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PERGAMON Progress in Energy and Combustion Science 25 (1999) 305–337

Design of scrubbers for condensing boilers

F. Haase*, H. Koehne
Lehr- und Forschungsgebiet für 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

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-of-
the-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 phases—flue 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

Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
2. State of science and technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
2.1. Condensing boiler technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
2.1.1. Dew point and combustion efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
2.1.2. Integration of condensing boiler technology in the heating system . . . . . . . . . . . . . . . . 311
2.1.3. Concepts for condensing boiler technology for sulfurous fuels . . . . . . . . . . . . . . . . . . . 312
2.2. Deposition of sulfur oxides from flue gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
2.2.1. Phase equilibria and oxidation at the absorption of SO2 . . . . . . . . . . . . . . . . . . . . . . . . 315
2.2.2. Mass transfer at SO2 absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 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: (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) 305–337

2.2.3. Neutralization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318

2.3. Wet separation of nitrogen oxides from flue gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
2.3.1. Solution of NO and NO2 in water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
2.3.2. Oxidation of NO in aqueous solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
2.3.3. Absorption and reduction of NO in aqueous solution . . . . . . . . . . . . . . . . . . . . . . . . . . 321
3. Experimental apparatus and measuring techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
3.1. Design of the test boiler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
3.2. Measuring techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
3.2.1. Gas analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
3.2.2. Water analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
4. Fluid-mechanical layout of a gas bubble washer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
4.1. Gas flow through the complete perforated bottom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
4.2. Drag reduction of the flue gas flowing through the water bath . . . . . . . . . . . . . . . . . . . . . . . . . 327
4.3. Mass transfer between dispersed gas and liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
5. Experiments on the absorption and neutralization of SO2 and NOx in the water bath . . . . . . . . . . . . . 329
5.1. Neutralization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
5.1.1. Formation of Mg(OH)2 via hydration of MgO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
5.1.2. Carbonate formation by CO2 absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
5.2. SO2 absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
5.2.1. Influence of pH on the SO2 absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
5.2.2. Sulfite oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
5.3. Wet absorption of nitrogen oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334
5.3.1. Oxidation and absorption of NO in the water bath . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334
5.3.2. Absorption of NO2 in water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
6. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336

Nomenclature m_ mass flux (kg/s)

M molar mass (kg/kmol)
Physical symbols n_ 00 transferred mole number per time and area
A area (m 2) (mol/s m 2)
a volume specific interphase (m 21) N mole number (mol)
b weir height (m) P power (W)
c concentration (mg/l, mol/m 3) p pressure (Pa)
c specific heat capacity (J/kg K) pH pH
d diameter (m) Q heat (J)
dS Sauter diameter (m) q_ 00 heat flow density (J/m 2 s)
E specific emission (mg/MJ) Q_ heat flow (J/s)
F force (N) Q_ std standard heat demand (J/s)
f power ratio of a radiator R gas constant (J/mol K)
Fr* modified Froude number r reaction velocity (mol/m 3 s)
g gravitation constant (m/s 2) r specific vaporization enthalpy (J/kg)
H enthalpy (J) s jet length (m)
h height of water column above perforated T temperature (K)
bottom (m) t time (s)
H Henry constant (N m/mol) t90 time until 90% of the stationary value is
h specific enthalpy (J/kg) reached (s)
hfg latent heat of vaporization (J/kg) v_d average velocity in tube (m/s)
HHV higher heating value (J/kg) V_ volume flow (m 3/s)
K equilibrium constant (mg/l) 21
k velocity constant (s 21)
l length (m) Symbols
LHV lower heating value (J/kg) w average gas velocity (m/s)
m mass (kg) We Weber number
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 307

x mole fraction MgO magnesium oxide

y height of perforated bottom above boiler MgO2 magnesium peroxide
bottom (m) MgSO3 magnesium sulfite
z number of holes MgSO4 magnesium sulfate
a absorption degree Mn manganese
b mass transfer coefficient (mol/N s, m/s) MnO2 manganese dioxide
D difference MOH metal hydroxide
1i Henry activity coefficient N(SO3)332 nitrilo trisulfonate
1 volume fraction N2 nitrogen
h efficiency degree N2O dinitrogen monoxide
l air–fuel ratio N2O4 dinitrogen tetroxide
q temperature (8C) Na2O2 sodium peroxide
Dq ln logarithmic average temperature (K) Na2C2O6 sodium peroxocarbonate
r density (kg/m 3) Na2SO3 sodium sulfite
s interfacial tension (N/m) Na2SO4 sodium sulfate
j mass fraction NaOH sodium hydroxide
c mole fraction NH3 ammonia
(NH4)2SO4 ammonia sulfate
Chemical symbols NO nitrogen monoxide
Ag silver NO2 nitrogen dioxide
AgCl silver chloride NO22 nitrite ion
Al aluminum NO32 nitrate ion
Ca calcium NOx nitrogen oxide
Ca(OH)2 calcium hydroxide NTA nitrilotriacetate
CaCO3 calcium carbonate O2 oxygen (molecular)
CaO calcium oxide O3 ozone
CaSO3 calcium sulfite OH 2 hydroxide ion
CaSO4 calcium sulfate PbO2 lead dioxide
CH4 methane Pt platinum
ClO42 perchlorate ion Rh rhodium
CO2 carbon dioxide S2O422 dithionite ion
CO322 carbonate ion S2O622 dithionate ion
e electron SiO2 silicon dioxide
EDTA ethylene diamine tetra-acetate SO2 sulfur dioxide
Fe iron SO3 sulfur trioxide
H1 hydrogen ion SO322 sulfite ion
H2CO3 carbonic acid SO422 sulfate ion
H2O water
H2O2 hydrogen peroxide Index
H2SO3 sulfurous acid * state of saturation
H2SO4 sulfuric acid 0 standard conditions
HN(SO3)222 imido disulfonate aq dissolved
HNO2 nitrous acid b base
HNO3 nitric acid bu gas bubble
HO22 hydrogen dioxide ion c combustion
HON(SO3)222 hydroxylamine disulfonate c continuously
H3PO4 phosphoric acid crit critical
HSO32 hydrogen sulfite ion d dispersed
K potassium dp dew point
KClO4 potassium perchlorate fg flue gas
KMnO4 potassium permanganate fp flow pipe
M1 metal cation g gas side
M2SO3 metal sulfite g gaseous
Mg magnesium gran granulated
Mg(OH)2 magnesium hydroxide h heating medium
MgNO3 magnesium nitrate i component
308 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

in entering combine with drained rainfall into surface waters or via

kin kinetic the sewage system into a sewage treatment plant.
l lifting force Fig. 1 shows the effects of sulfurous and nitrogenous
l liquid side compounds in the air, on plants, earth and water for the
lim limit emissions of SO2 and NOx.
max maximum value This mass flow proves that the wet deposition of SO2 and
min minimum value NOx in condensing boilers under the formation of sulfate
out leaving and nitrates and the necessary neutralization correspond to
p pressure the processes in nature.
r return The wet deposition of SO2 and NOx, immediately after
s interfacial tension their formation in the combustion chamber of the washer for
std standard state condensing boilers, is described here. The specialty of these
wb water bath 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 diox-
ides is possible in the condensate if the flue gas contacts
1. Introduction immediately neutralized condensate under good heat and
mass transfer conditions. Meeting these requirements results
Burning fossil energy sources, the acid-forming com- in washing the flue gas and preventing the boiler parts in the
ponents sulfur dioxide (SO2) and nitrogen oxides (NOx) condensation area from corrosion.
are formed, as well as others, and are emitted into the at- Combining the condensing boiler technology (CBT) with
mosphere. Following the mass flow of the nitrogenous and flue gas washing increases the choice of usable materials for
sulfurous compounds after their emission, it is necessary to fuels with a very aggressive condensate and the operative
differentiate between their effects on the air and on plants, expense is kept low at the same time. As a result of low
earth and water. energy prices, condensing boiler technology is difficult to
As the average retention times of the trace gases SO2 and realize economically for the fuels mentioned and a small
NOx are only very short (hours up to several days), their power output. But the additional flue gas washing provides
influence on air quality is regionally limited. SO2 and NOx a motivation which should be encouraged by means of
are toxic to human beings at a certain concentration. The legislation.
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
2. State of science and technology
(H2O), carbon dioxide (CO2), ozone (O3), dinitrogen oxide
(N2O) and methane (CH4). These gases cause the so-called
2.1. Condensing boiler technology
greenhouse effect of the atmosphere. But SO2, NOx (and
ammonia NH3) lead to the formation of aerosols which are According to their energy content, fuels are described by
solid or liquid parts in the air outside of clouds with a the lower heating value (LHV) and the higher heating value
diameter between 0.001 and 100 mm. They scatter and (HHV). The LHV of a substance is the amount of heat set
absorb solar irradiation and emit thermal radiation so they free at complete combustion when reactants and products
behave contrary to the anthropogene heating of the earth [1]. show the same temperature and water formed at combustion
The largest part of the emission is chemically converted exists as steam. The difference to the gross caloric value of
in the air before it is deposited via rain. At the chemical the fuel is that it considers the water as liquid, so the gross
conversion of sulfur dioxide, sulfuric acid (H2SO4) is caloric value is, by the condensation heat of the water,
formed; its salts are called sulfates (SO422). Finally, gypsum greater than the net caloric value (HHV=LHV ˆ
or Na2SO4 is formed. Nitrogen monoxide is oxidized to hfg jh =LHV with j h ˆ mass fraction of hydrogen in the
nitrogen dioxide, which forms nitric acid; its salts are called fuel). Condensing boilers are those which make the latent
nitrates (NO32). heat contained in the flue gas usable by condensation.
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 2.1.1. Dew point and combustion efficiency
out. Also, the supply of nutritive substances of the ground The condensation of water begins when the state of
decreases. With increasing acidity of the ground, first saturation for the steam in the flue gas is reached while
calcium magnesium and potassium, and in later stages, cooling the flue gas. This point is called the “dew point“,
manganese and aluminum are dissolved out of the ground and its temperature is the dew point temperature q dp. At the
particles. They are washed out and lost to the ecosystem [2]. dew point the steam pressure equals the saturation steam
Together with the washed out alkali sulfates and nitrates pressure of water, which is—as an approximation—for
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 309

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 (SO3) in the flue gas acts as a condensation nucleus resulting
temperature. in an increase of the dew point temperature. For an exact
For the combustion of fuels, the partial pressure of steam determination of the so-called “acid dew point“, knowledge
in the flue gas depends on fuel composition (hydrogen of the conversion of sulfur dioxide (SO2) to sulfur trioxide
content), air–fuel ratio l and the humidity of the combus- (SO3) is necessary. As an approximation, it is assumed that
tion air. Disregarding the air humidity, the dependence the volume concentration of SO3 is about 1% of the concen-
between the dew point temperature q dp and air–fuel ratio tration of SO2 [3]. It can be seen in Fig. 3 that the dew point
l is obtained, as shown in Fig. 2 for the standard heating oil increases under these conditions for a sulfur content in the
in Germany called “EL“ (extra light). With an increase in flue gas of j S ˆ 0.2 % by 72 K and lies for an air–fuel ratio
air–fuel ratio l , the flue gas must be cooled to achieve l ˆ 1.1 at q dp ˆ 1208C.
steam condensation. As a measure against acid corrosion or sooting, conven-
By burning sulfurous fuels, the hydrophile sulfur trioxide tional heating technology avoids falling short of a flue gas
310 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

Fig. 2. Dew point temperature q dp of the flue gas from the combustion of heating oil EL versus air–fuel ratio l .

temperature q fg ˆ 1508C before leaving the flue gas system. j i the mass fraction of the gaseous component i in kg/kgfuel,
By introducing condensing boiler technology into an exist- q 0 the flue gas temperature and hfg the latent heat of vapor-
ing heating system, a large fraction of the sensible heat ization of water at standard temperature.
connected to the high flue gas temperature of conventional Here we assume that fuel and dry air are supplied at a
heating systems can be used. standard temperature q 0, which usually is the thermody-
To evaluate a heat generator, the combustion efficiency namic standard temperature q 0 ˆ 258C. The enthalpy of
supplied energy 2 energy at flue gas outlet the condensed water is disregarded here. For heating oil
hc ˆ …1† EL, the result is dependence between combustion efficiency
supplied energy
h c, flue gas temperature q fg and air–fuel ratio l shown in
can be used (the so called “boiler efficiency“ takes into
Fig. 4.
account in addition heat losses through the jacket).
When falling short of the dew point temperature, a strong
Determining the delivery energy by the HHV, one
increase of the combustion efficiency h c can be observed,
P   which is attributed to the addition of condensation heat to
ji hi …qfg † 2 hi …q0 † 1 jH2 O hfg the sensible heat.
hc ˆ 1 2 i …2† The concept of flue gas washing, used with condensing
Hg …q0 † boiler technology, dealt with here, aims at complete
where hi is the specific enthalpy of the gaseous component i, 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].
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 311

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

flue gas. Good mass transfer conditions between flue gas and heat demand for the layout of the boiler (provided that the
necessary condensate result in complete saturation of the piping losses are negligible), the boiler has to supply the
flue gas with steam, so that for only a slight increase of power
the temperature above the dew point, condensate will vapor-  
ize and combustion efficiency decreases compared to a dry Q_ h ˆ Q_ std ˆ m_ h ch qfp 2 qr …3†
flue gas system. This phenomenon is shown in dashed
curves in Fig. 4 and provides the necessity of avoiding to the heating circuit. In the aforementioned equation, mh
flue gas temperature above the dew point by appropriate represents mass flux of the heating medium, ch the specific
control systems. 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.
2.1.2. Integration of condensing boiler technology in the The values of the process parameters mh, q fp, q r and their
heating system combinations can only be chosen within certain limits. If the
For the layout of a heating system, the so-called standard flue gas is cooled below its steam dew point by the heating
heat demand of a building, Q_ std is used; it describes the heat medium, the maximum return temperature is then deter-
power supplied to heat the rooms to comfortable tempera- mined according to Fig. 2 depending on the air–fuel ratio
tures at a low outdoor temperature [4]. Using the standard l chosen.

Fig. 5. Influence of flow-pipe and return temperature on the power ratio f of a radiator.
312 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

Fig. 6. Condensing boiler technology with flue gas desulfurization; Fig. 7. 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 following rules can be summed up for the integration
the heating medium has a decisive influence on the heat of condensing boilers into heating systems [7–10]:
supply of a radiator; its heat flux Q_ can be described by
ÿ  • The temperature of the heating medium must be as low
Q_ , A Dqln n …4† as possible, with a considerable difference between flow-
pipe and return temperature. In new buildings, conden-
with the radiator surface A and the logarithmic average
sing boilers are often connected to floor radiators, or
heating systems with low temperature radiators. Even
qfp 2 qr in old buildings, there must be no limitations for appro-
Dqln ˆ   …5† priate integration of the condensing boiler technology.
ln qfp 2 qroom =qr 2 qroom
Heat demands of the building are less than during
construction as a result of subsequent thermal insulation;
The value of the exponent n lies within the limits 1.1 to 1.5;
and because the existing heating system—designed for
for radiators, n < 1.3 is obtainted [5], for floor radiators, n <
temperatures q fp ˆ 908C and q r ˆ 708C—is over-
1.1 [6]. Making the heat flux from Eq. (4) specific to stan-
dimensioned because of formerly common security
dard conditions (q fp,std ˆ 908C, q r,std ˆ 708C, q room,std ˆ
factors, lowering the heating medium temperatures is
208C) [5], the so called power ratio of a radiator for equal-
sized radiator surfaces
• In contrast to humidity-sensitive boilers (standard or low
Q_ q_ Dqln Dqln temperature boilers), measures leading to a raised return
f ˆ _ ˆ ˆ ˆ …6† temperature (mixing valves) must be avoided generally
Qstd q_std Dqln;std 59:44 K
when using condensing boilers.
This relation is valid for m_ H =m_ H;N $ 0:2 and can be used to • An over-dimensioned installed boiler power does not
determine the heat a radiator supplies for various pairs of reduce the annual efficiency degree, in contrast to
flow-pipe and return temperature. Fig. 5 shows the power conventional boilers, because the boiler walls are cooled
ratio f dependent on the return temperature q r for different down intermittently so that lower flue gas temperatures
flow-pipe temperatures q VL. It can be seen from Fig. 5 that are reached at the beginning of each phase of burner
the supplied heat flux of a radiator decreases operation.
• To adapt to a lower heat demand (part load), not the
• if the temperature difference (q fp 2 q r) is increased heating medium flux, but the flow-pipe temperature
when the return temperature is lowered by reducing the should be reduced. A high heating medium flux is
heat medium mass flux and keeping the flow-pipe related to higher requirements on the thermostat
temperature constant (line A), valves [11].
• if the temperature difference is decreased by lowering • The use of liquid layer reservoirs with a separate
the flow-pipe temperature, keeping the return tempera- heat exchanger has proved to be efficient in combi-
ture constant (line B), nation with the condensing boiler technology. The
• if the temperature level is decreased, keeping the war water reservoir is connected via a priority-
temperature difference constant (line C). controlled three-way valve to the flow-pipe. The
If the same heat flux is to be obtained as in the standard heat exchange takes place in counter-flow with
case, the radiator surface must be increased according to the cold water for domestic use from the bottom
of the reservoir, so condensing boiler technology is
1 possible even for warm water temperatures of
Aˆ A : …7†
f std 608C.
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 313

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-heat-
ing 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
Fig. 8. Condensing boiler technology with flue gas desulfurization;
concept III [15]. 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
2.1.3. Concepts for condensing boiler technology for unit and is finally discharged into the public sewage system.
sulfurous fuels To achieve neutralization, either calcium or magnesium
Condensing boilers have been offered for sulfurous fuel granulate or ion exchangers are used. The granulates loose
for ten years. While the use of condensing boiler technology their efficiency if the condensate contains metal ions which
is state-of-the-art today for the nearly sulfur-free energy may arise from low temperature corrosion. In this case,
source gas, it has not found acceptance from planners, metallic compounds settle down on the active surface of
installers and users because of the higher standards on the the granulate because of the low flow velocity and do not
boiler construction and the discharge of condensate into the allow its further disassociation. To avoid this problem, ion
public sewage system connected to the condensing boiler exchangers are often used before the granulate.
technology. Following are four concepts for the condensing boiler
The boilers offered on the market offer the following technology, which aim for desulfurization of the flue gas.
constructive principles. The combustion chamber is cooled The common points of these concepts is that the flue gas is
first by a heat exchanger, so the flue gas produces a tempera- brought in contact with the neutralized condensate when the
ture between 150 and 1808C. A lower flue gas temperature is temperature falls short of the dew point.
avoided because condensation forming sulfuric and sulfur- The condensate from the combustion chamber of the first
ous acids would then require the use of non-corrosive ma- boiler is drawn off via a drawing wheel and is dispersed in a
terials. Nevertheless, a low temperature is targeted so as neutralized water bath (Fig. 6). A good mixing of water and
little energy as possible must be coupled out at a lower flue gas guarantees a complete heat transfer and the absorp-
temperature level in a second heat exchanger. This second tion of sulfur oxides. To achieve cooling of the flue gas,
heat exchanger is constructed of non-corrosive material three heat exchangers are used. The return flow of the heat-
because the condensation of the steam contained in the ing medium flows continuously through a heat exchanger in
flue gas takes place here, and sulfuric acid is formed. Gener- 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 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

water bath and at last through the heat exchanger in the For gas temperatures higher than 12008C, no relevant oxi-
combustion chamber. The electric motor used to power dation takes place because of the state of the equilibrium.
the drawing wheel has a power demand of 600 W [13]. Also, no relevant oxidation can be observed when cooling
For a nominal power of 17 kW, efficiency decreases by the flue gas in the boiler, because the velocity of reaction (8)
3.5% without considering the low efficiency for the is low [18]. SO3 shows a very good solubility in water and
generation of electricity. reacts under the presence of steam to form sulfuric acid.
In the second concept for condensing boiler technology Thus, the technology used for a deposition of SO2 generally
with flue gas desulfurization, the condensate is led through a also achieves good results for SO3, therefore in the follow-
neutralization cartridge via a circulation pump, is dispersed ing, the deposition of SO2 will be seen as the central point of
via nozzles in a gas-washing tower and is returned to the the investigations. In the USA and in Japan, flue gas desul-
condensation heat exchanger (Fig. 7). In the gas-washing furization units have been used in power plants for over 30
tower the condensate absorbs the sulfur oxides from the flue years; in Germany, their use began about 20 years ago [19].
gas. In Fig. 7 are shown two heat exchangers, the first one for The long development time has led to a number of process
preheating the returned heating medium, the other one for variants which generally can be divided into washing, spray
heating the water for domestic use. The heat exchangers are absorption and drying processes.
arranged in a reservoir of neutralized condensate. Thus excel-
lent heat exchange makes a compact apparatus possible. Washing processes
The third concept for condensing boiler technology with Washing processes usually work with suspensions of
flue gas desulfurization is a very compact burner/boiler calcium oxide (CaO, caustic lime), calcium hydroxide
setup. A vertically-arranged combustion chamber is cooled (Ca(OH)2, slaked lime) or calcium carbonate (CaCO3, lime-
by surrounding water bath (Fig. 8). The flue gas leaves the stone). The primary product of the lime washing process is
combustion chamber at its open bottom end and rises in the calcium sulfite (CaSO3). In Germany, gypsum CaSO4·2H2O
water bath in the form of bubbles. Also in this concept, the is usually gained via oxidation, which is either dumped or
contact of flue gas and water realizes a complete heat transfer made usable by subsequent processes [20]. Alternatively,
and allows the absorption of sulfur oxides. The possibility of the Walther Company uses an ammonia solution for wash-
producing boilers of plastic materials is seen as a central ing and acquires ammonium sulfate ((NH4)2SO4) as a
advantage of this concept [15]. The complete combustion product which can be used as synthetic fertilizer [21]. As
heat is transferred by one heat exchanger from the water a result of the good solubility of the ammonia salts, no
bath to the heating medium. Preparing high flow-pipe tempera- fouling problems occur. Montan–Werke Brixlegg, in
tures and cooling the flue gas below its dew point at the same Austria, uses a washer which is operated with an
time is not possible, so this boiler is to be regarded only as a Mg(OH)2 suspension which is produced from MgO by
low-temperature heating system. As the combustion chamber adding water [22].
is completely submerged in the water bath, a water column as
high as the length of the combustion chamber must be over- Spray absorption processes
come by a fan. The electric power demand is also connected to During spray absorption processes (also called mixed meth-
a decrease of efficiency. ods), calcium hydroxide suspensions with a high solid frac-
The fourth concept for the condensing boiler technology, tion are sprayed into the hot flue gas stream [23]. The water
developed by the authors, is also based on a gas bubble vaporizes and the salts formed are drawn off, together with
washer. Fig. 9 shows a module which can be used in the excess lime and some fine dust, by textile or electric
combination with a standard boiler or integrated in a filters positioned further downstream. A disadvantage is
condensing boiler. The heat changes by two temperatures, the over-stoichiometric consumption of lime and the lower
so the flow-pipe temperature above the dew point and deposition degree of SO2 as compared with wet processes.
condensation is possible simultaneously.
For raising efficiency of condensing boiler different Dry processes
measures are described. Variants on concept II [14] and During dry processes, we differentiate between lime absorp-
concept IV [17] use the heat transfer and mass transfer tion (dry additive process) and the absorption via activated
(water steam) between flue gas and combustion air for coke (mining technology). During dry additive processes,
reducing flue gas temperature. small-grained lime is blown into the hot flue gas. As an
alternative, lime may be added to the fuel. The calcium
2.2. Deposition of sulfur oxides from flue gas sulfite, calcium sulfate and the remaining lime which are
formed are drawn off a dust filter. Low quality coal and
Sulfur contained in the flue gas is burned together with brown coal naturally contain lime. In pulverized coal
oxygen to sulfur dioxide (SO2). Sulfur dioxide reacts with furnaces, which are common in boilers of large dimensions,
oxygen to sulfur trioxide (SO3) according to the following lime reaches the combustion chamber as fine dust and
equilibrium: absorbs part of SO2 in the ash. A complete desulfurization
2SO2 1 O2 N 2SO3 …8† seems possible with the fuel-own lime if a low combustion
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 315

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 chemical absorption, phase equilibria are described in
low flue gas temperatures [24]. different ways.
The mining-technological process [25] binds SO2 adsorp- For physical absorbents, the phase equilibrium of a single
tively to activated coke and converts it to sulfuric acid. component can be expressed by the Raoult’s law. For ideal
Sulfuric acid is stored in the pores of the activated coke. mixtures of gases and liquids, it reads
The activated coke is then thermally regenerated so it can be
used again. The gas mixture set free contains 20–30 vol.% pi ˆ xi pi * …9†
SO2, which is converted in further steps to sulfuric acid or where pi is the partial pressure of the component i, xi the
elementary sulfur. This process can also be used for similar mole fraction of the component i in the liquid and p*i the
removal of sulfur and nitrogen oxides from flue gas, if saturation partial pressure of the component i as function of
ammonia is also used. temperature.
Both sorption processes used for flue gas desulfurization, Raoult’s law states that the partial pressure of the compo-
adsorption and absorption, selectively take over one or more nent i in the gaseous phase is proportional to the mole frac-
components from a gaseous mixture into a condensed phase, tion of the component i in the liquid for a constant
as happens during the simultaneous deposition of sulfur and temperature. As the absorption of SO2 takes place exother-
nitrogen oxides. In the following, the solution of a gaseous mically, the solubility decreases with increased temperature.
phase in a liquid by absorption is examined because in the Solubilities determined with Raoult’s law can be taken as
concept of flue gas washing with condensing boiler technol- approximate values but they do not consider the type of
ogy described here, the deposition of sulfur oxides and nitro- solvent. The law assumes that a certain gas has the same
gen oxides takes place in the liquid condensate of the flue solubilities in all solvents for the same temperature and
gas. partial pressure [26].
To take into account the difference between the ideal
2.2.1. Phase equilibria and oxidation at the absorption of behavior of the gas and the liquid mixture, Raoult’s law
SO2 can be extended by the Henry activity coefficient 1 i:
When dissolving a gas in a liquid, the physical and the pi ˆ 1i xi pi * and 1i ˆ 1i …xi ; p; T† …10†
chemical absorption are differentiated. In physical absorp-
tion, the absorbed gas molecules are surrounded by a where 1 i is the Henry activity coefficient, p the total pressure
hydrate cover, but no reaction takes place, so the gas mol- and T the temperature.
ecules can leave the liquid very easily. In contrast, we speak If the concentration of the absorbed component in the
of chemical absorption or chemisorption if the gas is liquid is low, 1 i is constant and one obtains the Henry law
engaged in a chemical reaction in the liquid. found for dilute solutions:
To observe maximum load of the absorbent and the
pi ˆ 1i xi pi * …11†
composition of the gaseous mixture after the cleaning,
knowledge about the solubility of a gas in a liquid is where 1i ˆ 1i …p; T†. For a given temperature, the partial
necessary. Such knowledge is dependent upon temperature, pressure of a component is connected via the Henry activity
pressure and composition of the gaseous and the liquid coefficient in a linear path to the mole fraction of the com-
mixture. According to the classification of physical and ponent in the liquid. If the determination must be even more
316 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

exact than the Henry law, the dependence of the Henry in both—in acid and in alkaline solution—and for the
activity coefficient on the mole fraction of the component temperature range in which condensing boiler technology
in the liquid must be taken into account. is used on the side of the product.
For the absorption of SO2 in water, the hydration The oxidation of a reductive (e.g. SO322) and the reduction
of an oxidizer (here SO422) takes place according to the
SO2 …g† 1 H2 O N SO2 …aq† 1 H2 O …12†
following equilibrium:
is described by the physical absorption. reduction
The following hydrolysis of the sulfur dioxide SO2(aq) reductive N oxidizer 1 electron …18†
corresponds to the chemical absorption. The chemical
absorption of sulfur dioxide in water takes place as follows: A system which donates and accepts electrons according
to this equation is called “redox system“ or “redox pair“.
SO2 …aq† 1 H2 O N H2 SO3 …13† As free electrons do not exist under normal chemical
The law of mass action states that a chemical reaction conditions, the donation of electrons only takes place in
stops at a given temperature (equilibrium), if the quotient the presence of an appropriate reductant. The donated elec-
from the product of the concentrations of the reaction trons are accepted by the reductant while it changes to the
products, and the product of the concentrations of the reac- corresponding oxidant. Thus, a redox reaction always
tants, reaches a certain value K, which is characteristic for consists of two corresponding part reactions. The total reac-
the reaction. The characteristic value K, is called tion shown in Eq. (17) consists of the following part
“equilibrium constant“ and can be determined for the reactions:
hydrolysis of SO2 according to Eq. (13) as follows: 2 2
3 1 2OH N SO4 1 H2 O 1 2e
SO22 …19†

cH2 SO3
Kˆ …14† 1
cSO2 …aq† cH2 O O 1 2e2 1 2H1 N H2 O …20†
2 2
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: 1
3 1
SO22 O 1 2OH2 1 2H1 N SO22
4 1 2H2 O …21†
2 2
H2 SO3 N HSO3 2 1 H1 N SO3 22 1 2H1 …15† 2.2.2. Mass transfer at SO2 absorption
The hydrogen ions set free by the dissociation results in an At existing flue gas washers, gas mixture and washing
acid reaction of the solution. Adding a hydroxide MOH to liquid are in contact repeatedly with a limited contact area
the absorbent which reacts with the hydrogen ions to and for a limited contact time, so an almost complete mass
achieve a neutralization transfer of SO2 from the gas phase to the liquid phase takes
place. The mass transfer model presented here is greatly
H1 1 MOH N H2 O 1 M1 …16† simplified and will not be used for predicting the SO2
the concentration of the hydrogen ions decreases, and the concentration in the gas mixture but will permit a clear
reactions described in the Eqs. (12)–(14) react towards their discussion of the influencing parameters.
right side in order to re-establish the equilibrium, so as a The concentration differences between phase and inter-
conclusion, SO2(g) can further be absorbed. phase act as the moving force for the mass transfer. The two-
If the absorption of SO2 and the neutralization are contin- film theory can be used to describe the mass transfer from
ued, the total concentration of the dissolved SO2 (SO2(aq), fluid to fluid [27]. According to the two-film theory (Fig.
H2SO3, HSO32, SO322) increases until the state of saturation 10), a laminar interphase is formed between the gas bound-
of the salt M2SO3 formed out of sulfite SO322 and the cation ary layer and the liquid boundary. The boundary layers
M 1 in the solution is reached. Exceeding the state of satu- represent the main resistance for mass transfer. The inter-
ration results in precipitation of the formerly dissociated salt phase does not show a resistance if the boundary layers are
as a solid. in steady state.
Among the precipitation as a sulfite salt, it is possible that Within the boundary layers, mass transfer takes place by
the dissolved sulfite reacts with dissolved oxygen to sulfate diffusion. Turbulences which are based on the penetration
(SO422): model [28] result in a certain decrease of the boundary layer
thickness, so an acceleration of the mass transfer is the
3 1
SO22 O …aq† N SO22 …17† result. The boundary layer that shows the highest resistance
2 2 4
against diffusion determines the velocity of the mass trans-
While the direction of the equilibrium reactions (11), (12) fer. If one of the resistances is dominant, the other can often
and (14) can be influenced easily by temperature changes, be neglected. Gases which are easy to dissolve—such as
redox reactions show a strong dependence on the pH of the SO2 —diffuse faster through the liquid boundary layer than
solution. The equilibrium of the oxidation reaction (17) lies through the gas boundary layer. Thus, the resistance of the
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 317

gas boundary layer becomes dominant and can be regarded As an equilibrium exists at the interphase, according to the
as the main resistance [28]. two-film theory (assumption 2), the partial pressure pSO2 ;int
Generally, three kinds of phase distribution must be is connected via the Henry law to the SO2 concentration in
considered for the absorption: the liquid:
(a) Both phases exist coherently (film absorber). pSO2 ;gr ˆ H SO2 cSO2 …28†
(b) The gaseous phase is dispersed in the coherent liquid
phase (bubble column). Substituting this in Eq. (26), one obtains:
h i
(c) The liquid phase is distributed dispersely in the coher- pSO2 …t ˆ tout † ˆ HSO2 cSO2 1 pSO2 …t ˆ tin † 2 H SO2 cSO2
ent gaseous phase (spray washer).
A disperse distribution of a phase can achieve a larger  exp 2bG pG bu …tout 2 tin †
contact surface per volume unit than a continuous Nbu
distribution. …29†
For the following model of a disperse distribution of the The SO2 partial pressure after leaving one stage of the
gas phase in the coherent liquid phase, several assumptions washer, pSO2 (t ˆ tout) is determined by
are made:
1. the concentration of SO2 in the liquid cSO2 ,
1. The SO2 concentration in the coherent phase is homo- 2. the SO2 partial pressure before entering the liquid pSO2
geneous. (t ˆ tin) as a function of the sulfur content of the used fuel
2. An equilibrium exists at the interphase. and
3. Pressure variations are negligible. 3. the parameters b G, (tout 2 tin), Abu =Nbu , pg which can be
4. The mass transfer is dominated by the resistance of the influenced by design and operation modus of the washer.
gaseous phase.
The concentration cSO2 of the physically absorbed
Regarding a single gas bubble, we can write for the SO2(aq) is dependent on the state of the reaction equilibria
amount of SO2 transferred through the interphase: according to Eqs. (13), (15) and (16). Assuming an ideal
n_ 00SO2 ;g ˆ bg …pSO2 2 pSO2 ;int † …22† neutralization which guarantees a constant pH, a constant
distribution of the various forms of sulfite (SO2(aq), H2SO3,
n_ 00SO2 ;l ˆ bl …cSO2 ;int 2 cSO2 † …23† HSO32, SO322) is expected. In Section 2.2.3, the different
possible neutralizers and their effects on the mentioned
n_ 00SO2 ˆ n_ 00SO2 ;g ˆ n_ 00SO2 ;l …24† equilibrium chain are described.
Next to the equilibrium reactions, oxidation from sulfite
where n_ 00SO2
is the mole number per area and time of the to sulfate, according to Eq. (17) also takes place in the
transferred SO2 b g, b l mass transfer coefficient for the gas presence of dissolved oxygen. The reaction velocity is deter-
side in mol/Ns, for the liquid side in m/s. mined by the sulfite concentration, but not by the oxygen
Further concentration, as long as enough dissolved oxygen is
present [29]:
dn 00SO2 dpSO2 1 Nbu
n_ 00SO2 ˆ ˆ2 …25†
dt dt pg Abu r ˆ k…cSO22
†1:5 c0O2 : …30†
where Nbu is the mole number in the gas bubble, Abu the If gas is led stationary and under constant boundary
surface of the gas bubble and pgtotal pressure of the gas in conditions through the liquid, a quasi-stationary concen-
the bubble. tration of the total sulfite will ensue. Its experimental deter-
Substituting Eq. (22) in Eq. (25) and integrating over time mination using the law of mass action (Section 3.2.2) allows
within the limits of entering the liquid and leaving the conclusions to be drawn regarding the concentration
liquid, we obtain: cSO2 (aq) of the physically absorbed SO2.
…pSO2 2 pSO2 ;int †utˆtout The parameters b g, (tout 2 tin),…, pg, which are influenced
  …26† by design and operation modus of the washer, will be
A discussed in Section 4.3 for an ideally chosen dispersion
ˆ …pSO2 2 pSO2 ;int †utˆtin exp 2bg pg bu …tout 2 tin †
Nbu unit. The choice of a long contact time (tout 2 tin) between
gas mixture and liquid has, according to Eq. (29), the same
The partial pressure of SO2 at the interphase pSO2 ;int cannot
influence as an increased contact area specific to the gas
be determined by experiments. Neglecting the resistance
amount Abu/Nbu or a large mass transfer coefficient b g caused
from the liquid side and assuming a homogeneous concen-
by turbulences in the gaseous phase. These variables deter-
tration of SO2 in the liquid phase, as mentioned above, the
mine the mass transfer from the gaseous phase to the liquid
following equations are valid:
phase and have an exponential influence on the SO2 partial
cSO2 ;gr ˆ cSO2 ˆ cSO2 …t ˆ tout † ˆ cSO2 …t ˆ tin †: …27† pressure pSO2 (t ˆ tout) after leaving the liquid.
318 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

Table 1
Solubility of the compounds at 20 and 508C in 100 g water

Cation Reactants Products

Hydroxide (g) Carbonate (g) Sulfite (g) Sulfate (g)

208C 52.2 [30] 18.1 [30] 27.1 [30] 19.1 [30] as Na2SO4
508C 59.2 [30] 32.2 [30] 34.7 [30] 46.4 [30] as Na2SO4 rhombic
Mg 21
208C 0.000017 a [30] 0.000072 a [31] 0.6 [30] as MgSO4(H2O)3 25.2 [30] as MgSO4(H2O)7
508C 0.000015 b [30] 0.844 [30] as MgSO3(H2O)3 33.4 [30] as MgSO4(H2O)6
Ca 21
208C 0.126 [18] 0.0065 [30] 0.0043 a [30] 0.2 [32] as CaSO4(H2O)2
508C 0.0917 [30] 0.0038 [30] 0.0057 [30] 0.21 [32] as CaSO4(H2O)2
At 188C.
At 458C.

Eq. (29) makes clear that even under ideal mass transfer and do not dissolve as well in water as those prepared at
conditions, the SO2 partial pressure after the washer is not lower temperatures. MgO and CaO can be gained by dehy-
zero; so the conversion of the sulfite in the liquid is of a dration of hydroxides or, as it is technically usual for large
particular importance. amounts, by heating (burning) the carbonates to tempera-
tures between 800 and 10008C [18].
2.2.3. Neutralization If MgO is added to water, magnesium hydroxide is
By absorption of sulfur dioxide or other acid gases, the formed:
pH decreases and the adsorbent will be quickly saturated
MgO 1 H2 O ! Mg…OH†2 …32†
with SO2. Raising the pH to a neutral area (neutralization)
will change the equilibria described in Section 2.2.2, so SO2 This hydration does not continue until the complete
can be further dissolved. The neutralizer must either be conversion of MgO because the active surface of the
added continuously during the absorption of SO2, or it oxide decreases, pores are filled for compact material and
must be in excess in the absorbent. magnesium hydroxide forms a protective coating.
During neutralization, an acid reacts with a base under the Calcium oxide reacts with water in high temperatures,
formation of a salt and water. The main reaction is the heat development and forms calcium hydroxide (slaked
synthesis of hydrogen ions and hydroxide ions: lime) [18]:
H1 1 OH2 N H2 O …31† CaO 1 H2 O ! Ca…OH†2 …33†
Substances used as neutralizers must either contain Magnesium hydroxide (Mg(OH)2) is a compound which
hydroxide ions or form hydroxide ions in an aqueous sol- is difficult to dissolve. Ca(OH)2 shows greater solubility
ution. In choosing a neutralizer we must consider the follow- compared to Mg(OH)2 (Table 1), so dissolving this
ing criteria: compound results in a higher pH.
Sodium hydroxide (NaOH) is achieved by the chlor-alkali
1. affiliation of educates or products to a certain class of
electrolysis. Easily dissolved in water, its solution is caustic
hazardous materials,
soda and is a strongly etching substance and therefore a
2. availability and price,
hazardous material.
3. aperitif expense of the neutralizer dosage.
If carbon dioxide added to into an aqueous hydroxide
Considering these criteria, a large number of possible solution, it forms dissolved CO2, carbonic anhydride
substances are reduced to oxides, hydroxides and carbonates H2CO3, hydrogen carbonate HCO32 and carbonate CO322
of sodium, magnesium and calcium. While hydroxides and dependent on pH. With the absorption, the pH of the sol-
carbonates dissociate partly or (because of their high ution decreases until finally no carbon dioxide can dissolve
solubility), completely in an aqueous solution while tending any longer (equilibrium reactions). Adding a stronger acid
toward a steady state, oxides are hydrated in an aqueous (H2SO3, H2SO4), carbon dioxide exhales (replacement)
solution. while the pH remains constant; so the carbonates act as
The characteristic features of magnesium oxide (MgO) buffers:
and calcium oxide (CaO) depend on their preparation and
M2 CO3 1 H2 SO4 ! CO2 1 H2 O 1 M2 SO4 …34†
their preparatory treatment. Magnesium and calcium oxides
which were prepared at high temperatures are less reactive The carbonates of magnesium and calcium are hardly
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 319

Fig. 11. Methods of absorbing nitrogen oxides in an aqueous solution.

soluble in water. Sodium carbonate dissolves in water with salts formed at the absorption of SO2 be drawn off as solids
an alkaline reaction and shows greater solubility as the to be used as products—as they are used in the power plant
carbonates of magnesium and calcium. Handling sodium sector—or that they be dumped. To discharge the formed
carbonate is much less dangerous than handling sodium salts into the public sewage system, sodium and magnesium
hydroxide. compounds are appropriate neutralizers.
The different solubilities of the mentioned neutralizers The compounds described here are available in a very
shown in Table 1 require different dosage concepts: wide price range, depending on their method of preparation
and their purity. Generally, calcium hydroxide is known as
Na compounds
the least expensive industrially used neutralizer. As a result
Sodium hydroxide and sodium carbonate must be adminis-
of its various applications in soap production, in dyes, in the
tered doses in corresponding to the absorbed amount of SO2
preparation of cellulose and as a cleaner, caustic soda is very
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.
2.3. Wet separation of nitrogen oxides from flue gases
For such a dosage, a continuous pH measurement, a dosage
valve or a dosage pump, a storage tank and a control system, In burning fossil energy sources, the noxious matter NO
is necessary. and NOx are formed which together are spoken of as NOx.
As the Bodenstein reaction of NO
Mg compounds
2NO 1 O2 N 2NO2 …35†
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 is exothermic, NO does not react with oxygen at tempera-
Mg(OH)2 and the neutralizer can be added in excess to the tures above 6508C [18]. Nitrogen oxides emitted from
neutralization solution. In the slightly alkaline solution, the furnaces primarily exist as NO.
equilibrium (Mg…OH†2 ! Mg21 1 OH2 ) is disturbed with
the initial absorption of acid gases and a fast dissociation of 2.3.1. Solution of NO and NO2 in water
Mg(OH)2 begins, so the solution does not become acid. The Gas is well absorbed in liquid, especially if the gas and
reaction velocity decreases when approaching the the liquid show about the same polarity. The polarity of a
equilibrium. molecule is determined by its structure and the difference
between the electronegativity of the atoms in the molecule.
Ca compounds As a result of its angular structure, water shows a large
Using calcium oxide and hydroxide in excess like the dipole moment and therefore can easily dissolve molecules
magnesium compounds, a higher pH in the solution will with a high polarity.
result because the slightly greater solubility of the calcium Nitrogen monoxide (NO) has a low solubility in water as
compounds. Calcium sulfite and sulfate show very low solu- a result of its low polarity. The linear structure of the mol-
bility in comparison to the sodium and magnesium salts. ecule and the relatively small differences between the elec-
Therefore, the use of calcium compounds requires that the tronegativity of oxygen and nitrogen result in NO, which
320 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

Fig. 12. Reaction scheme of absorption and reduction of NO using Fe(II)EDTA.

can only partially be absorbed under the formation of gas reacts with water according to Eqs. (37) and (38):
hydrates—similar to oxygen and nitrogen in water. The
3N2 O4 1 3H2 O N 3HNO2 1 3HNO3 …40†
solubility of NO in water decreases greatly with increasing
temperature until its minimum is reached at 818C. After-
wards, it slowly increases. The solubility decrease is pro- 3HNO2 N HNO3 1 2NO 1 H2 O …41†
portional to the concentration decreased of a certain kind of Eqs. (40) and (41) result in following total reaction:
water molecule (probably (H2O)6) which reacts with NO
under the formation of a gas hydrate [33]. 3N2 O4 1 2H2 O N 4HNO3 1 2NO …42†
Nitrogen dioxide (NO2) shows a better solubility in water
than NO because the additional oxygen atom leads to an Not before now, the reaction of oxygen begins by oxidizing
angular structure similar to water and so increases the po- the formed NO to NO2
larity of the molecule. Also, NO2 is the anhydride of nitrous 2NO 1 O2 N 2NO2 N N2 O4 …43†
acid and nitric acid, whereas anhydrides generally show a
good solubility in water. which now serves as reactant for the reaction in Eq. (40).
Nitrogen dioxide is in equilibrium with dinitrogen The reaction in Eq. (43) is for gases with a small NO2 frac-
tetroxide (N2O4): tion—the technical velocity determining reaction for the
total reaction in Eq. (39).
2NO2 N N2 O4 …36† Fig. 11 shows the selected methods for the absorption of
nitrogen oxides which seem appropriate in combination
As a result of the exothermic dimerization reaction, the
with the concept of flue gas washing in the condensing boiler
equilibrium moves to its left side with increasing tempera-
technique described here. The left branch shows the oxi-
ture. Thus 20% of NO2 at 278C, 40% at 508C and nearly
dation of NO to NO2 in the gaseous phase and the subse-
100% at 1408C [18]. NO2 (1/2 N2O4) reacts with water,
quent absorption of the NO2. In the middle, the method of
transferring the nitrogen of a valence 4 to one part to a
NO absorption via NO oxidation in the water is shown. On
lower oxidation number of valence 3 (nitrous acid HNO2)
the right side, we see methods of dissolving NO in water and
and to another part to a higher oxidation number with a
finally reducing them. All methods neutralize the water
valence 5 (nitric acid HNO3):
necessary to convert the nitric and sulfuric acids produced
N2 O4 1 H2 O N HNO2 1 HNO3 …37† to nitrate and sulfate. The methods, which are shadowed in
gray represent the results gained experimentally and
Here the formed nitrous acid (HNO2) reacts with a part of described in this paper, so the following explanations will
NO: deal with the principles of each process.
1 2 1
HNO2 N HNO3 1 NO 1 H2 O …38† 2.3.2. Oxidation of NO in aqueous solutions
3 3 3
The oxidation of gaseous NO flowing through water can
Under the presence of oxygen, NO2 reacts with H2O be achieved by adding various substances to the water. NO2
according to the following total reaction to nitric acid: formed then will dissolve immediately according to Eq.
2N2 O4 1 2H2 O 1 O2 N 4HNO3 …39† (39). Using potassium permanganate (KMnO4) as a strong
oxidizer, brownstone (MnO2) and dissolved manganate ions
Here, N2O4 is not oxidized with H2O to HNO3. First, N2O4 are formed. Thus, potassium permanganate only can be used
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 321

Fig. 13. Basic layout of the test boiler with water bath [37].

in closed systems, therefore using it in the condensate of the For a systematic investigation of the use of peroxides in
flue gas which serves as absorbent is not appropriate. order to achieve an oxidation of NO, it is recommended that
Perchlorates such as potassium perchlorate (KClO4) are H2O2 be first considered. Using MgO2 directly leads to a
chemically unstable and tend to decompose explosively if neutralization of the nitric acid, especially because MgO2
kept in larger concentrations. As a result of the danger aris- is available only together with MgO.
ing from incorrect handling, use in domestic situations is
recommended only with special care. 2.3.3. Absorption and reduction of NO in aqueous solution
The formation of ozone O3 at a light bow or with help of The lead dioxide oxide–hyposulfite method works on an
an UV lamp requires electric energy. The costs of the electrochemical foundation [35]. The NO contained in the
apparatus and the electricity do not favor this technique in flue gas is chemically absorbed in a hyposulfiteous solution
small plants. Additionally, ozone is toxic even in small (S2O422) and is reduced to nitrogen. This method requires
concentrations so its use can only take place with corre- expensive apparatus and a complex process control
sponding safety systems. The use of peroxides is appropriate system.
because neither they themselves nor the products formed are Complexing agents, so-called chelates [e.g. EDTA (ethy-
dangerous—using hydrogen peroxide produces water and lene diamine tetra-acetate) or NTA (nitrilotriacetate)], are
oxygen. Magnesium peroxide (MgO2) can also be used added to the water to bind NO to the flue gas reversibly to
instead of H2O2. EDTA or NTA, which are used as Fe(II) complexes. Then it
The oxidation number of oxygen is 21 for peroxides, and reacts with sulfite SO322, which dissolves in the water by
lies in between that in O2 (0) and H2O (22). Thus it is absorption of SO2 from the flue gas to molecular nitrogen
expected that aqueous solutions of peroxides show a spon- N2 and sulfate SO422. The Fe(II) complex is free to bind
taneous dismutation (the change of an elementary another NO after the reaction.
compound to a higher and a lower oxidation number). But The main reactions
H2O2 decomposes very slowly without catalyzers. Even
though trace contaminants can lead to an explosive Fe…II†EDTA22 1 NO ! Fe…II†EDTA22 ·NO …45†
decomposition [34]. 2
SO2 1 SO22
3 1 H2 O ! 2HSO3 …46†
Magnesium peroxide reacts with water to hydrogen
peroxide according to
2Fe…II†EDTA·NO 1 2SO22
3 ! 2Fe…II†EDTA

MgO2 1 H2 O N MgO 1 H2 O2 …44† 1 N2 1 2SO22

4 …47†
322 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

Table 2 EDTA (which has a higher efficiency at the NO absorption

Hole diameter d0, number of holes z and minimum volume flow compared to NTA) is not decomposable biologically, so the
V_ bottom;std of the perforated bottoms used metals remain dissolved in water.
Perforated Bottom d0 in mm z V_ bottom;std in m 3/h

1 2.5 80 12.0
3. Experimental apparatus and measuring techniques
2 2.5 120 18.0
3 1.5 192 11.0 3.1. Design of the test boiler
4 3.5 40 11.0
5 2.5 128 19.2 For the experiments on absorption and neutralization of
SO2 and NOx, the boiler shown in Fig. 13 is used. Fluid-
mechanical investigations are carried out on a model with-
out a heat exchanger in the water bath. A transparent boiler
of this absorption–reduction method are shown for the use wall allows the supervision of the bubble flow.
of EDTA in Fig. 12. The burner and combustion chamber are arranged verti-
As secondary reactions, we find: cally. A perforated bottom is positioned horizontally at the
end of the combustion chamber; its circumference is
1. Oxidation of sulfite ions by absorbed oxygen to sulfate
surrounded by a weir. The end of the combustion chamber
and dimerization to dithionate S2O622
and the perforated bottom are submerged in the water bath.
2. Oxidation of Fe(II)EDTA to the far less active
During the burner operation, the water is displaced out of the
combustion chamber already during the pre-ventilation time
3. Partial reduction of NO to various nitrogen–sulfur
and a gas bubble is formed beneath the perforated bottom.
compounds such as HON(SO3)222, N(SO3)332,
The gas moving upward is dispersed into bubbles by the
HN(SO3)222 or N2O.
perforated bottom; it cools down on contact with water to
The sulfate ions concentrating in the washing solution are water temperature while rising. Also, the water is used for
deposited as calcium sulfate or ammonia sulfate in existing absorption and neutralization of the acid-forming sulfurous
units. The concentration enrichment of the products and nitrous oxides. For this reason, the complete test boiler
mentioned in secondary reaction (3) is avoided by precipi- was made of stainless steel with the material number 1.4571
tation or hydrolysis. As the oxidation of sulfite by NO (commonly called V4A steel). Test gas portions can be
completes the reaction to the oxidation by oxygen, an taken at the end of the combustion chamber and immedi-
SO2 –NO ratio of 3 or higher—dependent on the oxygen ately above the surface of the water bath. Test water portions
content of the flue gas—must be guaranteed to achieve an are drawn at irregular intervals.
NO deposition degree of more than 70% [36]. All experiments were carried out with an air pressure
The absorption–reduction reactions should be separated atomization burner, modified by a rotation-controlled fan.
locally from the condensation of the steam in the flue gas. With rotation control, the fan pressure is adjusted to the
As complexing agents are not consumed, their use should counterpressure, which varies because of the use of different
take place in a closed system. Using condensate which is perforated bottoms and various water heights above the
discharged afterwards into the sewage system, would mean perforated bottom h. The water bath and the combustion
an unnecessarily high consumption of complexing agent. chamber can be cooled separately. In the experiments, the
Thus, the condensation of steam in the flue gas should heat exchangers are flown through one after the other.
take place in a heat exchanger arranged after the absorbing The geometry of the perforated bottoms used is shown in
solution. Table 2. Perforated bottoms 1 to 4 are used for the fluid-
A result of the high stability of the complexing agents is mechanical investigations (Section 4). For this, the
that if EDTA is discharged it remobilizes barely soluble dimensions marked in Fig. 13 are d1 ˆ 640 mm, d2 ˆ
metal compounds in sewage sludge or river beds stronger 440 mm, d3 ˆ 243 mm, d4 ˆ 231 mm and b ˆ 60 mm.
than other complexing agents. It is a disadvantage that Bottom 5 is used for experiments on absorption and

Table 3
Manufacturer’s data of the gas analyzers used, NDIR [38], electrochemical measuring cell [39] and chemiluminescence [40]

Measuring value cSO2 cNO ; cNOx cCO2 cCO

Measuring method NDIR Electro-chemical cell Chemiluminescence NDIR NDIR
Measuring range 0–1000 ppm 0–20 ppm 0–100 ppm 0–20% 0–300 ppm
Linearity ^20 ppm no data ^1 ppm ^0.4% ^6 ppm
Resolution 2 ppm 0.2 ppm 0.1 ppm 0.05% 2 ppm
Exactness 5 ppm 2% of measured value/month 1 ppm 0.1% 1.5 ppm
T90 time 1–60 s 60 s 1s 1–60 s 1–60 s
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 323

neutralization of sulfurous and nitrous oxides (Section 5). of the pH, the concentration of the dissolved oxygen and the
The height of the weir remains unchanged; there, the dimen- concentration of the anions. The pH is measured by a pH
sions are d1 ˆ 570 mm, d2 ˆ 520 mm, d3 ˆ 285 mm and d4 ˆ combination electrode with Ag/AgCl reference system [41];
230 mm. the oxygen concentration is measured with a Clark measur-
ing cell.
3.2. Measuring techniques An ion chromatograph with a conduction detector is
used for the ion analysis. A phthalic acid eluent
3.2.1. Gas analysis (3 mmol/l phthalic acid) is used with 5% acetonitrile for
Table 3 shows the manufacturer’s data on the gas ana- stabilization. The calibration is carried out by a multi-ion
lyzers used. For the measurement of the SO2 concentration, standard; for most of the measurements, it contains 5 mg/l of
two different measuring concepts are used. The non-disper- each sulfite, chloride and nitrite and 10 mg/l of each
sive infrared analysis (NDIR) is used to measure large bromide, nitrate and sulfate. The multi-ion standard is
concentrations and allows measuring fast concentration prepared by weighing in the corresponding potassium or
changes within an area between 1 and 60 s by the para- sodium neutral salts into distilled water. Sulfite is an excep-
metrizable t90 time. The electrochemical measuring cell is tion. A separate sulfite standard is prepared in which the
used to measure small, stationary SO2 concentrations. The oxidation of sulfite with dissolved oxygen to sulfate is
exactness of the electrochemical measuring cell refers to avoided by adding a caustic soda solution and formalde-
one month, as it is calibrated only by the manufacturer at hyde. This sulfite standard is then mixed to the multi-ion
the time of delivery and then is usable for several months, standard.
while the other analyzers are calibrated at the beginning of Thus, the determination of sulfite, sulfate, nitrite, nitrate,
the daily measurements. chloride and bromide is possible with one chromatogram. If
The concentrations of CO and CO2 are also measured by sulfite will be determined as well, the test water portion is
NDIR. The measuring of the nitrogen oxide concentrations brought to a pH ˆ 9 to 10 and formaldehyde is added to the
is carried out by a gas analyzer, based on the principle of test water portion. The retention time of sulfite is shortened
chemiluminescence. The measuring apparatus used allows by the formation of an addition compound of formaldehyde
measurement of NO and NOx concentrations. Both values and sulfite, and the parallel eluation with chloride is
are determined by the same detector, for the measurement of avoided.
NOx, the test gas portion is led through a converter first. The Standard and test water portion are microfiltered. The test
NO2 concentration is determined via the difference between portions are also treated with a cartridge cation exchanger in
NO and NOx concentration. H 1 form so that the front peak, caused by the cations
Using the electrochemical measuring cell, no preparation (Mg 21), does not cover the early eluating anions. A non-
of the test gas portion is carried out. The detector is applied polar solid-phase extraction is also carried out by cartridges,
immediately to the flue gas channel. The measuring methods so disturbances of the chromatograms and damage of the
used in other analyzers show a high cross-sensitivity to separation columns by hydrocarbons are avoided.
steam. The test gas portion therefore is cooled down elec-
trically before analysis to a temperature q ˆ 58C, so the
largest part of water is condensed. The remaining humidity 4. Fluid-mechanical layout of a gas bubble washer
can be suppressed by moistening the test gas used for the
calibration. To improve the heat and mass transfer between two
The danger caused by the high solubility of SO2 in water phases, the interphase is increased by dispersing one of
arises when an indeterminate portion of SO2 dissolves in the the two phases. For absorption—that is dissolving a gas in
condensate at the analysis and an incorrect analysis results. a liquid—either units with atomization of the liquid, or so-
This absorption is avoided by acidifying the condensation called gas bubble washers which disperse the gas, are used.
route from the point of taking the test gas portion until the At liquid atomization, gas is led in counter-flow to falling
end of the cooler. For this, phosphoric acid (H3PO4) is used, droplets from the bottom to the top. This arrangement
which is appropriate because of its very low steam pressure. allows adaptation of the gaseous mass transfer coefficient
Immediately at the point of taking the test gas portion, the b g by changing the relative velocity between droplets and
5% phosphoric acid is introduced into the test gas tube via a surrounding gas. In contrast, the liquid mass transfer coef-
dosage valve. The test gas pipe has a very small inner ficient b l is small because of the lack of movement inside
diameter of d ˆ 2 mm, so a condensate film will be estab- the small droplets. Thus, liquid atomization is appropriate
lished over the entire pipe wall. Thus, the condensate droplet for the absorption of easily soluble gases for which the
will be reached immediately by the phosphoric acid and liquid mass transfer resistance can be neglected as a result
could not absorb SO2. of their good solubility.
In bubble columns, the gaseous mixture and fluid are in
3.2.2. Water analysis contact at the surface of gas bubbles which rise through a
The water analysis which is used covers the determination standing or slow moving liquid. A high specific surface can
324 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

Fig. 14. Schematic presentation of different kinds of bubble formation [43].

be reached by producing small bubbles. This large surface, other for the gas volume flow V_ c . They are separated only by
the simple design construction with small dimensions, and a small liquid lamella.
the good heat transfer conditions, are reasons for the univer- Until this volume flow is reached, single bubbles are
sal usability of the bubble column as a reactor. Additionally, formed. If the volume flow is increased further, the thin
bubble columns show excellent transfer conditions in liquid lamella is destroyed and a jet is formed which leads
transversal direction, this means that concentration and to the formation of bubble clusters with bubbles of different
temperature are constant in a cross-section [42]. The reason sizes.
for this is so-called “exchange cells“, which are formed by a The limit between the formation of single bubbles and
counter-flow movement of liquid streams in the column. bubble clusters can be determined by comparing the forces
The rising gas bubbles cause a liquid stream flowing at the liquid lamella [44]. It is assumed that the liquid shows
upward, which deviates when it reaches the liquid surface, only a low viscosity. From the side of the hole, the kinetic
resulting in a circular flow in the column. The circular flow force Fkin and the force of interfacial tension Fs must be
of the liquid is subdivided into many small circular flows; considered. From the side of the gas jet, we take the pressure
the exchange cells guarantee a brisk longitudinal and force Fp, arising from the curved surface, and the lifting
transversal exchange. force Fl on the liquid lamella into account. These forces
The gas bubble washer was chosen as a absorbing ap- can be determined as follows:
paratus because, among the advantages mentioned, it allows p
the possibility to achieve the dispersion of the flue gas with Fkin ˆ rd w20 d02 …48†
the burner fan in combination with the condensing boiler
technology, and therefore no further aggregate is required to Fs ˆ psd0 …49†
supply the dispersion energy.
Fp ˆ sd …50†
4.1. Gas flow through the complete perforated bottom 2 0
A perforated bottom is used to achieve the dispersion of Fl ˆ …r 2 rd †g·s·d02 …51†
the flue gas in the condensate. First, the fluid-mechanical 4 c
processes will be considered for a single hole before the where d0 is the hole diameter, w0 the average velocity in the
description of the phenomena observed at the formation of hole, r c density of the liquid (coherent phase), r d the density
bubbles is applied to the perforated bottom. Fig. 14 shows of the gas (dispersed phase), g the gravitation constant, s the
the bubble formation for a single hole for various gas interfacial tension and s the jet length.
volume flows. The variable s describes the length of the gas jet at the
The volume flow of the gas increases from V_ a to V_ e . The time the bubble cluster tears off. Ruff [44] gives the follow-
separating bubbles get larger as the gas volume flow is ing estimation:
increased. Ignoring the lifting force of the bubbles which   !1=5
increases with growing bubble diameter, the distance of the 1 p 2=5 d04 ·w20
sˆ …52†
bubble clusters remains constant, so the bubbles touch each 2 4 g
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 325

Fig. 15. Calculated Weber numbers We, Wecrit and measured critical Weber number Wecrit for a just completely passed perforated bottom, d0 ˆ
2.5 mm [37].

The forces Fkin and Fp have a destructive effect on the where

liquid lamella, the forces Fs and Fl are constructive. Setting
up a balance for these forces, we obtain: rd w20 d0
We ˆ …57†
Fs 1 Fl ˆ Fkin 1 Fp …53†
p p p
) psd0 1 …rc 2 rd †gsd02 ˆ rd w20 d02 1 sd0 …54†  5=4
4 4 2 w20 rd
Fr* ˆ : …58†
d0 g rc 2 rd
2s r 2 rd d0 g
, 1 c 0:45395 ˆ 1 …55† The Weber number We is the ratio of kinetic force and
rd w20 d0 rd w20
interfacial tension force, the modified Froude number Fr*
is the ratio of kinetic force and lifting force. The ratio of the
2 1 4=5 forces is influenced by the size of the holes. In a small hole,
, 1 0:45395 ˆ 1 …56†
We Fr* 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 ˆ 3.5 mm [37].
326 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

Fig. 17. Drag reduction of the flue gas flowing through the water bath [37] perforated bottom 1: z ˆ 80, d0 ˆ 2.5 mm, V_ bottom;std ˆ 12 m 3/h
perforated; bottom 2: z ˆ 120, d0 ˆ 2.5 mm,V_ bottom;std ˆ 18 m 3/h.

hole, the influence of the interfacial tension force Fs For the dispersion of air in water, this diameter is dgr ˆ
becomes negligibly small and 1/We ! 0. 2.74 mm for a temperature of 258C; this changes very little
For small holes, the limit between single bubble for- within a range of flue gas and condensate temperatures
mation and bubble cluster formation is to be found for between 25 and 508C.
We ˆ Wecrit ˆ 2. For We . Wecrit, we observe bubble Comparing the phenomena of the gas flow through a
cluster formation, while for We , Wecrit, single bubbles single hole and a perforated bottom, it becomes evident
are formed. In the same way, for big holes the limit is to that if the bottom is completely passed by the gas volume
be found at Fr* ˆ Fr*crit ˆ 0.37. flow, each hole is in the state between single bubble for-
Equalizing the criteria Wecrit ˆ 2 and Fr*crit ˆ 0.37, one mation and bubble cluster formation [44]. This means that
obtains the determining equation for the hole diameter dgr every hole of the bottom shows bubble cluster formation if
that separates small and large holes: the perforated bottom is passed completely by gas. Falling
   5=8 short of this characteristic volume flow means that only a
s 1=2 rd portion of the holes are passed by gas and inactive zones can
dgr ˆ : …59†
rd g rc 2 rd 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 ˆ 192, d0 ˆ 1.5 mm, V_ min ˆ
11 m 3/h, perforated bottom 4: z ˆ 40, d0 ˆ 3.5 mm, V_ min ˆ 11 m 3/h.
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 327

At the layout of a perforated bottom for flue gas disper- aggravate a locally constant gas flow through the perforated
sion, amount and diameter of the holes must be chosen so bottom. Fluctuations can be observed in both longitudinal
that the bottom is passed completely by the gas. If too many and transversal direction [43]. This causes pressure vari-
holes (or too big in diameter) are chosen, the bottom is not ations in the gas beneath the perforated bottom which
passed completely by gas and inactive zones will result, disturb the combustion. Our measurements have shown
while for too few holes, an increase of the gas volume much lower pressure variations at a completely developed
flow means an additional drag reduction while passing the circulating flow compared to a gas distribution over the
hole, which results in the formation of larger bubbles. complete liquid cross-section. The size of the pressure varia-
Choosing burner power, air–fuel ratio and flue gas tempera- tions does not show a dependence on the water height above
ture before entering the water bath determines the volume the bottom h.
flow of the gas.
Figs. 15 and 16 show the experimental results for com-
pletely passed perforated bottoms of different geometry. For 4.2. Drag reduction of the flue gas flowing through the water
these experiments, the test boiler shown in Fig. 13 was used. bath
To allow good observation of the bubble formation, the heat
The height of the water column above the perforated
exchanger was not built, and a plexiglass boiler wall was
bottom h, and the drag reduction by the flue gas dispersion
have to be overcome by the burner fan. Fig. 17 gives an
In Fig. 15, the Weber number We for a completely passed
example of drag reduction Dp for two perforated bottoms
bottom is the determining number, as small holes were
dependent on the flue gas volume flow V_ bottom;std .
chosen with a diameter d0 ˆ 2.5 mm. The curves show the
To be added is the drag reduction, caused by bubble
calculated Weber number as a function of the number of
formation and by flow through the perforated bottom, and
holes and volume flow of the gas V_ bottom;std which flows
the pressure difference necessary to overcome the water
through the bottom under the conditions (q std ˆ 258C,
column above the perforated bottom. With increased gas
pstd ˆ 1 bar). The measured points as shown represent the
volume flow, the drag reduction by bubble formation and
volume flow of the gas for which the bottom is passed
by flow through the bottom increases. The calculation are
completely by the gas for the chosen number of holes z.
carried out according to Mersmann [45].
In Fig. 16, the modified Froude number Fr* is used for the
By choosing a larger number of holes (bottom 2), or a
determination of a perforated bottom, as large holes were
larger hole diameter, constant drag reduction can be
chosen with a diameter d0 ˆ 3.5 mm.
* achieved for increased volume flow V_ bottom;std , which may
The values of the critical numbers Wecrit and Frcrit , deter-
result either from a higher burner power or from external
mined in the experiments, are higher than the theoretically
flue gas recirculation.
calculated values Wecrit ˆ 2 and Frcrit
ˆ 0.37. The difference
By using large holes, a decisive decrease in the drag
between theoretical and experimental values increases with
reduction can be achieved. In Fig. 18, a comparison between
a growing volume flow V_ bottom;std . This phenomenon can be
the drag reduction (Dp ˆ Dpperforated bottom 1 Dpbubble formation)
explained because the perforated bottom does not cover the
of a bottom with small holes (bottom 3) and large holes
complete cross-section of the liquid. The liquid taken into
(bottom 4) is shown. The number of holes z, is chosen so
motion by the rising gas bubbles is diverted when it reaches
that both bottoms are passed completely by a gas volume
the liquid surface, and it flows back downward in the section
flow of V_ bottom;std ˆ 11 m 3/h. Measured and calculated
which is not passed by the gas (d2 , d , d1). For such a
volume flow shows good agreement for bottom 3. For
distribution of the dispersed gas over a cross-section of the
bottom 4, the measured values are lower than the calculated.
liquid, a stationary flow of the liquid will result, which we
This is attributed to the fact that the resistance coefficient for
call “circulating flow“. As a result of this circulating flow, a
the calculation of the drag reduction by bubble formation
fifth force at the liquid lamella must be taken into account,
was determined by Mersmann [45], based on small holes.
which supports the lifting force Fl and therefore is a
The separate display of the calculated drag reduction by
constructive force for the lamella. Thus, bubble cluster
* bubble formation and by perforated bottom, compared to
formation begins at higher gas velocities, so Wecrit and Frcrit
our own measurements shows that for large holes the drag
increase. With an increasing gas volume flow V_ bottom;std , the
* reduction by bubble formation can be ignored.
circulating flow becomes stronger and Wecrit and Frcrit
The formation of the circulating flow is enforced by the 4.3. Mass transfer between dispersed gas and liquid
geometrical arrangement of the perforated bottom to
achieve a stable flow of the liquid. If the complete cross- In Section 2.2.2, the mass transfer between dispersed
section of the fluid is covered by the perforated bottom, gas and fluid was described by the two-film theory in the
rising and falling liquid flows come in contact with each example of SO2. Dispersing the flue gas by perforated
other. Even the smallest disturbances can then lead to a bottom, the flow of the gas bubbles and of the liquid are
complete breakdown of the stationary flow and can strongly influenced by the geometric dimensions. Eq. (29)
328 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

Fig. 19. Influence of MgOgran hydration on the pH [37], m_ Oil ˆ 1.0 kg/h, j S ˆ 0.12%, mMgO ˆ 1582 g.

describes the SO2 partial pressure in the flue gas after and is calculated in liquids with a low viscosity, as used
leaving the liquid as a function of following parameters: here according to [47]:
1. gaseous mass transfer coefficient b g, s
2. contact time of flue gas and liquid Dt, dS ˆ : …61†
…rc 2 rd †g
3. mole specific interphase Abu/Nbu of the single bubble.
The bigger the bubbles, and the more turbulent the liquid If the dispersed gas only flows through a very low liquid
flow around them, the bigger is their inner circulation and its column, the average bubble diameter cannot be expressed
mass transfer coefficient b g. The mass transfer coefficient b g by only the Sauter diameter. In the immediate vicinity of the
is dependent on time, and decreases with increased retention perforated bottom, the average diameter is also influenced
of the bubble in the liquid. The reason for this is that each by the size of the holes [43].
bubble—regarded as a closed system—does not show mass The mixture consists of the volume fraction of the gas 1 d
transition, therfore the concentration profile in the bubble and the volume fraction of the liquid 1 c (1 d 1 1 c ˆ 1). The
interior changes with time. A very detailed description of volume fraction of the gas 1 d determines the interphase; it is
experimental and theoretical results for mass transfer dependent on the composition and can additionally be influ-
processes in bubbles is given by Hong and Brauer [46]. enced by the average velocity vd. The average velocity vd is
The contact time Dt can be influenced directly by the determined immediately by the gas volume flow V_ bottom;std
height of the water column above the perforated bottom h. for a given bubble column cross-section A:
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 V_ bottom;std
vd ˆ : …62†
the interfacial tension s . A
The experimental determination of the interphase of If the average velocity is low, the gas bubbles, which are
dispersed gas and coherent liquid is carried out by determin- strongly decelerated when entering the liquid, can distribute
ing the average bubble diameter ds and the gas volume over the whole cross-section. Then a homogeneous structure
contained in the two-phase system. The gas volume is deter- exists and the volume fraction 1 d increases with growing
mined by measuring the difference of mixture volume and average velocity. Further increase in the average velocity
liquid volume. Thus the interphase a is specific to the gas leads to a zone with a higher gas fraction as a result of the
volume and corresponds directly to the mole specific inter- deceleration of the gaseous phase in which bigger gas jets
phase Abu/Nbu, via the ideal gas law. and agglomerations of bubbles can be observed. These can
We write for the volume specific interphase a [47]: rise faster than single bubbles because they show a higher
1d lifting force as a result of their smaller volume specific
aˆ6 …60†
dS surface. The formation of this heterogeneous surface is asso-
ciated with a decrease in the volume fraction, 1 d.
where ds is the Sauter diameter and 1 d the volume fraction of Mersmann [48] gives an upper limit for the average vel-
the gas. ocity of a bubble column:
The Sauter diameter ds is the average diameter of the
bubbles at a greater distance from the perforated bottom vd;max ˆ 0:2we …63†
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 329

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 water. Like SO2, NO2 reacts with water to form an acid.
being stable and is determined by the substance combi- Its deprotonation is guaranteed by neutralization to allow
nation. For the combination of air and water, it is a further absorption of gases and their reaction to acids.
we ˆ 0.2 m/s at 258C. Increasing the average velocity
above the limit mentioned results in a decisive increase 5.1. Neutralization
of the mixture of the two phases, even so, the decrease
of the interphase leads to a deterioration of the heat and Sulfur and nitrogen oxides react forming of acids when
mass transfer. absorbed in water. The deprotonation of these acids leads to
To enable a compact layout of the absorber, the aim is to a strong increase of the concentration of H 1 ions, so the pH
receive a small cross-section A. To guarantee good mass decreases. Thus, according to Eqs. (12), (13) and (15), a
transfer conditions, a minimum cross-section A must be further absorption of SO2 and NOx is aggravated.
achieved. By substituting Eq. (63) in Eq. (62), one obtains By adding a neutralizer, ideally, the same amount of OH 2
with we ˆ 0.2 m/s: ions are dissolved as H 1 ions are produced by deprotonation
of the acids, so the solution stays neutral. The neutralization
V_ bottom;std
Amin ˆ …64† is a basic principle for a continuous absorption of acid-form-
0:04 m=s ing flue gas components in the condensate. For this reason,
The gas volume flow V_ bottom;std is determined by the the experiments carried out on the neutralization shall be
burner power. described before Sections 5.2 and 5.3, which will deal more
For an ideal burner power of P ˆ 15 kW and an air–fuel closely with the absorption of sulfur and nitrogen oxides.
ratio l ˆ 1.1, we obtain for the combustion of heating oil The water bath used for the absorption of acid-forming
EL, a flue gas volume flow V_ bottom;std ˆ 18.2 m 3/h and a flue gas components is an open system. The condensation of
minimum cross-section of the perforated bottom A ˆ the flue gas taking place during the flow of the flue gas
0.126 m 2. through the water bath represents the water supply flow.
An overflow regulating the water height above the per-
forated bottom corresponds to the water outlet. The con-
5. Experiments on the absorption and neutralization of tinuous exchange of the absorbent allows a continuous,
SO2 and NOx in the water bath dosed solution of hydroxides (OH 2), otherwise the excess
neutralizer would be discharged via the overflow.
During physical absorption of gases, the gas remains In Section 2.2.3, the general suitability of oxides, hy-
unchanged in the liquid, and no further gas is absorbed by droxides and carbonates of sodium, magnesium and calcium
the liquid when the saturation concentration is reached. For for the use as neutralizers, has been described. Here, we do
a continuous deposition of a gas component out of a gaseous not deal experimentally with calcium compounds as contin-
mixture, the absorbed gas must react chemically in the sol- uous discharge of the formed salts is not possible as a result
ution to allow the absorption of further gas. of their low solubility.
Thus, the chemical reaction is the key to a continuous The use of sodium hydroxide and sodium carbonate is
absorption of a gas component in a limited portion of generally favored because overflow resulting from
330 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

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. One hour later, the first operation sequence begins. At the
But the effective solubility of the neutralizer itself requires start of this operation sequence, a pH ˆ 9.7 was measured.
the use of a dosage system consisting of pH meter, dosage During the contact time of one hour, MgO and water have
pump and storage tank. formed Mg(OH)2, which has caused the increase of the pH
By using magnesium compounds, expensive apparatus is tending to the dissociation equilibrium
not necessary. The very low solubility of magnesium hy-
Mg…OH†2 N Mg21 1 2OH2 …65†
droxide, in combination with the high solubility of the
formed salts MgSO3, MgSO4 and MgNO3, allows the With the absorption of the acid-forming flue gas com-
discharge of these salts, together with the condensate, ponents, a strong decrease of the pH, down to pH ˆ 5.7,
adding the neutralizer in excess at the same time, because can be observed within the first three minutes of the first
the neutralizer is solid in water and is not drawn off via the burner operation sequence. Having reached this minimum,
overflow. In the following, experiments on neutralization the pH increases slowly until it reaches a value pH ˆ 5.6, at
with magnesium oxide (which forms magnesium hydroxide the end of the operation sequence. Within the first 3 min of
(Mg(OH)2) when dissolved) are shown. the burner operation sequence, the hydroxide formed before
The experiments on neutralization and absorption were is consumed for the neutralization of the formed acid. The
carried out in a test boiler whose design is shown in Section MgO which was covered with Mg(OH)2 before the start of
3.1. Of the perforated bottoms described in this chapter, the burner is set free and the velocity of the hydroxide
bottom 5 is used. The burner was operated at an oil mass formation increases, so the pH increases as well.
flux moil ˆ 1.0 kg/h and an air–fuel ratio l ˆ 1.13 for all the After 72 h, the burner is started again. The pH decreases
experiments. The fuel used was heating oil EL with a sulfur slower than at the first operation sequence and reaches its
content j S ˆ 0.12%. minimum at pH ˆ 6.8 before increasing to its final value
pH ˆ 6.9. The reason for the slower decrease of the MgO
5.1.1. Formation of Mg(OH)2 via hydration of MgO and the less significant minimum is to be seen in the higher
Before magnesium oxide shows a neutralizing effect in amount of Mg(OH)2 that has been formed within the 72 h.
water, it has to react to hydroxide via hydration. Here it shall Also, the following operation sequences, 96 and 102 h later,
be investigated whether the hydration of the MgO takes show a similar course of the pH. The stationary pH at the
place so slowly under unfavorable conditions that the end of each operation sequence increases only slightly with
neutralization of the water bath is not guaranteed because increasing employment time of the MgO in the water bath,
the consumption of Mg(OH)2 for the absorption of acid- and remains below pH ˆ 7.5 even for an operation time of
forming substances is greater than its production. The vel- several weeks.
ocity of the hydration shown in Eq. (32) depends on the form The pH at the start of each burner operation sequence (t ˆ
of the MgO used. With a very compact granulate, a slower 0) decreases with the total burner operation time. The reason
hydration occurs, compared to pulverized MgO. for this is the increasing concentration of Mg 21 in the water
Fig. 19 shows the course of the pH versus time for four bath. During the standstill times of the burner, magnesium
different burner operation sequences, each lasting 1 h. At the hydroxide dissolves until the solubility product of Mg 21 and
start of the experiment, a mass mMgO ˆ 1582 g of granulated OH 2 is reached. Thus, an increasing concentration of Mg 21
magnesium oxide (MgOgran)was added to the water bath. has a higher part on the solubility product and the OH 2
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 331

Fig. 22. Dissociation equilibria of SO2, HSO32 and SO322 versus pH and base fraction xb.

concentration decreases. The difference between the pH at a small part of the CO2(aq), about 0.2% [18], react to form
the burner standstill and burner operation therefore carbonic acid (H2CO3), which dissociates into hydrocar-
decreases with increasing employment time of the MgO. bonate (HCO32) and carbonate (CO322). Theoretically,
carbonic acid is a weak acid. But as the largest part of
5.1.2. Carbonate formation by CO2 absorption the dissolved CO2 exists as hydrated CO2(aq) and not as
Flowing through the neutralized water bath, a part of H2CO3, its solution acts as a weak acid. Fig. 20 shows the
the CO2 contained in the flue gas also dissolves under the dissociation equilibrium in dependence on the pH and the
formation of carbonic acid. While the complete absorption base fraction xb which is defined as
of SO2 is desired, this is different for the absorption of CO2 cbase
xb ˆ …67†
(mCO2 ˆ 3.2moil); for this reason, the system CO2 –H2O shall cacid 1 cbase
be regarded here. The absorption of CO2 is part of the
Adding neutralizer to the water, the reaction equi-
following equilibrium chain:
librium—according to Eq. (66)—is disturbed by the reac-
CO2 …g† 1 H2 O N CO2 …aq† 1 H2 O N H2 CO3 N HCO2
3 tion of hydroxide and H 1 ions to H2O. Tending towards the
1H1 N CO3 22 1 2H1 …66† equilibrium, CO2 dissolves again under the formation of
hydrogen carbonate and carbonate.
CO2 reacts with water to an aqueous complex CO2(aq). Only 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 ˆ 1.0 kg/h, j S ˆ 0.12%.
332 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

Fig. 24. O2 concentration in the water bath versus temperature q wb and air–fuel ratio l [16].

immediately after adding MgO to the water bath, a large sulfite (HSO32), and sulfite (SO322), especially if the H 1
amount of carbonate is formed. We speak of a carbonate ions react to water H2O with OH 2. Fig. 22 shows the
buffer as this carbonate leaves the solution as CO2 without dissociation equilibria dependent on the pH and the base
changes in the pH when a strong acid like H2SO3 is fraction xb.
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 5.2.1. Influence of pH on the SO2 absorption
amounts are lost with the drawn-off water. If the pH lies To investigate the influence of pH on the absorption of
between pH ˆ 7 and 9, mostly HCO32 is formed. SO2, the water bath was blown through with flue gas
Fig. 21 shows the course of the CO2 concentration in the containing SO2, without adding neutralizers. The concen-
flue gas after the water bath and the pH of the water bath for trations of SO2 before and after the water bath were
the addition of caustic soda. The CO2 concentration in the measured. Fig. 23 shows the dependence of the absorption
flue gas before entering the water bath is cCO2 ˆ 13.5%. degree a SO2 on the pH and the height of the water column
Starting with a low pH, a first decrease of the CO2 concen- above the perforated bottom h.
tration can be seen for a pH ˆ 8. As a result of the absorption Beginning at neutral conditions in the water bath, an
of CO2, the pH decreases rapidly and the absorption of CO2 almost complete absorption of SO2 can be observed up to
is stopped. a pH ˆ 4 independent of the height h. At this pH, The
Adding a large portion of caustic soda (t ˆ 17 min), CO2 absorbed SO2 exists almost completely as hydrogen sulfite
is absorbed for several minutes. The pH which then ensues (HSO32). With a further decrease of the pH, the absorption
is pH ˆ 7.7. A stationary pH in the water bath of pH . 8, degree aSO2 decreases rapidly. For a larger water height h,
due to the absorption of CO2, is not expected for the given more SO2 is absorbed compared to a small height. For a
flue gas composition, and the used neutralizers. CO2 does pH ˆ 2.1, the absorption degree is smaller than aSO2 ˆ
not seem to be absorbed for a pH , 7.5, but SO2 is. 0.05 for the investigated water heights.
If falling short of pH ˆ 4 is avoided by adding neutralizer
5.2. SO2 absorption to the water bath, sulfur dioxide is absorbed almost com-
pletely. In contrast, the pH quickly falls short of pH ˆ 4 if
Sulfur dioxide reacts to form acid when absorbed by the condensation of the steam is carried out without an
water. The acid behavior is to be attributed to the formed immediate neutralization of the sulfurous acid, and no
sulfurous acid (H2SO3). important absorption of SO2 occurs any longer.
SO2 1 H2 O N H2 SO3 N HSO3 1 H1 N SO22
3 1 2H
1 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
Here, the equilibrium lies on the right side of the reaction is nearly constant between neutral conditions and a pH ˆ 4
Eq. (68), so almost all of the dissolved sulfur dioxide and its value lies between csulfite ˆ 35 mg/l and csulfite ˆ
remains unchanged as SO2(aq) and only a small part is to 40 mg/l. With a further decrease of the pH, the sulfite
be found as sulfurous acid, H2SO3. As a two-base acid, concentration increases strongly and thereby verifies the
sulfurous acid dissociates according to Eq. (15) to hydrogen recognized decrease of the absorption degree aSO2 .
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 333

Fig. 25. NO absorption degree a NO versus pH and H2O2 concentration at experiment start [37], q wb ˆ 358C.

5.2.2. Sulfite oxidation the SO2 oxidation in an aqueous solution takes place
At the oxidation of sulfite to sulfate, oxygen dissolved in with the order of zero according to the oxygen concen-
the water bath (O2(aq)) is consumed. Fig. 24 shows the tration [26,49]. It is not dependent on the oxygen
measured oxygen concentration in the water bath dependent concentration or on the oxygen transport. The accor-
on the air–fuel ratio l and the water bath temperature q wb. dance between measured and calculated O2
Also, the measured oxygen concentration in the water bath is concentration shown in Fig. 24 was observed within
compared to the calculated saturation oxygen concentration. the limits pH ˆ 3 and 7.5.
For a saturated solution, the O2 partial pressure in the gas After the end of a burner operation sequence, the
and the O2 concentration in the water are in balance, which sulfite contained in the water is also oxidized, and the
is described by the Henry law as a function of temperature. remaining dissolved oxygen is consumed. Nevertheless,
Here, the oxygen partial pressure in the flue gas is deter- enough oxygen is available for the sulfite oxidation at
mined directly by the air–fuel ratio l . the beginning of the next burner operation sequence
Independent of the air–fuel ratio l , the measured O2 because enough oxygen is dissolved during a boiler
concentration is in accordance with the saturation O2 pre-ventilation period during which air is led through
concentration. This means that the balance between the water bath.
dissolved oxygen O2(aq) and oxygen in the flue gas is Sulfite and oxygen show a negative standard potential
established quickly enough to compensate for the difference with D1 ˆ 21.31 V (referred to pH ˆ 14) in
oxygen consumption by sulfite oxidation. In addition, an alkaline solution and D1 ˆ 21.12 V in an acid solution

Fig. 26. Specific emissions ENO before and after the water bath in dependence on the air–fuel ratio l [37], mMgO2 ˆ 270 g, pH ˆ 7.5, h ˆ 10 cm.
334 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

Fig. 27. Absorption of NO2 versus height of the water column and the NO2 start concentration when entering the water bath; pH ˆ 7.

(referred to pH ˆ 0), so the equilibrium of the reaction 5.3.1. Oxidation and absorption of NO in the water bath
In Section 2.3.3, peroxides of water and magnesium were
1 described as appropriate oxidizers for the oxidation of NO in
3 1
SO22 O N SO22 …69†
2 2 4 water, because no personal and environmental dangers arise
from the substances or from their products. Hydrogen per-
lies in both acid and alkaline solutions on the right side. In oxide (H2O2) is used as an aqueous solution and is also a
both cases, the sulfurization takes place completely. product of the reaction of magnesium peroxide (MgO2) and
Under neutral conditions the oxidation reaction from water. Thus, first experiments were carried out with H2O2
sulfite to sulfate takes place so that a reduction of the contact before MgO2 was used in the water bath, based on these
time between gas and water by decreasing the water height experiments.
has unmeasurably small influence on the oxidation. Inde- In the first experiments, gas is led via a thin glass tube into
pendent of the water height h and the sulfate concentration an acid solution and afterwards is led into a gas analyzer. A
csulfate, a stationary sulfite concentration between csulfite ˆ constant-temperature Wulff washing bottle was used as the
35 mg/l and 40 mg/l can be observed. water reservoir. The pH of the solution can be constantly
In contrast, the acid condensate with a pH , 4 shows an measured by a pH meter. The test gas used consists of NO
increase of the sulfite concentration. This increase indicates and N2 with c NO ˆ 90 ppm and cN2 ˆ 1 2 cNO and is led
that the oxidation of sulfite in an acid solution is kinetically into the water with a volume flow V_ ˆ 135 l/h in a height h ˆ
aggravated. The aggravation of the sulfite oxidation and the 50 mm below the water surface.
lack of the deprotonation of the sulfurous acid have the Fig. 25 shows the dependence of absorption degree a NO
result that only little SO2 can be absorbed, compared to on pH and H2O2 concentration in water at the time of the
neutral or alkaline solutions. 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
5.3. Wet absorption of nitrogen oxides degrees a NO. Far greater degrees of absorption have been
reached for short time periods by beginning with a low pH
Nitrogen monoxide (NO) does not react chemically in and adding an alkaline solution; pH ˆ 9 is reached. To
neutral water. The absorption of NO quickly leads to a satu- explain this phenomenon, the following reaction scheme
rated solution. As NO is the largest fraction of the nitrogen must be examined:
oxides (NOx) in the flue gas, the NOx absorption can either
H2 O2 1 H2 O N H3 O1 1 HO2
2 …70†
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 HO2
2 1 NO N NO2 1 OH
of NO in the water bath by adding peroxides which are
strongly oxidative. In Section 5.3.2, the absorption of 2HO2
2 N O2 1 2OH
NO2, dependent on feed concentration and contact time
between gas and liquid, are discussed. H3 O1 1 OH2 N 2H2 O …73†
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 335

By adding H2O2 to water, it decomposes according to Eq. because NO2 decomposes at the high temperatures inside
(70). The formed H2O can react according to Eqs. (71) and the combustion chamber.
(72) forming hydroxide ions (OH 2), which react with Fig. 27 shows the dependence of absorption degree of
hydronium ions (H3O 1) to water, according to Eq. (73). If NO2 on the water height and the concentration of NO2
pH ˆ 9 is reached by adding alkaline solutions, Eq. (70) is when entering the neutral water bath (pH ˆ 7). An increase
disturbed decisively towards the right side, and the of the inlet concentrations of NO2, and of the contact time of
increased HO22 concentrations causes a faster velocity of the gas mixture and water over an increasing water column
the reactions (71) and (72). Out of the weak base HO22, is connected to an increase of the NO2 absorption degree.
the strong base OH 2 is formed, and pH increases without The absorption degree increases as a result of a higher
adding further alkaline solution. As a result of the increasing contact time, caused by the NO2 absorption. Specially
reaction (71), the absorption degrees a NO increases. Having when applying packed beds (Raschig rings) to the water
passed the maximum of absorption, the equilibria of the bath for the experiments shown in Fig. 27, no increase of
reactions (70)–(73) are established again at a pH . 9. the NO concentration could be observed.
To observe the durability of a washing solution with A further increase of the maximum absorption degree, for
H2O2, the gas flow was cut off for 12 h. A higher pH and a which a value of 15% has been reached in the experiments
lower absorption degree a NO can be observed when the gas by a further increase of the contact time, is not supposed to
flow is continued. The reason for this phenomenon is the be possible for a moderate apparative expense.
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 6. Summary
disproportion of H2O2 to H2O and O2 shows a consumption
of neutralizer without NO absorption and does not favor the Many energy sources, like oil, wood or process gases,
use of H2O2 in order to realize a reduction of the NOx contain components which show acid-forming compounds
emission. in their flue gas after combustion, and which, to a small
Using MgO2, a decrease of the absorption degree a NO degree, are absorbed in the condensate when the dew
cannot be observed, after a longer standstill time without point falls short. The acid so-formed, and highly corrosive
leading NO through the washing solution. Magnesium condensate, raises the requirements on the materials used in
peroxide is used as a 1:2 mixture with MgO. the condensation area.
With an increasing air–fuel ratio l , the NO emission of The concepts described in this paper are based on the idea of
the burner decreases in an almost linear manner (Fig. 26). using the condensate for washing the flue gas; thus the flue gas
The amount of absorbed NO is in contrast to this nearly is brought in contact with an already neutralized condensate
independent on the air–fuel ratio l with DENO ˆ 6 mg/ and thereby is cooled below its dew point. This step process
kWh. Showing the same results by the absorption degree allows the wet separation of noxious matter and avoids acid
is not chosen here because the increase of a NO with an corrosion of the materials used in the condensation area.
increasing air–fuel ratio l is only to be attributed to the Thereby, the choice of usable materials is increased.
decreasing NO emission of the burner with an increasing With the example of a gas bubble washer, fluid-mechan-
air–fuel ratio l . ical investigations of the flue gas dispersion in the water
Further experiments have shown dependence of the bath and experiments on the wet separation of SO2 and
absorbed amount of NO on the surface of MgO2 (tested by NOx are presented. The absorption of the gases and neu-
varying amount of MgO2) while the same amount of NO tralization of the formed acids was regarded at the wet
was absorbed between h ˆ 5 cm and 30 cm. We draw the separation, whereas we primarily investigated the absorp-
conclusion that the reaction of MgO2 to H2O2 and MgO— tion of SO2.
which takes place more often with a larger amount of The fluid-mechanical investigations on the flue gas
employed MgO2 —determines velocity but not the contact dispersion in the water bath were aimed at realizing good
time between water and gas. The low solubility of MgO2 mass transfer conditions between flue gas and water, and a
suppresses the consumption of the peroxide during the small expense of energy for the realization of the dispersion.
times of burner standstill, as was observed for the use of The dispersion of the flue gas in the water is achieved by a
the well-soluble H2O2. 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
5.3.2. Absorption of NO2 in water for large holes. For the parameters chosen, a minimum gas
To observe NO2 absorption in water, a gas mixture volume flow is given.
consisting of NO2 and N2 was added to the flue gas before To enforce a circulating flow of the water, only a part of
entering the water bath. Thus, different concentrations of the water bath cross-section is covered by the perforated
NO2 up to cNO2 ˆ 100 ppm could be adjusted. A mix of bottom. Above the perforated bottom, water flows in an
this gas mixture with the combustion air is not possible upward direction and is diverted when reaching the water
336 F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337

surface before it flows downward in the area of the water observed, independent of the water height. The high sulfite
bath, which is not blown through by gas. The stable hydro- concentration in the acid condensate that is not neutralized
dynamic flow conditions decreases the pressure variations in leads to the conclusion that the sulfatization is kinetically
the gas beneath the perforated bottom, which is directly aggravated. A low SO2 absorption is directly connected to a
connected to the combustion chamber. The critical Weber high sulfite concentration in the water bath.
and modified Froude numbers are increased by the Among the almost complete decomposition of SO2, the
circulating flow, so it must be considered at the layout of washer offers the possibility to reduce the emission of nitro-
the perforated bottom. gen oxides. As NO—which is the dominating fraction of
Flowing through the water bath, the pressure of the water NOx emitted from furnaces—is only physically dissolved in
column, as well as the pressure difference for flow through the water, and is not engaged in a chemical reaction, a contin-
perforated bottom and for bubble formation, act as counter- uous absorption is not possible without further means. In
pressure. A minimization of the total drag reduction can be contrast, NO2 reacts in water under the formation of nitric
carried out considering contact time and contact surface and nitrous acid.
between gas and water, whereas for large hole diameters, The oxidation and absorption of NO in water can be
the drag reduction by bubble formation can be neglected. achieved by peroxides of hydrogen and magnesium. Hydro-
Ideal mass transfer conditions are connected to a possibly gen peroxide (H2O2) is not suitable for a long-term operation
high volume fraction of the gas in the two-component as a result of its low stability. Using the stable magnesium
mixture gas–water, which can be influenced for a given gas peroxide (MgO2), a reduction of the NOx emissions of DE ˆ
volume flow by the cross-section of the perforated bottom. 6 mg/kWh could be reached. While the water height was
Acids are formed at the wet separation of SO2 and NOx. shown to have no effect on the absorbed amount of NO, a
The deprotonation of the acids and the neutralization of the dependence on the employed amount of MgO2 could be
H 1 ions formed by hydroxides (OH 2) necessary to achieve a observed. We draw the conclusion that the reaction of
continuous absorption of the acid-forming gases, is possible MgO2 with water to MgO and H2O2 is velocity-determining
in a limited volume of water. In experiments, magnesium but not the contact time between gas and water. An increase
oxide (MgO) has proved to be especially adequate. MgO is of the absorbed amount of NO by a higher pH is not
hydrated to the hardly soluble magnesium hydroxide favorable, due to the absorption of CO2 connected thereto.
(Mg(OH)2). Its low solubility is the reason why no dosage The absorption of NO2 in neutral water requires good
system is required. At the operation of the burner, a pH mass transfer conditions between water and flue gas. By
between 7.0 and 7.5 will ensue depending on the form of applying a packed bed in the water columns, an absorption
MgO used. During the standstill times of the burner, an degree of 15% could be achieved for a start concentration
increase of the pH takes place until the solubility product cNO2 ˆ 62 ppm, and a height of the water column of 40 cm.
of Mg(OH)2 is reached. The increasing concentration of Using gas bubble washers, a reduction of the SO2
Mg 21 with longer burner operation time cause a decrease emissions of about 99% can be achieved within a wide
of the dissolved amount of Mg(OH)2, so the stationary pH of range of sulfur content in the fuel and for a low energy
burner operation and burner standstill phases get closer to expense for the dispersation of the flue gas. A corresponding
each other. CO2 contained in the flue gas is dissolved only reduction of the NOx emission is not possible until now. The
for a pH . 7.5 under the formation of a carbonate buffer. measures described showed a maximum reduction of the
These carbonates are displaced when a stronger acid is NOx emission of about 25%.
dissolved and leave the solution as CO2.
The aim of the investigations on the absorption of SO2 in References
the water bath was a possibly complete desulfurization of the
flue gas. Starting at neutral conditions in the water bath, an [1] Kiehl JT, Briegleb BP. The relative roles of sulfate aerosols
almost complete absorption of SO2 can be observed down to and greenhouse gases in climate forcing. Science, 260.
pH ˆ 4. At pH ˆ 4, the absorbed SO2 exists almost comple- Washington D.C: The American Association for the Advance-
tely as hydrogen sulfite (HSO32). With a further decrease of ment of Science, 1993. pp. 311.
pH, the absorption degree of SO2 decreases rapidly. For pH ˆ [2] Enquete-Kommission Schutz der Erdatmosphäre des 12.
2.1, the absorption degree is smaller than 0.05. Deutschen Bundestages: Schutz der grünen Erde—
For the investigations on the oxidation of sulfite to sulfate, Klimaschutz durch umweltgerechte Landwirtschaft und Erhalt
the concentration of the oxygen dissolved in the water was der Wälder. Bonn: Economica, 1994.
determined. The measured oxygen concentration is the [3] Norm DIN 4705 Teil 1, Oktober 1993: Feuerungstechnische
Berechnung von Schornsteinabmessungen.
saturation concentration which depends directly on air–
[4] Norm DIN 4701, März 1983: Regeln für die Berechnung des
fuel ratio and water bath temperature. This means the equi- Wärmebedarfs von Gebäuden.
librium of dissolved oxygen and oxygen in the gas is estab- [5] Norm DIN 4703 Teil 1, September 1988: Raumheizkörper.
lished quickly enough to replace the oxygen consumed for [6] Recknagel H, Sprenger E, Schramek E-R. Taschenbuch für
the sulfite oxidation to sulfate. In the neutralized water bath, Heizung und Klimatechnik. 67. Aufl.. München: Oldenbourg,
a stationary sulfite concentration of about 35 mg/l can be 1995.
F. Haase, H. Koehne / Progress in Energy and Combustion Science 25 (1999) 305–337 337

[7] Handrock W. Installations- und Betriebstechnik von Verfahrenstechnik. 10. Leipzig: Deutscher Verlag für Grund-
Brennwertkesseln. In: Asue e V, editor. Brennwertgeräte. stoffindustrie, 1994.
Technik – Vorschriften—Erfahrungen, Essen: Vulkan, 1989 [28] Mersmann A. Stoffübertragung. Berlin: Springer, 1986.
(Nr. 11 der ASUE-Schriftenreihe). [29] Barron CH, O’Hern HA. Reaction kinetics of sodium sulfite
[8] Jannemann Th. Stand der Brennwertkessel-Technik in der oxidation by the rapid-mixing method. Chemical Engineering
Bundesrepublik Deutschland. In: Asue e V, editor. Brennwert- Science 1966;21:397–404.
geräte. Technik - Vorschriften- Erfahrungen, Essen: Vulkan, [30] Linke WF. Solubilities. Inorganic and metal-organic
1989 (Nr. 11 der ASUE-Schriftenreihe). compounds. 4th ed., vol. II. Princeton: D. van Nostrand, 1965.
[9] Marx E. Brennwerttechnik beim Einsatz von gasförmigen und [31] Pietsch G, editor. Gmelin Handbuch der anorganischen
flüssigen Brennstoffen. Stuttgart: Gustav Kopf, 1986. Chemie Weinheim: Verlag Chemie, 1939 System-Nr. 27
[10] Göddeke H. (Verf.); Bundesministerium für Forschung und (Magnesium), Teil B, Lieferung 1.
Technologie (Hrsg.): Rationelle Nutzung und Bereitstellung [32] Pietsch G, editor. Gmelin Handbuch der anorganischen
von Energie. Bonn: 1984. Forschungsbericht im Auftrage des Chemie Weinheim: Verlag Chemie, 1961 System-Nr. 28
BMFT. (Calcium), Teil B, Lieferung 3.
[11] Winkens HP. Bedeutung der Rücklauftemperatur für die Fern- [33] Pietsch G. Gmelin Handbuch der anorganischen Chemie,
wärmeversorgung. Düsseldorf: VDI, 1980 (VDI-Berichte Nr. Weinheim: Verlag Chemie, 1936 System-Nr. 4 (Stickstoff),
388). Teil A1, Lieferung 1. 8.
[12] Küchen C; Deutsche Shell AG, PAE-Labor: Untersuchungen [34] Greenwood NN, Earnshaw A. Chemie der Elemente, 1. Wein-
zur Öl-Brennwerttechnik. Hamburg, 1993. Interner Bericht. heim: VCH, 1990.
[13] Küchen C, Deutsche Shell AG, PAE-Labor: Strebel Neotherm [35] Jüttner K, Kreysa G, Kleifges K-H, Rottmann R. Elektrochem-
Öl-Brennwertkessel. Hamburg, 1993. Interner Bericht. isches Abgasreinigungsverfahren zur simultanen Entfernung
[14] Farago Z. Brennwerttechnik mit Abgasentschwefelung für von SO2 und NOx. Chem.-Ing.-Tech. 1994;66(1):82–85.
Hausheizungen. HLH Heizung Lüftung/Klima Haustechnik, [36] Zeise W. Zur Reaktionskinetik der simultanen Absorption von
1. Düsseldorf: Springer VDI Verlag, 1999. SO2 und NOx in wäßrigen Eisen–EDTA-Lösungen in einer
[15] Hinderer D. Heizkessel aus Kunststoff. Si-Informationen Füllkörperkolonne im Technikumsmaßstab. Aachen, RWTH,
1995;10:106–110. Diss., 1989.
[16] Haase F, Köhne H, Graf von Schweinitz H. Reduction of SO2 [37] Haase F. Untersuchungen zur Naßabscheidung von SO2 und
and NOx at an oil-fired condensing boiler. Proceedings of First NOx bei Einsatz von brennwerttechnik. Aachen, RWTH,
European Conference on Small Burner Technology and Heat- Diss., 1996.
ing Equipment (ECSBT), pp. 425–432, vol. II. Zürich: ETH, [38] Hartmann&Braun A.G.: Uras 10 E - Uras 10 P. Frankfurt a.
1996. M., November 1994 (Druck). - Betriebsanleitung.
[17] Graf von Schweinitz H. Ein Beitrag zur Reduzierung der NOx- [39] Zellweger Analytics GmbH: Gas Scout. Dorset (GB), März
Emission durch Inertisierung des Verbrennungsprozesses bei 1995. - Betriebs- und Wartungsanleitung.
Einsatz von Brennwerttechnik. Aachen, RWTH, Diss., 1997. [40] Beckmann Industrial Prozeß-Geräte GmbH: NO/ NOx -Ana-
[18] Holleman AF, Wiberg E, Wiberg N, editors. Lehrbuch der lysator. München. - Firmenbulletin D4406B.
anorganischen Chemie. Berlin: de Gruyter, 1985. pp. 91–100. [41] Schott-Geräte GmbH: Gebrauchsanleitung für Elektroden zur
[19] Igelbüscher H, Schröder R. Gegenwärtiger Stand und Zukunft Messung von pH-Werten und Redoxspannungen. Hofheim a.
des S-H-L-Verfahrens. Technische Mitteilungen, 1/2. Essen: Ts., 1994. - Gebrauchsanleitung zur pH-Einstabmebkette Typ
Vulkan, 1985 pp. 45–49. Nr. N 6280.
[20] Eggersdorfer R. Methodik zur Auswahl des optimalen Ver- [42] Grassmann P, Widmer F. Einführung in die thermische
fahrens zur Rauchgasentschwefelung unter Berücksichtigung Verfahrenstechnik. 2. Berlin: de Gruyter, 1974.
der standortspezifischen Randbedingungen. Technische [43] Brauer H. Grundlagen der Einphasen- und Mehrphasenströ-
Mitteilungen, 1/2. Essen: Vulkan, 1985 pp. 67–71. mungen. Aarau: Sauerländer, 1971.
[21] Scholz F. Entwicklungsstand der Rauchgasreinigung. [44] Ruff K, Pilhofer T, Mersmann A. Vollständige Durchströ-
Brennstoff-Wärme-Kraft 1984;36(1/2):9–18. mung von Lochböden bei der Fluid-Dispergierung. Chem.-
[22] Wallner J, Stibich R, Veiter E. Erfahrungen mit dem Betrieb Ing.-Tech. 1976;48(9):759–764.
einer Entschwefelungsanlage hinter einem Kupfermetallkon- [45] Mersmann A. Druckverlust und Schaumhöhen von gasdurch-
verter. Zusammenfassung eines Vortrages auf einer Tagung strömten Flüssigkeitsschichten auf Siebböden. Beilage zu
des GDMB-Kupferausschusses, Hamburg. Forschung auf dem Gebiete des Ingenieurwesens, Ausgabe B,
[23] Pfeiffer K-D. Stand und Entwicklungsmöglichkeiten der Sprü- Band 28. Düsseldorf: VDI, 1962.—(VDI-Forschungsheft 491).
habsorptionsverfahrens. Technische Mitteilungen, 1/2. [46] Hong W-H, Brauer H. Stoffaustausch zwischen Gas und Flüs-
Vulkan: Essen, 1985 pp. 16–22. sigkeit in Blasensäulen. Düsseldorf: VDI, 1984 (VDI-
[24] Hofmann R. Entschwefelung wie von selbst. In: VDI- Forschungsheft Nr. 624).
Nachrichten, 28.06.91. [47] Mersmann A. Thermische Verfahrenstechnik. Berlin:
[25] Richter E, Knoblauch K. Verfahren der Bergbau-Forschung Springer, 1980.
zur Rauchgasentschwefelung und NOx-Entfernung. Tech- [48] Mersmann A. Auslegung und Mabstabsvergröberung von
nische Mitteilungen, 1/2. Essen: Vulkan, 1985 pp. 13–15. Blasen- und Tropfensäulen. Chem.-Ing.-Tech.
[26] Knapp H. Löslichkeiten von Gasen in flüssigen Lösungsmit- 1977;49(9):679–691.
teln. Staub—Reinhaltung der Luft, 36. Düsseldorf: VDI, 1976 [49] Van Dierendonck LL, Wilkinson PM, Doldersum B, Cramers
Nr. 8, pp. 325–331. PHMR. The kinetics of uncatalyzed sodium sulfite oxidation.
[27] Vauck WRA, Müller HA. Grundoperationen chemischer Chemical Engineering Science 1993;48(5):933.