even
though trace contaminants can lead to an explosive
decomposition [34].
Magnesium peroxide reacts with water to hydrogen
peroxide according to
MgO2 1 H2 O N MgO 1 H2 O2
44
For a systematic investigation of the use of peroxides in

order to achieve an oxidation of NO, it is recommended that
H2O2 be first considered. Using MgO2 directly leads to a
neutralization of the nitric acid, especially because MgO2
is available only together with MgO.
2.3.3. Absorption and reduction of NO in aqueous solution
The lead dioxide oxidehyposulfite method works on an
electrochemical foundation [35]. The NO contained in the
flue gas is chemically absorbed in a hyposulfiteous solution
(S2O422) and is reduced to nitrogen. This method requires
expensive apparatus and a complex process control
system.
Complexing agents, so-called chelates [e.g. EDTA (ethylene diamine tetra-acetate) or NTA (nitrilotriacetate)], are
added to the water to bind NO to the flue gas reversibly to
EDTA or NTA, which are used as Fe(II) complexes. Then it
reacts with sulfite SO322, which dissolves in the water by
absorption of SO2 from the flue gas to molecular nitrogen
N2 and sulfate SO422. The Fe(II) complex is free to bind
another NO after the reaction.
The main reactions
FeIIEDTA22 1 NO ! FeIIEDTA22 NO
45
2
SO2 1 SO22
3 1 H2 O ! 2HSO3
46
22
2FeIIEDTANO 1 2SO22
3 ! 2FeIIEDTA
1 N2 1 2SO22
4
47
322
Table 2
Hole diameter d0, number of holes z and minimum volume flow
V_ bottom;std of the perforated bottoms used
Perforated Bottom
d0 in mm
1
2
3
4
5
2.5
2.5
1.5
3.5
2.5
z
80
120
192
40
128
EDTA (which has a higher efficiency at the NO absorption

compared to NTA) is not decomposable biologically, so the
metals remain dissolved in water.
V_ bottom;std in m 3/h
12.0
18.0
11.0
11.0
19.2
of this absorptionreduction method are shown for the use

of EDTA in Fig. 12.
As secondary reactions, we find:
1. Oxidation of sulfite ions by absorbed oxygen to sulfate
and dimerization to dithionate S2O622
2. Oxidation of Fe(II)EDTA to the far less active
Fe(III)EDTA
3. Partial reduction of NO to various nitrogensulfur
compounds such as HON(SO3)222, N(SO3)332,
HN(SO3)222 or N2O.
The sulfate ions concentrating in the washing solution are
deposited as calcium sulfate or ammonia sulfate in existing
units. The concentration enrichment of the products
mentioned in secondary reaction (3) is avoided by precipitation or hydrolysis. As the oxidation of sulfite by NO
completes the reaction to the oxidation by oxygen, an
SO2 NO ratio of 3 or higherdependent on the oxygen
content of the flue gasmust be guaranteed to achieve an
NO deposition degree of more than 70% [36].
The absorptionreduction reactions should be separated
locally from the condensation of the steam in the flue gas.
As complexing agents are not consumed, their use should
take place in a closed system. Using condensate which is
discharged afterwards into the sewage system, would mean
an unnecessarily high consumption of complexing agent.
Thus, the condensation of steam in the flue gas should
take place in a heat exchanger arranged after the absorbing
solution.
A result of the high stability of the complexing agents is
that if EDTA is discharged it remobilizes barely soluble
metal compounds in sewage sludge or river beds stronger
than other complexing agents. It is a disadvantage that
3. Experimental apparatus and measuring techniques

3.1. Design of the test boiler
For the experiments on absorption and neutralization of
SO2 and NOx, the boiler shown in Fig. 13 is used. Fluidmechanical investigations are carried out on a model without a heat exchanger in the water bath. A transparent boiler
wall allows the supervision of the bubble flow.
The burner and combustion chamber are arranged vertically. A perforated bottom is positioned horizontally at the
end of the combustion chamber; its circumference is
surrounded by a weir. The end of the combustion chamber
and the perforated bottom are submerged in the water bath.
During the burner operation, the water is displaced out of the
combustion chamber already during the pre-ventilation time
and a gas bubble is formed beneath the perforated bottom.
The gas moving upward is dispersed into bubbles by the
perforated bottom; it cools down on contact with water to
water temperature while rising. Also, the water is used for
absorption and neutralization of the acid-forming sulfurous
and nitrous oxides. For this reason, the complete test boiler
was made of stainless steel with the material number 1.4571
(commonly called V4A steel). Test gas portions can be
taken at the end of the combustion chamber and immediately above the surface of the water bath. Test water portions
are drawn at irregular intervals.
All experiments were carried out with an air pressure
atomization burner, modified by a rotation-controlled fan.
With rotation control, the fan pressure is adjusted to the
counterpressure, which varies because of the use of different
perforated bottoms and various water heights above the
perforated bottom h. The water bath and the combustion
chamber can be cooled separately. In the experiments, the
heat exchangers are flown through one after the other.
The geometry of the perforated bottoms used is shown in
Table 2. Perforated bottoms 1 to 4 are used for the fluidmechanical investigations (Section 4). For this, the
dimensions marked in Fig. 13 are d1 640 mm, d2
440 mm, d3 243 mm, d4 231 mm and b 60 mm.
Bottom 5 is used for experiments on absorption and
Table 3
Manufacturers data of the gas analyzers used, NDIR [38], electrochemical measuring cell [39] and chemiluminescence [40]
Measuring value
Measuring method
Measuring range
Linearity
Resolution
Exactness
T90 time
cSO2
NDIR
01000 ppm
^20 ppm
2 ppm
5 ppm
160 s
Electro-chemical cell
020 ppm
no data
0.2 ppm
2% of measured value/month
60 s
cNO ; cNOx
Chemiluminescence
0100 ppm
^1 ppm
0.1 ppm
1 ppm
1s
cCO2
NDIR
020%
^0.4%
0.05%
0.1%
160 s
cCO
NDIR
0300 ppm
^6 ppm
2 ppm
1.5 ppm
160 s
neutralization of sulfurous and nitrous oxides (Section 5).

The height of the weir remains unchanged; there, the dimensions are d1 570 mm, d2 520 mm, d3 285 mm and d4
230 mm.
3.2. Measuring techniques
3.2.1. Gas analysis
Table 3 shows the manufacturers data on the gas analyzers used. For the measurement of the SO2 concentration,
two different measuring concepts are used. The non-dispersive infrared analysis (NDIR) is used to measure large
concentrations and allows measuring fast concentration
changes within an area between 1 and 60 s by the parametrizable t90 time. The electrochemical measuring cell is
used to measure small, stationary SO2 concentrations. The
exactness of the electrochemical measuring cell refers to
one month, as it is calibrated only by the manufacturer at
the time of delivery and then is usable for several months,
while the other analyzers are calibrated at the beginning of
the daily measurements.
The concentrations of CO and CO2 are also measured by
NDIR. The measuring of the nitrogen oxide concentrations
is carried out by a gas analyzer, based on the principle of
chemiluminescence. The measuring apparatus used allows
measurement of NO and NOx concentrations. Both values
are determined by the same detector, for the measurement of
NOx, the test gas portion is led through a converter first. The
NO2 concentration is determined via the difference between
NO and NOx concentration.
Using the electrochemical measuring cell, no preparation
of the test gas portion is carried out. The detector is applied
immediately to the flue gas channel. The measuring methods
used in other analyzers show a high cross-sensitivity to
steam. The test gas portion therefore is cooled down electrically before analysis to a temperature q 58C, so the
largest part of water is condensed. The remaining humidity
can be suppressed by moistening the test gas used for the
calibration.
The danger caused by the high solubility of SO2 in water
arises when an indeterminate portion of SO2 dissolves in the
condensate at the analysis and an incorrect analysis results.
This absorption is avoided by acidifying the condensation
route from the point of taking the test gas portion until the
end of the cooler. For this, phosphoric acid (H3PO4) is used,
which is appropriate because of its very low steam pressure.
Immediately at the point of taking the test gas portion, the
5% phosphoric acid is introduced into the test gas tube via a
dosage valve. The test gas pipe has a very small inner
diameter of d 2 mm, so a condensate film will be established over the entire pipe wall. Thus, the condensate droplet
will be reached immediately by the phosphoric acid and
could not absorb SO2.
3.2.2. Water analysis
The water analysis which is used covers the determination
323
of the pH, the concentration of the dissolved oxygen and the

concentration of the anions. The pH is measured by a pH
combination electrode with Ag/AgCl reference system [41];
the oxygen concentration is measured with a Clark measuring cell.
An ion chromatograph with a conduction detector is
used for the ion analysis. A phthalic acid eluent
(3 mmol/l phthalic acid) is used with 5% acetonitrile for
stabilization. The calibration is carried out by a multi-ion
standard; for most of the measurements, it contains 5 mg/l of
each sulfite, chloride and nitrite and 10 mg/l of each
bromide, nitrate and sulfate. The multi-ion standard is
prepared by weighing in the corresponding potassium or
sodium neutral salts into distilled water. Sulfite is an exception. A separate sulfite standard is prepared in which the
oxidation of sulfite with dissolved oxygen to sulfate is
avoided by adding a caustic soda solution and formaldehyde. This sulfite standard is then mixed to the multi-ion
standard.
Thus, the determination of sulfite, sulfate, nitrite, nitrate,
chloride and bromide is possible with one chromatogram. If
sulfite will be determined as well, the test water portion is
brought to a pH 9 to 10 and formaldehyde is added to the
test water portion. The retention time of sulfite is shortened
by the formation of an addition compound of formaldehyde
and sulfite, and the parallel eluation with chloride is
avoided.
Standard and test water portion are microfiltered. The test
portions are also treated with a cartridge cation exchanger in
H 1 form so that the front peak, caused by the cations
(Mg 21), does not cover the early eluating anions. A nonpolar solid-phase extraction is also carried out by cartridges,
so disturbances of the chromatograms and damage of the
separation columns by hydrocarbons are avoided.
4. Fluid-mechanical layout of a gas bubble washer

To improve the heat and mass transfer between two
phases, the interphase is increased by dispersing one of
the two phases. For absorptionthat is dissolving a gas in
a liquideither units with atomization of the liquid, or socalled gas bubble washers which disperse the gas, are used.
At liquid atomization, gas is led in counter-flow to falling
droplets from the bottom to the top. This arrangement
allows adaptation of the gaseous mass transfer coefficient
b g by changing the relative velocity between droplets and
surrounding gas. In contrast, the liquid mass transfer coefficient b l is small because of the lack of movement inside
the small droplets. Thus, liquid atomization is appropriate
for the absorption of easily soluble gases for which the
liquid mass transfer resistance can be neglected as a result
of their good solubility.
In bubble columns, the gaseous mixture and fluid are in
contact at the surface of gas bubbles which rise through a
standing or slow moving liquid. A high specific surface can
324
Fig. 14. Schematic presentation of different kinds of bubble formation [43].
be reached by producing small bubbles. This large surface,

the simple design construction with small dimensions, and
the good heat transfer conditions, are reasons for the universal usability of the bubble column as a reactor. Additionally,
bubble columns show excellent transfer conditions in
transversal direction, this means that concentration and
temperature are constant in a cross-section [42]. The reason
for this is so-called exchange cells, which are formed by a
counter-flow movement of liquid streams in the column.
The rising gas bubbles cause a liquid stream flowing
upward, which deviates when it reaches the liquid surface,
resulting in a circular flow in the column. The circular flow
of the liquid is subdivided into many small circular flows;
the exchange cells guarantee a brisk longitudinal and
transversal exchange.
The gas bubble washer was chosen as a absorbing apparatus because, among the advantages mentioned, it allows
the possibility to achieve the dispersion of the flue gas with
the burner fan in combination with the condensing boiler
technology, and therefore no further aggregate is required to
supply the dispersion energy.
4.1. Gas flow through the complete perforated bottom
A perforated bottom is used to achieve the dispersion of
the flue gas in the condensate. First, the fluid-mechanical
processes will be considered for a single hole before the
description of the phenomena observed at the formation of
bubbles is applied to the perforated bottom. Fig. 14 shows
the bubble formation for a single hole for various gas
volume flows.
The volume flow of the gas increases from V_ a to V_ e . The
separating bubbles get larger as the gas volume flow is
increased. Ignoring the lifting force of the bubbles which
increases with growing bubble diameter, the distance of the
bubble clusters remains constant, so the bubbles touch each
other for the gas volume flow V_ c . They are separated only by
a small liquid lamella.
Until this volume flow is reached, single bubbles are
formed. If the volume flow is increased further, the thin
liquid lamella is destroyed and a jet is formed which leads
to the formation of bubble clusters with bubbles of different
sizes.
The limit between the formation of single bubbles and
bubble clusters can be determined by comparing the forces
at the liquid lamella [44]. It is assumed that the liquid shows
only a low viscosity. From the side of the hole, the kinetic
force Fkin and the force of interfacial tension Fs must be
considered. From the side of the gas jet, we take the pressure
force Fp, arising from the curved surface, and the lifting
force Fl on the liquid lamella into account. These forces
can be determined as follows:
p
Fkin rd w20 d02
48
4
Fs psd0
49
Fp
p
sd
2 0
50
Fl
p
r 2 rd gsd02
4 c
51
where d0 is the hole diameter, w0 the average velocity in the

hole, r c density of the liquid (coherent phase), r d the density
of the gas (dispersed phase), g the gravitation constant, s the
interfacial tension and s the jet length.
The variable s describes the length of the gas jet at the
time the bubble cluster tears off. Ruff [44] gives the following estimation:
!1=5

1 p 2=5 d04 w20
s
52
2 4
g
325
Fig. 15. Calculated Weber numbers We, Wecrit and measured critical Weber number Wecrit for a just completely passed perforated bottom, d0
2.5 mm [37].
The forces Fkin and Fp have a destructive effect on the

liquid lamella, the forces Fs and Fl are constructive. Setting
up a balance for these forces, we obtain:
Fs 1 Fl Fkin 1 Fp
where
We
53
p
p
p
) psd0 1 rc 2 rd gsd02 rd w20 d02 1 sd0
4
4
2
2s
r 2 rd
1 c
rd
rd w20 d0

2
1 4=5
1
0:45395 1
We
Fr*
d0 g
w20
0:45395 1
57

5=4
w20
rd
:
d0 g rc 2 rd
58
and
54
Fr*
!4=5
rd w20 d0
s
55
56
The Weber number We is the ratio of kinetic force and

interfacial tension force, the modified Froude number Fr*
is the ratio of kinetic force and lifting force. The ratio of the
forces is influenced by the size of the holes. In a small hole,
the lifting force can be ignored so 1/Fr* ! 0. For a large
*
*
Fig. 16. Calculated modified Froude numbers Fr*, Frcrit
and measured critical modified Froude number Frcrit
for a completely passed perforated
bottom, d0 3.5 mm [37].
326
Fig. 17. Drag reduction of the flue gas flowing through the water bath [37] perforated bottom 1: z 80, d0 2.5 mm, V_ bottom;std 12 m 3/h
perforated; bottom 2: z 120, d0 2.5 mm,V_ bottom;std 18 m 3/h.
hole, the influence of the interfacial tension force Fs

becomes negligibly small and 1/We ! 0.
For small holes, the limit between single bubble formation and bubble cluster formation is to be found for
We Wecrit 2. For We . Wecrit, we observe bubble
cluster formation, while for We , Wecrit, single bubbles
are formed. In the same way, for big holes the limit is to
be found at Fr* Fr*crit 0.37.
Equalizing the criteria Wecrit 2 and Fr*crit 0.37, one
obtains the determining equation for the hole diameter dgr
that separates small and large holes:
5=8

s 1=2
rd
dgr
:
59
rd g
rc 2 rd
For the dispersion of air in water, this diameter is dgr

2.74 mm for a temperature of 258C; this changes very little
within a range of flue gas and condensate temperatures
between 25 and 508C.
Comparing the phenomena of the gas flow through a
single hole and a perforated bottom, it becomes evident
that if the bottom is completely passed by the gas volume
flow, each hole is in the state between single bubble formation and bubble cluster formation [44]. This means that
every hole of the bottom shows bubble cluster formation if
the perforated bottom is passed completely by gas. Falling
short of this characteristic volume flow means that only a
portion of the holes are passed by gas and inactive zones can
develop in which no mass transfer takes place.
Fig. 18. Drag reduction of the flue gas by bubble formation and by the perforated bottom perforated bottom 3: z 192, d0 1.5 mm, V_ min
11 m 3/h, perforated bottom 4: z 40, d0 3.5 mm, V_ min 11 m 3/h.
At the layout of a perforated bottom for flue gas dispersion, amount and diameter of the holes must be chosen so
that the bottom is passed completely by the gas. If too many
holes (or too big in diameter) are chosen, the bottom is not
passed completely by gas and inactive zones will result,
while for too few holes, an increase of the gas volume
flow means an additional drag reduction while passing the
hole, which results in the formation of larger bubbles.
Choosing burner power, airfuel ratio and flue gas temperature before entering the water bath determines the volume
flow of the gas.
Figs. 15 and 16 show the experimental results for completely passed perforated bottoms of different geometry. For
these experiments, the test boiler shown in Fig. 13 was used.
To allow good observation of the bubble formation, the heat
exchanger was not built, and a plexiglass boiler wall was
used.
In Fig. 15, the Weber number We for a completely passed
bottom is the determining number, as small holes were
chosen with a diameter d0 2.5 mm. The curves show the
calculated Weber number as a function of the number of
holes and volume flow of the gas V_ bottom;std which flows
through the bottom under the conditions (q std 258C,
pstd 1 bar). The measured points as shown represent the
volume flow of the gas for which the bottom is passed
completely by the gas for the chosen number of holes z.
In Fig. 16, the modified Froude number Fr* is used for the
determination of a perforated bottom, as large holes were
chosen with a diameter d0 3.5 mm.
*
The values of the critical numbers Wecrit and Frcrit
, determined in the experiments, are higher than the theoretically
*
*
calculated values Wecrit
2 and Frcrit
0.37. The difference
between theoretical and experimental values increases with
a growing volume flow V_ bottom;std . This phenomenon can be
explained because the perforated bottom does not cover the
complete cross-section of the liquid. The liquid taken into
motion by the rising gas bubbles is diverted when it reaches
the liquid surface, and it flows back downward in the section
which is not passed by the gas (d2 , d , d1). For such a
distribution of the dispersed gas over a cross-section of the
liquid, a stationary flow of the liquid will result, which we
call circulating flow. As a result of this circulating flow, a
fifth force at the liquid lamella must be taken into account,
which supports the lifting force Fl and therefore is a
constructive force for the lamella. Thus, bubble cluster
*
formation begins at higher gas velocities, so Wecrit and Frcrit
increase. With an increasing gas volume flow V_ bottom;std , the
*
circulating flow becomes stronger and Wecrit and Frcrit
increase.
The formation of the circulating flow is enforced by the
geometrical arrangement of the perforated bottom to
achieve a stable flow of the liquid. If the complete crosssection of the fluid is covered by the perforated bottom,
rising and falling liquid flows come in contact with each
other. Even the smallest disturbances can then lead to a
complete breakdown of the stationary flow and can
327
aggravate a locally constant gas flow through the perforated

bottom. Fluctuations can be observed in both longitudinal
and transversal direction [43]. This causes pressure variations in the gas beneath the perforated bottom which
disturb the combustion. Our measurements have shown
much lower pressure variations at a completely developed
circulating flow compared to a gas distribution over the
complete liquid cross-section. The size of the pressure variations does not show a dependence on the water height above
the bottom h.
4.2. Drag reduction of the flue gas flowing through the water
bath
The height of the water column above the perforated
bottom h, and the drag reduction by the flue gas dispersion
have to be overcome by the burner fan. Fig. 17 gives an
example of drag reduction Dp for two perforated bottoms
dependent on the flue gas volume flow V_ bottom;std .
To be added is the drag reduction, caused by bubble
formation and by flow through the perforated bottom, and
the pressure difference necessary to overcome the water
column above the perforated bottom. With increased gas
volume flow, the drag reduction by bubble formation and
by flow through the bottom increases. The calculation are
carried out according to Mersmann [45].
By choosing a larger number of holes (bottom 2), or a
larger hole diameter, constant drag reduction can be
achieved for increased volume flow V_ bottom;std , which may
result either from a higher burner power or from external
flue gas recirculation.
By using large holes, a decisive decrease in the drag
reduction can be achieved. In Fig. 18, a comparison between
the drag reduction (Dp Dpperforated bottom 1 Dpbubble formation)
of a bottom with small holes (bottom 3) and large holes
(bottom 4) is shown. The number of holes z, is chosen so
that both bottoms are passed completely by a gas volume
flow of V_ bottom;std 11 m 3/h. Measured and calculated
volume flow shows good agreement for bottom 3. For
bottom 4, the measured values are lower than the calculated.
This is attributed to the fact that the resistance coefficient for
the calculation of the drag reduction by bubble formation
was determined by Mersmann [45], based on small holes.
The separate display of the calculated drag reduction by
bubble formation and by perforated bottom, compared to
our own measurements shows that for large holes the drag
reduction by bubble formation can be ignored.
4.3. Mass transfer between dispersed gas and liquid
In Section 2.2.2, the mass transfer between dispersed
gas and fluid was described by the two-film theory in the
example of SO2. Dispersing the flue gas by perforated
bottom, the flow of the gas bubbles and of the liquid are
strongly influenced by the geometric dimensions. Eq. (29)
328
Fig. 19. Influence of MgOgran hydration on the pH [37], m_ Oil 1.0 kg/h, j S 0.12%, mMgO 1582 g.
describes the SO2 partial pressure in the flue gas after

leaving the liquid as a function of following parameters:
1. gaseous mass transfer coefficient b g,
2. contact time of flue gas and liquid Dt,
3. mole specific interphase Abu/Nbu of the single bubble.
The bigger the bubbles, and the more turbulent the liquid
flow around them, the bigger is their inner circulation and its
mass transfer coefficient b g. The mass transfer coefficient b g
is dependent on time, and decreases with increased retention
of the bubble in the liquid. The reason for this is that each
bubbleregarded as a closed systemdoes not show mass
transition, therfore the concentration profile in the bubble
interior changes with time. A very detailed description of
experimental and theoretical results for mass transfer
processes in bubbles is given by Hong and Brauer [46].
The contact time Dt can be influenced directly by the
height of the water column above the perforated bottom h.
The velocity of the bubbles rising in the liquid is primarily a
function of the liquid density r l and the gas density r g and
the interfacial tension s .
The experimental determination of the interphase of
dispersed gas and coherent liquid is carried out by determining the average bubble diameter ds and the gas volume
contained in the two-phase system. The gas volume is determined by measuring the difference of mixture volume and
liquid volume. Thus the interphase a is specific to the gas
volume and corresponds directly to the mole specific interphase Abu/Nbu, via the ideal gas law.
We write for the volume specific interphase a [47]:
a6
1d
dS
60
where ds is the Sauter diameter and 1 d the volume fraction of

the gas.
The Sauter diameter ds is the average diameter of the
bubbles at a greater distance from the perforated bottom
and is calculated in liquids with a low viscosity, as used

here according to [47]:
s
6s
:
61
dS
rc 2 rd g
If the dispersed gas only flows through a very low liquid
column, the average bubble diameter cannot be expressed
by only the Sauter diameter. In the immediate vicinity of the
perforated bottom, the average diameter is also influenced
by the size of the holes [43].
The mixture consists of the volume fraction of the gas 1 d
and the volume fraction of the liquid 1 c (1 d 1 1 c 1). The
volume fraction of the gas 1 d determines the interphase; it is
dependent on the composition and can additionally be influenced by the average velocity vd. The average velocity vd is
determined immediately by the gas volume flow V_ bottom;std
for a given bubble column cross-section A:
vd
V_ bottom;std
:
A
62
If the average velocity is low, the gas bubbles, which are

strongly decelerated when entering the liquid, can distribute
over the whole cross-section. Then a homogeneous structure
exists and the volume fraction 1 d increases with growing
average velocity. Further increase in the average velocity
leads to a zone with a higher gas fraction as a result of the
deceleration of the gaseous phase in which bigger gas jets
and agglomerations of bubbles can be observed. These can
rise faster than single bubbles because they show a higher
lifting force as a result of their smaller volume specific
surface. The formation of this heterogeneous surface is associated with a decrease in the volume fraction, 1 d.
Mersmann [48] gives an upper limit for the average velocity of a bubble column:
vd;max 0:2we
63
329
Fig. 20. Dissociation equilibria of CO2, HCO32 and CO322 versus pH and base fraction xb.
we is the final rising velocity for bubbles that are end of

being stable and is determined by the substance combination. For the combination of air and water, it is
we 0.2 m/s at 258C. Increasing the average velocity
above the limit mentioned results in a decisive increase
of the mixture of the two phases, even so, the decrease
of the interphase leads to a deterioration of the heat and
mass transfer.
To enable a compact layout of the absorber, the aim is to
receive a small cross-section A. To guarantee good mass
transfer conditions, a minimum cross-section A must be
achieved. By substituting Eq. (63) in Eq. (62), one obtains
with we 0.2 m/s:
Amin
V_ bottom;std
0:04 m=s
64
The gas volume flow V_ bottom;std is determined by the

burner power.
For an ideal burner power of P 15 kW and an airfuel
ratio l 1.1, we obtain for the combustion of heating oil
EL, a flue gas volume flow V_ bottom;std 18.2 m 3/h and a
minimum cross-section of the perforated bottom A
0.126 m 2.
5. Experiments on the absorption and neutralization of

SO2 and NOx in the water bath
During physical absorption of gases, the gas remains
unchanged in the liquid, and no further gas is absorbed by
the liquid when the saturation concentration is reached. For
a continuous deposition of a gas component out of a gaseous
mixture, the absorbed gas must react chemically in the solution to allow the absorption of further gas.
Thus, the chemical reaction is the key to a continuous
absorption of a gas component in a limited portion of
water. Like SO2, NO2 reacts with water to form an acid.

Its deprotonation is guaranteed by neutralization to allow
a further absorption of gases and their reaction to acids.
5.1. Neutralization
Sulfur and nitrogen oxides react forming of acids when
absorbed in water. The deprotonation of these acids leads to
a strong increase of the concentration of H 1 ions, so the pH
decreases. Thus, according to Eqs. (12), (13) and (15), a
further absorption of SO2 and NOx is aggravated.
By adding a neutralizer, ideally, the same amount of OH 2
ions are dissolved as H 1 ions are produced by deprotonation
of the acids, so the solution stays neutral. The neutralization
is a basic principle for a continuous absorption of acid-forming flue gas components in the condensate. For this reason,
the experiments carried out on the neutralization shall be
described before Sections 5.2 and 5.3, which will deal more
closely with the absorption of sulfur and nitrogen oxides.
The water bath used for the absorption of acid-forming
flue gas components is an open system. The condensation of
the flue gas taking place during the flow of the flue gas
through the water bath represents the water supply flow.
An overflow regulating the water height above the perforated bottom corresponds to the water outlet. The continuous exchange of the absorbent allows a continuous,
dosed solution of hydroxides (OH 2), otherwise the excess
neutralizer would be discharged via the overflow.
In Section 2.2.3, the general suitability of oxides, hydroxides and carbonates of sodium, magnesium and calcium
for the use as neutralizers, has been described. Here, we do
not deal experimentally with calcium compounds as continuous discharge of the formed salts is not possible as a result
of their low solubility.
The use of sodium hydroxide and sodium carbonate is
generally favored because overflow resulting from
330
Fig. 21. Absorption of CO2 from the flue gas in the water bath for a stepwise increasing pH by caustic soda.
discharging these highly soluble salts is not problematic.

But the effective solubility of the neutralizer itself requires
the use of a dosage system consisting of pH meter, dosage
pump and storage tank.
By using magnesium compounds, expensive apparatus is
not necessary. The very low solubility of magnesium hydroxide, in combination with the high solubility of the
formed salts MgSO3, MgSO4 and MgNO3, allows the
discharge of these salts, together with the condensate,
adding the neutralizer in excess at the same time, because
the neutralizer is solid in water and is not drawn off via the
overflow. In the following, experiments on neutralization
with magnesium oxide (which forms magnesium hydroxide
(Mg(OH)2) when dissolved) are shown.
The experiments on neutralization and absorption were
carried out in a test boiler whose design is shown in Section
3.1. Of the perforated bottoms described in this chapter,
bottom 5 is used. The burner was operated at an oil mass
flux moil 1.0 kg/h and an airfuel ratio l 1.13 for all the
experiments. The fuel used was heating oil EL with a sulfur
content j S 0.12%.
5.1.1. Formation of Mg(OH)2 via hydration of MgO
Before magnesium oxide shows a neutralizing effect in
water, it has to react to hydroxide via hydration. Here it shall
be investigated whether the hydration of the MgO takes
place so slowly under unfavorable conditions that the
neutralization of the water bath is not guaranteed because
the consumption of Mg(OH)2 for the absorption of acidforming substances is greater than its production. The velocity of the hydration shown in Eq. (32) depends on the form
of the MgO used. With a very compact granulate, a slower
hydration occurs, compared to pulverized MgO.
Fig. 19 shows the course of the pH versus time for four
different burner operation sequences, each lasting 1 h. At the
start of the experiment, a mass mMgO 1582 g of granulated
magnesium oxide (MgOgran)was added to the water bath.
One hour later, the first operation sequence begins. At the

start of this operation sequence, a pH 9.7 was measured.
During the contact time of one hour, MgO and water have
formed Mg(OH)2, which has caused the increase of the pH
tending to the dissociation equilibrium
MgOH2 N Mg21 1 2OH2
65
With the absorption of the acid-forming flue gas components, a strong decrease of the pH, down to pH 5.7,
can be observed within the first three minutes of the first
burner operation sequence. Having reached this minimum,
the pH increases slowly until it reaches a value pH 5.6, at
the end of the operation sequence. Within the first 3 min of
the burner operation sequence, the hydroxide formed before
is consumed for the neutralization of the formed acid. The
MgO which was covered with Mg(OH)2 before the start of
the burner is set free and the velocity of the hydroxide
formation increases, so the pH increases as well.
After 72 h, the burner is started again. The pH decreases
slower than at the first operation sequence and reaches its
minimum at pH 6.8 before increasing to its final value
pH 6.9. The reason for the slower decrease of the MgO
and the less significant minimum is to be seen in the higher
amount of Mg(OH)2 that has been formed within the 72 h.
Also, the following operation sequences, 96 and 102 h later,
show a similar course of the pH. The stationary pH at the
end of each operation sequence increases only slightly with
increasing employment time of the MgO in the water bath,
and remains below pH 7.5 even for an operation time of
several weeks.
The pH at the start of each burner operation sequence (t
0) decreases with the total burner operation time. The reason
for this is the increasing concentration of Mg 21 in the water
bath. During the standstill times of the burner, magnesium
hydroxide dissolves until the solubility product of Mg 21 and
OH 2 is reached. Thus, an increasing concentration of Mg 21
has a higher part on the solubility product and the OH 2
331
Fig. 22. Dissociation equilibria of SO2, HSO32 and SO322 versus pH and base fraction xb.
concentration decreases. The difference between the pH at

the burner standstill and burner operation therefore
decreases with increasing employment time of the MgO.
5.1.2. Carbonate formation by CO2 absorption
Flowing through the neutralized water bath, a part of
the CO2 contained in the flue gas also dissolves under the
formation of carbonic acid. While the complete absorption
of SO2 is desired, this is different for the absorption of CO2
(mCO2 3.2moil); for this reason, the system CO2 H2O shall
be regarded here. The absorption of CO2 is part of the
following equilibrium chain:
CO2 g 1 H2 O N CO2 aq 1 H2 O N H2 CO3 N HCO2
3
1H1 N CO3 22 1 2H1
66
CO2 reacts with water to an aqueous complex CO2(aq). Only
a small part of the CO2(aq), about 0.2% [18], react to form

carbonic acid (H2CO3), which dissociates into hydrocarbonate (HCO32) and carbonate (CO322). Theoretically,
carbonic acid is a weak acid. But as the largest part of
the dissolved CO2 exists as hydrated CO2(aq) and not as
H2CO3, its solution acts as a weak acid. Fig. 20 shows the
dissociation equilibrium in dependence on the pH and the
base fraction xb which is defined as
cbase
xb
67
cacid 1 cbase
Adding neutralizer to the water, the reaction equilibriumaccording to Eq. (66)is disturbed by the reaction of hydroxide and H 1 ions to H2O. Tending towards the
equilibrium, CO2 dissolves again under the formation of
hydrogen carbonate and carbonate.
If the pH in the water bath is 10 or higher, as can be found
Fig. 23. Absorption of SO2 versus pH and height of the water above the perforated bottom h [37], m_ Oil 1.0 kg/h, j S 0.12%.
332
Fig. 24. O2 concentration in the water bath versus temperature q wb and airfuel ratio l [16].
immediately after adding MgO to the water bath, a large

amount of carbonate is formed. We speak of a carbonate
buffer as this carbonate leaves the solution as CO2 without
changes in the pH when a strong acid like H2SO3 is
dissolved. Thus the formation of carbonates by absorption
of CO2 from the flue gas does not have to be connected to an
increased consumption of neutralizer, as long as no larger
amounts are lost with the drawn-off water. If the pH lies
between pH 7 and 9, mostly HCO32 is formed.
Fig. 21 shows the course of the CO2 concentration in the
flue gas after the water bath and the pH of the water bath for
the addition of caustic soda. The CO2 concentration in the
flue gas before entering the water bath is cCO2 13.5%.
Starting with a low pH, a first decrease of the CO2 concentration can be seen for a pH 8. As a result of the absorption
of CO2, the pH decreases rapidly and the absorption of CO2
is stopped.
Adding a large portion of caustic soda (t 17 min), CO2
is absorbed for several minutes. The pH which then ensues
is pH 7.7. A stationary pH in the water bath of pH . 8,
due to the absorption of CO2, is not expected for the given
flue gas composition, and the used neutralizers. CO2 does
not seem to be absorbed for a pH , 7.5, but SO2 is.
5.2. SO2 absorption
Sulfur dioxide reacts to form acid when absorbed by
water. The acid behavior is to be attributed to the formed
sulfurous acid (H2SO3).
1
SO2 1 H2 O N H2 SO3 N HSO3 1 H1 N SO22
3 1 2H
68
Here, the equilibrium lies on the right side of the reaction

Eq. (68), so almost all of the dissolved sulfur dioxide
remains unchanged as SO2(aq) and only a small part is to
be found as sulfurous acid, H2SO3. As a two-base acid,
sulfurous acid dissociates according to Eq. (15) to hydrogen
sulfite (HSO32), and sulfite (SO322), especially if the H 1

ions react to water H2O with OH 2. Fig. 22 shows the
dissociation equilibria dependent on the pH and the base
fraction xb.
5.2.1. Influence of pH on the SO2 absorption

To investigate the influence of pH on the absorption of
SO2, the water bath was blown through with flue gas
containing SO2, without adding neutralizers. The concentrations of SO2 before and after the water bath were
measured. Fig. 23 shows the dependence of the absorption
degree a SO2 on the pH and the height of the water column
above the perforated bottom h.
Beginning at neutral conditions in the water bath, an
almost complete absorption of SO2 can be observed up to
a pH 4 independent of the height h. At this pH, The
absorbed SO2 exists almost completely as hydrogen sulfite
(HSO32). With a further decrease of the pH, the absorption
degree aSO2 decreases rapidly. For a larger water height h,
more SO2 is absorbed compared to a small height. For a
pH 2.1, the absorption degree is smaller than aSO2
0.05 for the investigated water heights.
If falling short of pH 4 is avoided by adding neutralizer
to the water bath, sulfur dioxide is absorbed almost completely. In contrast, the pH quickly falls short of pH 4 if
the condensation of the steam is carried out without an
immediate neutralization of the sulfurous acid, and no
important absorption of SO2 occurs any longer.
Fig. 23 shows the measured total sulfite concentration in
the water bath. This total sulfite concentration consists of
SO2(aq), H2SO3, HSO32 and SO322. The sulfite concentration
is nearly constant between neutral conditions and a pH 4
and its value lies between csulfite 35 mg/l and csulfite
40 mg/l. With a further decrease of the pH, the sulfite
concentration increases strongly and thereby verifies the
recognized decrease of the absorption degree aSO2 .
333
Fig. 25. NO absorption degree a NO versus pH and H2O2 concentration at experiment start [37], q wb 358C.
5.2.2. Sulfite oxidation

At the oxidation of sulfite to sulfate, oxygen dissolved in
the water bath (O2(aq)) is consumed. Fig. 24 shows the
measured oxygen concentration in the water bath dependent
on the airfuel ratio l and the water bath temperature q wb.
Also, the measured oxygen concentration in the water bath is
compared to the calculated saturation oxygen concentration.
For a saturated solution, the O2 partial pressure in the gas
and the O2 concentration in the water are in balance, which
is described by the Henry law as a function of temperature.
Here, the oxygen partial pressure in the flue gas is determined directly by the airfuel ratio l .
Independent of the airfuel ratio l , the measured O2
concentration is in accordance with the saturation O2
concentration. This means that the balance between
dissolved oxygen O2(aq) and oxygen in the flue gas is
established quickly enough to compensate for the
oxygen consumption by sulfite oxidation. In addition,
the SO2 oxidation in an aqueous solution takes place

with the order of zero according to the oxygen concentration [26,49]. It is not dependent on the oxygen
concentration or on the oxygen transport. The accordance
between
measured
and
calculated
O2
concentration shown in Fig. 24 was observed within
the limits pH 3 and 7.5.
After the end of a burner operation sequence, the
sulfite contained in the water is also oxidized, and the
remaining dissolved oxygen is consumed. Nevertheless,
enough oxygen is available for the sulfite oxidation at
the beginning of the next burner operation sequence
because enough oxygen is dissolved during a boiler
pre-ventilation period during which air is led through
the water bath.
Sulfite and oxygen show a negative standard potential
difference with D1 21.31 V (referred to pH 14) in
an alkaline solution and D1 21.12 V in an acid solution
Fig. 26. Specific emissions ENO before and after the water bath in dependence on the airfuel ratio l [37], mMgO2 270 g, pH 7.5, h 10 cm.
334
Fig. 27. Absorption of NO2 versus height of the water column and the NO2 start concentration when entering the water bath; pH 7.
(referred to pH 0), so the equilibrium of the reaction

SO22
3 1
1
O N SO22
4
2 2
69
lies in both acid and alkaline solutions on the right side. In

both cases, the sulfurization takes place completely.
Under neutral conditions the oxidation reaction from
sulfite to sulfate takes place so that a reduction of the contact
time between gas and water by decreasing the water height
has unmeasurably small influence on the oxidation. Independent of the water height h and the sulfate concentration
csulfate, a stationary sulfite concentration between csulfite
35 mg/l and 40 mg/l can be observed.
In contrast, the acid condensate with a pH , 4 shows an
increase of the sulfite concentration. This increase indicates
that the oxidation of sulfite in an acid solution is kinetically
aggravated. The aggravation of the sulfite oxidation and the
lack of the deprotonation of the sulfurous acid have the
result that only little SO2 can be absorbed, compared to
neutral or alkaline solutions.
5.3. Wet absorption of nitrogen oxides

Nitrogen monoxide (NO) does not react chemically in
neutral water. The absorption of NO quickly leads to a saturated solution. As NO is the largest fraction of the nitrogen
oxides (NOx) in the flue gas, the NOx absorption can either
be achieved by oxidizing NO to NO2 or by using substances
in the water bath which cause a chemical reaction of NO.
Section 5.3.1 describes the oxidation and the absorption
of NO in the water bath by adding peroxides which are
strongly oxidative. In Section 5.3.2, the absorption of
NO2, dependent on feed concentration and contact time
between gas and liquid, are discussed.
5.3.1. Oxidation and absorption of NO in the water bath

In Section 2.3.3, peroxides of water and magnesium were
described as appropriate oxidizers for the oxidation of NO in
water, because no personal and environmental dangers arise
from the substances or from their products. Hydrogen peroxide (H2O2) is used as an aqueous solution and is also a
product of the reaction of magnesium peroxide (MgO2) and
water. Thus, first experiments were carried out with H2O2
before MgO2 was used in the water bath, based on these
experiments.
In the first experiments, gas is led via a thin glass tube into
an acid solution and afterwards is led into a gas analyzer. A
constant-temperature Wulff washing bottle was used as the
water reservoir. The pH of the solution can be constantly
measured by a pH meter. The test gas used consists of NO
and N2 with c NO 90 ppm and cN2 1 2 cNO and is led
into the water with a volume flow V_ 135 l/h in a height h
50 mm below the water surface.
Fig. 25 shows the dependence of absorption degree a NO
on pH and H2O2 concentration in water at the time of the
start of the experiment. The absorption degree a NO increases
with pH and with the start concentration of H2O2.
We emphasize that Fig. 25 shows stationary absorption
degrees a NO. Far greater degrees of absorption have been
reached for short time periods by beginning with a low pH
and adding an alkaline solution; pH 9 is reached. To
explain this phenomenon, the following reaction scheme
must be examined:
H2 O2 1 H2 O N H3 O1 1 HO2
2
70
2
HO2
2 1 NO N NO2 1 OH
71
2
2HO2
2 N O2 1 2OH
72
H3 O1 1 OH2 N 2H2 O
73
By adding H2O2 to water, it decomposes according to Eq.

(70). The formed H2O can react according to Eqs. (71) and
(72) forming hydroxide ions (OH 2), which react with
hydronium ions (H3O 1) to water, according to Eq. (73). If
pH 9 is reached by adding alkaline solutions, Eq. (70) is
disturbed decisively towards the right side, and the
increased HO22 concentrations causes a faster velocity of
the reactions (71) and (72). Out of the weak base HO22,
the strong base OH 2 is formed, and pH increases without
adding further alkaline solution. As a result of the increasing
reaction (71), the absorption degrees a NO increases. Having
passed the maximum of absorption, the equilibria of the
reactions (70)(73) are established again at a pH . 9.
To observe the durability of a washing solution with
H2O2, the gas flow was cut off for 12 h. A higher pH and a
lower absorption degree a NO can be observed when the gas
flow is continued. The reason for this phenomenon is the
formation of O2 according to Eq. (71), which is supported by
catalytic materials such as steel or impurities during the 12 h
in which no NO is led through the solution. This possible
disproportion of H2O2 to H2O and O2 shows a consumption
of neutralizer without NO absorption and does not favor the
use of H2O2 in order to realize a reduction of the NOx
emission.
Using MgO2, a decrease of the absorption degree a NO
cannot be observed, after a longer standstill time without
leading NO through the washing solution. Magnesium
peroxide is used as a 1:2 mixture with MgO.
With an increasing airfuel ratio l , the NO emission of
the burner decreases in an almost linear manner (Fig. 26).
The amount of absorbed NO is in contrast to this nearly
independent on the airfuel ratio l with DENO 6 mg/
kWh. Showing the same results by the absorption degree
is not chosen here because the increase of a NO with an
increasing airfuel ratio l is only to be attributed to the
decreasing NO emission of the burner with an increasing
airfuel ratio l .
Further experiments have shown dependence of the
absorbed amount of NO on the surface of MgO2 (tested by
varying amount of MgO2) while the same amount of NO
was absorbed between h 5 cm and 30 cm. We draw the
conclusion that the reaction of MgO2 to H2O2 and MgO
which takes place more often with a larger amount of
employed MgO2 determines velocity but not the contact
time between water and gas. The low solubility of MgO2
suppresses the consumption of the peroxide during the
times of burner standstill, as was observed for the use of
the well-soluble H2O2.
5.3.2. Absorption of NO2 in water

To observe NO2 absorption in water, a gas mixture
consisting of NO2 and N2 was added to the flue gas before
entering the water bath. Thus, different concentrations of
NO2 up to cNO2 100 ppm could be adjusted. A mix of
this gas mixture with the combustion air is not possible
335
because NO2 decomposes at the high temperatures inside

the combustion chamber.
Fig. 27 shows the dependence of absorption degree of
NO2 on the water height and the concentration of NO2
when entering the neutral water bath (pH 7). An increase
of the inlet concentrations of NO2, and of the contact time of
the gas mixture and water over an increasing water column
is connected to an increase of the NO2 absorption degree.
The absorption degree increases as a result of a higher
contact time, caused by the NO2 absorption. Specially
when applying packed beds (Raschig rings) to the water
bath for the experiments shown in Fig. 27, no increase of
the NO concentration could be observed.
A further increase of the maximum absorption degree, for
which a value of 15% has been reached in the experiments
by a further increase of the contact time, is not supposed to
be possible for a moderate apparative expense.
6. Summary
Many energy sources, like oil, wood or process gases,
contain components which show acid-forming compounds
in their flue gas after combustion, and which, to a small
degree, are absorbed in the condensate when the dew
point falls short. The acid so-formed, and highly corrosive
condensate, raises the requirements on the materials used in
the condensation area.
The concepts described in this paper are based on the idea of
using the condensate for washing the flue gas; thus the flue gas
is brought in contact with an already neutralized condensate
and thereby is cooled below its dew point. This step process
allows the wet separation of noxious matter and avoids acid
corrosion of the materials used in the condensation area.
Thereby, the choice of usable materials is increased.
With the example of a gas bubble washer, fluid-mechanical investigations of the flue gas dispersion in the water
bath and experiments on the wet separation of SO2 and
NOx are presented. The absorption of the gases and neutralization of the formed acids was regarded at the wet
separation, whereas we primarily investigated the absorption of SO2.
The fluid-mechanical investigations on the flue gas
dispersion in the water bath were aimed at realizing good
mass transfer conditions between flue gas and water, and a
small expense of energy for the realization of the dispersion.
The dispersion of the flue gas in the water is achieved by a
perforated bottom. Its design, referring to the number of
holes, is determined via the critical Weber number for
small holes and via the critical modified Froude number
for large holes. For the parameters chosen, a minimum gas
volume flow is given.
To enforce a circulating flow of the water, only a part of
the water bath cross-section is covered by the perforated
bottom. Above the perforated bottom, water flows in an
upward direction and is diverted when reaching the water
336
surface before it flows downward in the area of the water

bath, which is not blown through by gas. The stable hydrodynamic flow conditions decreases the pressure variations in
the gas beneath the perforated bottom, which is directly
connected to the combustion chamber. The critical Weber
and modified Froude numbers are increased by the
circulating flow, so it must be considered at the layout of
the perforated bottom.
Flowing through the water bath, the pressure of the water
column, as well as the pressure difference for flow through the
perforated bottom and for bubble formation, act as counterpressure. A minimization of the total drag reduction can be
carried out considering contact time and contact surface
between gas and water, whereas for large hole diameters,
the drag reduction by bubble formation can be neglected.
Ideal mass transfer conditions are connected to a possibly
high volume fraction of the gas in the two-component
mixture gaswater, which can be influenced for a given gas
volume flow by the cross-section of the perforated bottom.
Acids are formed at the wet separation of SO2 and NOx.
The deprotonation of the acids and the neutralization of the
H 1 ions formed by hydroxides (OH 2) necessary to achieve a
continuous absorption of the acid-forming gases, is possible
in a limited volume of water. In experiments, magnesium
oxide (MgO) has proved to be especially adequate. MgO is
hydrated to the hardly soluble magnesium hydroxide
(Mg(OH)2). Its low solubility is the reason why no dosage
system is required. At the operation of the burner, a pH
between 7.0 and 7.5 will ensue depending on the form of
MgO used. During the standstill times of the burner, an
increase of the pH takes place until the solubility product
of Mg(OH)2 is reached. The increasing concentration of
Mg 21 with longer burner operation time cause a decrease
of the dissolved amount of Mg(OH)2, so the stationary pH of
burner operation and burner standstill phases get closer to
each other. CO2 contained in the flue gas is dissolved only
for a pH . 7.5 under the formation of a carbonate buffer.
These carbonates are displaced when a stronger acid is
dissolved and leave the solution as CO2.
The aim of the investigations on the absorption of SO2 in
the water bath was a possibly complete desulfurization of the
flue gas. Starting at neutral conditions in the water bath, an
almost complete absorption of SO2 can be observed down to
pH 4. At pH 4, the absorbed SO2 exists almost completely as hydrogen sulfite (HSO32). With a further decrease of
pH, the absorption degree of SO2 decreases rapidly. For pH
2.1, the absorption degree is smaller than 0.05.
For the investigations on the oxidation of sulfite to sulfate,
the concentration of the oxygen dissolved in the water was
determined. The measured oxygen concentration is the
saturation concentration which depends directly on air
fuel ratio and water bath temperature. This means the equilibrium of dissolved oxygen and oxygen in the gas is established quickly enough to replace the oxygen consumed for
the sulfite oxidation to sulfate. In the neutralized water bath,
a stationary sulfite concentration of about 35 mg/l can be
observed, independent of the water height. The high sulfite

concentration in the acid condensate that is not neutralized
leads to the conclusion that the sulfatization is kinetically
aggravated. A low SO2 absorption is directly connected to a
high sulfite concentration in the water bath.
Among the almost complete decomposition of SO2, the
washer offers the possibility to reduce the emission of nitrogen oxides. As NOwhich is the dominating fraction of
NOx emitted from furnacesis only physically dissolved in
water, and is not engaged in a chemical reaction, a continuous absorption is not possible without further means. In
contrast, NO2 reacts in water under the formation of nitric
and nitrous acid.
The oxidation and absorption of NO in water can be
achieved by peroxides of hydrogen and magnesium. Hydrogen peroxide (H2O2) is not suitable for a long-term operation
as a result of its low stability. Using the stable magnesium
peroxide (MgO2), a reduction of the NOx emissions of DE
6 mg/kWh could be reached. While the water height was
shown to have no effect on the absorbed amount of NO, a
dependence on the employed amount of MgO2 could be
observed. We draw the conclusion that the reaction of
MgO2 with water to MgO and H2O2 is velocity-determining
but not the contact time between gas and water. An increase
of the absorbed amount of NO by a higher pH is not
favorable, due to the absorption of CO2 connected thereto.
The absorption of NO2 in neutral water requires good
mass transfer conditions between water and flue gas. By
applying a packed bed in the water columns, an absorption
degree of 15% could be achieved for a start concentration
cNO2 62 ppm, and a height of the water column of 40 cm.
Using gas bubble washers, a reduction of the SO2
emissions of about 99% can be achieved within a wide
range of sulfur content in the fuel and for a low energy
expense for the dispersation of the flue gas. A corresponding
reduction of the NOx emission is not possible until now. The
measures described showed a maximum reduction of the
NOx emission of about 25%.
References
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PERGAMON

Progress in Energy and Combustion Science 25 (1999) 305337

Design of scrubbers for condensing boilers

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

mass flux (kg/s)

average gas velocity (m/s)

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

combine with drained rainfall into surface waters or via

2. State of science and technology

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

a total pressure below 10 bar, only dependent on the

(SO3) in the flue gas acts as a condensation nucleus resulting

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

temperature q fg 1508C before leaving the flue gas system.

j i the mass fraction of the gaseous component i in kg/kgfuel,

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

Fig. 4. Combustion efficiency h c specific to HHV.

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

Fig. 6. Condensing boiler technology with flue gas desulfurization;

Fig. 7. Condensing boiler technology with flue gas desulfurization;

The value of the flow-pipe and the return temperature of

The following rules can be summed up for the integration

with the radiator surface A and the logarithmic average

The temperature of the heating medium must be as low

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

Fig. 8. Condensing boiler technology with flue gas desulfurization;

2.1.3. Concepts for condensing boiler technology for

ally, non-corrosive steels are used, but ceramics, glass or

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

water bath and at last through the heat exchanger in the

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

temperature avoids burning the lime to death and realizes

chemical absorption, phase equilibria are described in

where pi is the partial pressure of the component i, xi the

where 1 i is the Henry activity coefficient, p the total pressure

where 1i 1i p; T. For a given temperature, the partial

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

exact than the Henry law, the dependence of the Henry

is described by the physical absorption.

The law of mass action states that a chemical reaction

The hydrogen ions set free by the dissociation results in an

the concentration of the hydrogen ions decreases, and the

While the direction of the equilibrium reactions (11), (12)

in bothin acid and in alkaline solutionand for the

A system which donates and accepts electrons according

2.2.2. Mass transfer at SO2 absorption

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

gas boundary layer becomes dominant and can be regarded

n_ 00SO2 ;l bl cSO2 ;int 2 cSO2

n_ 00SO2 n_ 00SO2 ;g n_ 00SO2 ;l

The partial pressure of SO2 at the interphase pSO2 ;int cannot

As an equilibrium exists at the interphase, according to the

Substituting this in Eq. (26), one obtains:

If gas is led stationary and under constant boundary

F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305337

19.1 [30] as Na2SO4

0.6 [30] as MgSO4(H2O)3

25.2 [30] as MgSO4(H2O)7