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Seawater flue gas desulfurization: Its technical implications and performance

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Article  in  Environmental Progress · April 2003

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Seawater Flue Gas Desulfurization:
Its Technical Implications and
Performance Results
Katsuo Oikawa, a Chaturong Yongsiri, b Kazuo Takeda, a and Takayoshi Harimoto a
a Fujikasui Engineering Co., Ltd., 4-3, 1-Chome, Higashi-Gotanda, Shinagawa-Ku, Tokyo 141-0022, Japan; eng2@fkk.co.jp
b Dept. of Environmental Engineering, Aalborg University, Sohngaardsholmsvej 57, DK-9000 Aalborg, Denmark; cy@bio.auc.dk
Increasingly, flue gas desulfurization (FGD) systems are
being installed to control sulfur dioxide emissions in power
plants utilizing coal or oil. For power plants located on an
ocean coast, utilization of seawater from the cooling system of
the plant to scrub sulfur dioxide has become a promising and
attractive alternative to using other alkaline chemicals, such
as limestone and magnesium hydroxide. Sulfur dioxide is
absorbed and subsequently oxidized to sulfate, which is a
native constituent of seawater. Prior to discharge, the acidi-
fied seawater effluent undergoes neutralization using the
natural alkalinity present in seawater (the carbonate-related
system). Compared to the conventional wet limestone system,
the seawater FGD system offers many advantages in terms of
process, design, operation and cost effectiveness.
This paper describes the technical and environmental aspects
of a seawater FGD system. The performance test results of an
existing seawater FGD system employed at a 600-MWe power
plant in China are also presented, focusing on the desulfuriza-
tion efficiency and the seawater effluent quality. Diff e re n t
design configurations for a seawater FGD absorption system are
compared.
INTRODUCTION
An increase in energy demand due to population
growth has led to the construction of many fossil fuel-
fired power plants, e.g., coal/oil-fired power plants [1].
Combustion of coal and oil results in emissions of sulfur
dioxide (SO2), which can harm human health, depend-
ing on its concentration and duration of exposure. In
addition, SO2 contributes to the formation of acid rain,
which is considered a transboundary problem. Acid rain
is clearly linked to acid deposition in the environment,
giving rise to acidification of receiving waters (e.g., lakes,
streams and waterways), as well as deterioration of soil
and forests. Consequently, stringent environmental regu-
lations on SO2 emissions have been promulgated in sev-
eral countries.
Environmental Progress (Vol.22, No.1)
An effective approach to controlling SO2 emissions
is use of a flue gas desulfurization (FGD) system. Vari-
ous types of FGD systems are currently available. They
can be categorized as either wet, dry, or semi-dry
p rocesses. Worldwide statistics for the installation of
FGD systems at power plants in 1998 revealed that wet
limestone processes were the dominant technology,
accounting for 83% of wet FGD systems, and 72% of
total systems installed (226,819 MWe) [2]. To date, FGD
systems have undergone extensive research and devel-
opment to improve SO2 removal efficiency, reliability,
and reduced capital and operating costs [3].
A new development in FGD technology for power
plants located along the coast has been the utilization
of seawater from the plant’s cooling system to scrub
S O 2 f rom flue gas. Dating back to the early 1970s,
re s e a rch conducted at the University of Californ i a ,
Berkeley, showed the feasibility of using seawater to
absorb SO2 from stack gas [4]. In Japan, the seawater
FGD process was first installed in 1978 at a chemicals-
processing plant. This plant reused seawater from the
production line of a factory. The effluent was neutral-
ized with magnesium hydroxide prior to its discharge.
A seawater FGD system was also utilized at a refinery
plant in Norway in 1988 [5].
Despite being a promising technology, the U.S. Envi-
ronmental Protection Agency (EPA) reported that, in
1998, seawater FGD systems installed worldwide
accounted for only 0.6% of the total systems in use [6].
Current development of seawater FGD is still focused
on maximizing its performance as well as minimizing
its costs. Basically, this development involves simpler
design and improved operation.
This paper contains a description and performance
test results of an existing seawater FGD system applied at
a 600-MWe coal-fueled power plant in China. The focus
of the performance test is on desulfurization efficiency
and seawater effluent quality. Technical and economic
April 2003 67
Table 1. Major constituents of seawater (salinity ≈ 3.5%).

Constituent (as Dissolved Ion) Conc. in Seawater (g/kg)

Chloride 19.35
Sodium 10.76
Sulfate 2.71
Magnesium 1.29
Calcium 0.411
Potassium 0.399
Bicarbonate 0.142
Bromide 0.067
Strontium 0.008
Boron 0.0045
Fluoride 0.0013

Figure 1. Simplified schematic diagram of a seawater FGD system.

considerations concerning different types of seawater System Characteristics

FGD are also presented.
PROCESS DESCRIPTION AND MECHANISM
Seawater
Seawater is normally used as a medium in the cool-
ing systems of power plants located along the coast. It
has a typical pH of 7.6 to 8.4, with an alkalinity of
a p p roximately 100-110 mg/l as CaCO 3. The natural
alkalinity of seawater, in terms of carbonate ions
( C O 3 2 - ) and bicarbonate ions (HCO 3 - ), can be
employed to neutralize acidified seawater re s u l t i n g
from scrubbing flue gas. The major constituents of sea-
water are shown in Table 1. Every ton of seawater con-
tains approximately 0.9 kg of sulfur, which is an essen-
tial substance to the marine environment.
Figure 1 shows a simplified schematic diagram of a
seawater FGD system. Flue gas is introduced to an
absorber and contacted with seawater. The most com-
monly employed flow regime of flue gas and seawater is
countercurrent. Scrubbed flue gas then passes through a
mist eliminator to prevent carryover of droplets before
being released to a stack. The SO2 in flue gas reacts with
seawater in the absorption section, which contains either
perforated plates or packings to promote vigorous gas-
liquid transfer and larger gas-liquid interfacial are a ,
depending on its design.
F i g u re 2 depicts the chemistry of a seawater FGD
system. The chemistry mainly consists of the sulfur-
related system (Equations 1 and 2) and the carbonate-
related system (Equations 3 and 4). The SO2 in flue gas
is absorbed in water to form bisulfite (HSO 3 - ), as
described in Equation 1. This reaction takes place in

68 April 2003 Environmental Progress (Vol.22, No.1)

Figure 2. Chemistry of the seawater FGD system.
Figure 3. Example of an existing seawater FGD system
for a 600-MWe power plant.
the absorption section. Bisulfite can also be converted
to sulfite (SO32 - ) which is known to be a source of
chemical oxygen demand (COD) in the seawater efflu-
ent. Thus, COD measurements in this case must be
based on only SO32- ions. Owing to oxygen in flue gas
and seawater, HSO 3- (and also SO 32 -) formed is, in
Environmental Progress (Vol.22, No.1)
Table 2. Characteristics of coal.
Description Value
Calorific Value 25,500 kJ/kg
Sulfur Content (as received) 0.62% (wt.)
Ash Content 11.24% (dry)
Total Moisture Content 11.53% (dry)
turn, oxidized rapidly to sulfate (SO42-) as shown in
Equation 2.
H o w e v e r, the amount of oxygen from those
sources is generally not sufficient for complete oxida-
tion toSO42-. Forcing oxidation of HSO3- and SO32-
to SO42- by blowing air into the sump of the absorber
is, therefore, considered important (Figure 1). In addi-
tion to reducing COD originating from SO32- , SO42-,
which typically exists at relatively high levels in seawa-
ter (See Table 1), is less toxic than SO32-, and a small
increase in the dissolved solid concentration in seawater
does not harm marine life [4]. On the whole, the absorp-
tion process of SO2 is viewed as an environmental short-
cut as it precludes possible sinks for sulfur in the atmos-
phere by transferring it directly into the seawater body.
This process also avoids production of slightly soluble salt
solids—calcium sulfate—because its solubility is increased
when present with sodium chloride in seawater.
According to Equations 1 (the absorption step), and
2 (the oxidation step), shown in Figure 2, hydro g e n
ions (H+) are produced and acidify the seawater efflu-
ent. Since the effluent is returned to the seawater body,
the acidified effluent (H+) must undergo neutralization
before discharge, utilizing HCO 3- and CO32- already
available in the seawater (as natural alkalinity). Equa-
tions 3 and 4 describe the neutralization step that is
chiefly performed in a separate basin by adding more
seawater from the cooling system of the power plant to
obtain the excess alkalinity required. Furthermore, it is
April 2003 69
Table 3. Design data and performance test results of the seawater FGD system (for a 600-MWe power plant).

Description Design Data Performance Test Results

Load of Boiler Operation
600 MWe 450 MWe 350 MWe
Flue Gas
Flue Gas Flowrate (Nm3/hr) 1,916,000 2,220,000* 1,848,000 1,609,000
Flue Gas Temperature (° C) 130 120 120 120
O2 (dry vol. %) 4.7 - - -
H2O (wet vol. %) 8.5 - - -
SO2 (dry 6% O2) at Inlet (ppm) 820 500-700 500-700 500-700
Dust (dry 6% O2) at Inlet (mg/Nm3) 32 n/a 10.2 n/a
Absorber (Perforated Plates)
SO2 Removal Efficiency (%) ≥ 90 92-97 92-97 92-97
Dust (dry 6% O2) at Outlet (mg/Nm3) 25 n/a 3.7 n/a
Pressure Drop in Absorber (mm H2O) 150 n/a 110 97
Seawater
Temperature at Absorber Inlet (° C) 38 30-33 30-33 30-33
Temperature Change Between Absorber
Inlet and Basin Outlet (° C) ≤1 ≤1 ≤1 ≤1
Alkalinity at Absorber Inlet (mg/l) 110 107 n/a 104
Alkalinity at Basin Outlet (mg/l) n/s 43 51 64
pH at Absorber Inlet 8.0-8.2 8.0-8.1 8.0-8.1 8.0-8.1
pH at Absorber Sump 3.0-4.0 3.4 3.8 4.6
pH at Basin Outlet > 6.0 > 6.5 > 6.5 > 6.5
SO32- at Absorber Sump (mg/l) n/s 17.3 12.1 7.1
SO32- at Basin Outlet (mg/l) n/s 0.83 0.50 0.50
DO at Basin Outlet (mg/l) n/s > 6.2 > 6.2 > 6.2

* The flowrate condition was approximately 16% higher than that of the design value during the test.
n/a = not available; n/s = not specified.

essential to blow air into the basin as shown in Figure
1. This process has significant technical and environ-
mental benefits, including:
1. Oxidation of HSO3 - and SO 3 2 - to SO 4 2 - can be
assured.
2. Aerating the seawater effluent results in stripping of
carbon dioxide (CO2) and increasing the efficiency
of neutralization (Equations 3 and 4).
3. Dissolved oxygen (DO) in the seawater effluent is
replenished.
Description and Performance of an Existing System
A performance test of an existing seawater FGD sys-
tem (Figure 3) designed for a 600-MWe power plant uti-
lizing coal was conducted. This power plant is situated
in the southeastern part of China. The test was carried
out at different boiler loadings, i.e., 600, 450, and 350
MWe. This performance test utilizing seawater FGD was
conducted at the same time as the power plant per-
formed the test on its boiler. The characteristics of coal
used in this power plant are given in Table 2. To
achieve a high SO2 removal efficiency and cost effec-
tiveness, the concentration of sulfur in the coal for seawa-
ter FGD should not be higher than 1%. The design values,
with reference to the flue gas, absorber, and seawater
conditions are given in Table 3.
The absorption section of this seawater FGD system
has perforated plates (with no downspouts set aside for
seawater flow by vertical plates). Seawater used for the
absorber is obtained from the cooling system. The rest
of cooling system seawater is supplied to the basin to
neutralize the effluent.
Only desulfurization efficiency and the quality of the
seawater effluent are of concern in this study. Therefore,
other acidic gases found in flue gas, e.g., NOx (nitrogen
oxides), HCl (hydrogen chloride gas), HF (hydrogen fluo-
ride gas) and Cl2 (chlorine gas), were not considered in
the design of the system because they have no significant
effect on the efficiency of seawater FGD. Since the exist-
ing system is not equipped with a prescrubber, in which
chlorides and fluorides can be considerably removed with
p rocess water, these chemicals are, to some extent,
removed in the prequenching part and subsequent sea-
water absorber. In general, the seawater FGD system
removes 90% of HCl and HF, and 20-30% of the Cl2.
The seawater FGD system does not significantly
remove NOx . In spite of the fact that NO 2 ( n i t ro g e n
dioxide) can be reacted with SO32- and, hence, con-

70 April 2003 Environmental Progress (Vol.22, No.1)

verted to N2 (nitrogen gas) in the absorber, most of the
NOx in flue gas is in the form of NO (nitric oxide) that
is less reactive and not readily absorbed [4, 7].
Typical pH values found in the seawater absorber are
3.0-4.0 (Table 3). The selection of materials that can resist
highly acidified seawater effluent is important for both
capital costs and system reliability. Both materials, coated
with non-metallic substances (e.g., polypropylene and
fiberglass-reinforced plastic) and high-quality stainless
steels (e.g., SUS316L: 18Cr-12Ni-2.5Mo-C and SUS329J1:
25Cr-4.5Ni-2Mo), are used for the construction of the
a b s o r b e r. For parts that are exposed to highly
corrosive/erosive environments in the absorber, high-
quality stainless steels are recommended.
Table 3 shows the perf o rmance test results of the
seawater FGD system. It can be seen that the system
has shown excellent perf o rmance in terms of SO 2
removal efficiency (92-97%) and environmental aspects
of the seawater effluent under all loads investigated. Its
performance was very stable under different loads dur-
ing the test even though the flue gas flowrate, when
operating the boiler at 600 MWe, was approximately
16% greater than the design value. This high perform-
ance should be due to low SO2 concentrations com-
pared to the design value, thus compensating for the
i n c reased flowrate. One of the system advantages is
withstanding variations of the flowrate, and concentra-
tion within practical limits.
The concentration of dust was examined at 450
MWe. Its inlet concentration was approximately three
times lower than that of the design value as it was
mostly removed in a preceding electrostatic precipitator
(ESP). The existing seawater FGD system, however,
had a dust removal efficiency of about 60% compared
to the guarantee value of 20%.
Further tests were conducted to investigate whether
complete oxidation of SO32- to SO42- in the absorber
sump could be achieved. The results show some
remaining levels of the SO32-, for example, 17.3 mg/l
at the 600-MWe load, (Table 3), indicating that oxida-
tion was not complete. However, almost complete
oxidation subsequently takes place in the basin, as
shown by low SO32- concentrations at the basin outlet.
Although SO32- not oxidized will theoretically result in
p recipitation in the sump, this process is unlikely to
cause an operation problem in practice because of 1) the
very low pH of the seawater in the sump (3.0-4.0), which
does not favor precipitation and 2) a short retention time
and high turbulence originating from aeration, which will
not allow solids to settle in the sump. Other possible
salt precipitates are SO42- salts (e.g., calcium sulfate),
which are slightly soluble. However, the presence of
sodium chloride in seawater normally increases the sol-
ubility of calcium sulfate. The potential of scaling in the
absorber, as well as piping systems is, therefore, not
expected.
From an environmental point of view, the pH, tem-
perature, and DO of the seawater effluent before dis-
c h a rge to the sea are of concern, particularly with
respect to the local ecology. The very low COD of the
seawater effluent is confirmed by low SO32-concentra-
tions at the basin outlet (less than 1 mg/l). The
Environmental Progress (Vol.22, No.1)
increased amount of SO42- in the seawater body has a
practically negligible effect because the content is
insignificant (less than 5%) when compared to the
native amount present. Chemodynamics within the
three primary phases of the environment, i.e., air, sea-
water, and sediments, on the chemical reactivity of SO2
(i.e., hydration and oxidation) will, in the long term,
play a role in the movement and fate of the SO 2
removed from flue gas by the seawater absorber.
The low pH of the acidified seawater effluent (Table
3) necessitates the neutralization process, which takes
place in the basin. By controlling the amounts of seawa-
ter and air added, the pH of the seawater effluent can
p roperly be adjusted. Oxidation and neutralization
processes are operated to ensure an effluent pH value of
over 6.5 at the outlet of the basin. After being returned to
the seawater body, this discharge pH increases toward
ambient values in a zone whose area and magnitude are
governed by mixing and diffusion processes. The critical
pH value for marine and estuarine animals is, in general,
6.5 [4, 8].
The temperature diff e rence of less than 1° C
between the seawater and the effluent, and the effluent
DO of higher than 6 mg/l can be expected. These con-
ditions are primarily caused by aeration in the basin,
where oxidation and neutralization are continuously
performed. Although variations in pH, temperature and
DO are within natural variations, further research on
their long-term effects on the ecology and seawater
chemistry should be studied by taking specific sites
into consideration.
EVALUATION OF TECHNICAL AND ECONOMIC CONSIDERATIONS
As an alternative for power plants located along the
coast, the seawater FGD system offers a simpler alterna-
tive to the conventional system, wet limestone processes,
in process, design, and operation since it requires no
addition of chemicals. A comparison of system character-
istics between seawater FGD and wet limestone FGD is
given in Table 4. The comparison is based on a 600-MWe
power plant utilizing coal having 1% sulfur. Based on the
information presented in Table 4, it is obvious that the
seawater FGD system is technically and economically
better than the wet limestone system. When planning
power plants, site-specific conditions must be taken into
account in the selection of the FGD systems. For exam-
ple, in terms of the operations, management of very large
amount of generated gypsum can be considered a limit-
ing factor for the wet limestone FGD system, whereas
availability of seawater is a limitation for the seawater
FGD system.
Typically, the absorption section of the seawater FGD
system is designed with either perforated plates or pack-
ings. Systems with perforated plates benefit fro m
extremely vigorous gas-liquid transfer, whereas the pack-
ings make use of a larger gas-liquid interfacial area. Tak-
ing full advantage of these characteristics to achieve a
greater degree of reliability, higher removal efficiency,
and cost-effectiveness, the absorption section was re-
designed using both perforated plates and packings.
Table 5 demonstrates a technical comparison of these
three design configurations for seawater FGD. The sys-
April 2003 71
Table 4. Comparison between seawater FGD and wet limestone FGD systems for large power plants.

Description Seawater FGD Wet Limestone FGD

SO2 Removal Efficiency 90-98% 80-95%
By-Product - Gypsum (Large Amount)
Effluent Characteristics Slightly Increased SO42- Increased Suspended Solids
Required Supporting Systems Seawater Supply and Wet Limestone Preparation,
Neutralization Oxidation and Dewatering
Process Water Consumption Extremely Low High
Electricity Consumption Medium Low
Capital Cost (as %) 75-80% 100%
Operating Cost Low Medium

Note: Based on a 600-MWe power plant utilizing coal having 1% sulfur.

Table 5. Comparison of seawater FGD designed with different absorption sections.

Description Packings Perforated Plates Combined Packings and

Perforated Plates
Gas Velocity (m/s) 1.0-1.5 3.0-3.5 1.6-1.8
Seawater Volume Small Large Small
Pressure Drop in Absorber Small Large Small
Absorber Size Large Small Medium
SO2 Removal Efficiency 95-98% 90-98% 95-98%
Clogging Very Likely Unlikely Unlikely

Table 6. Economic comparison of a seawater FGD system designed with two different absorption sections (for a
600-MWe power plant utilizing coal having 0.6-0.7% sulfur).

Description Perforated Plates Combined Packings

and Perforated Plates
Flue Gas Flowrate (Nm3/hr) ------------------------------1,916,000--------------------------
SO2 at Inlet/Outlet (ppm) ------------------------------700/50------------------------------
Temperature at Inlet/Outlet (° C) ------------------------------130/40------------------------------
Capital Cost a, b (USD) 39,000,000 42,000,000
Operating Cost c (USD)
(Operated 6,312 hr x 10 years) 19,000,000 12,000,000
Total Cost 100% 93%
a Based on Japanese conditions.
b Excluding an electrostatic precipitator, gas-gas heat exchanger, stack and civil work.
c Applied for electricity 65%, maintenance 30% and process water 5%.

tem with combined packings/perforated plates has a high
SO2 removal efficiency, while reducing the absorber size
and seawater consumption.
Measurements of cost-effectiveness for different sea-
water FGD design configurations are shown in Table 6.
At the same flue gas conditions for a 600-MWe power
plant utilizing coal containing 0.6-0.7% sulfur, the system
with combined packings/perforated plates had lower
operating costs (approximately 35% lower) over a 10-
year period compared to the perforated plate system. The
lower operating cost is mainly due to decreases in elec-
tricity and maintenance, e.g., smaller seawater pumps.
When the capital cost is taken into consideration, this
results in the total cost of the system with combined
packings/perforated plates being 7% lower than that of
the system with only perforated plates.
CONCLUSIONS
Utilization of seawater to remove sulfur dioxide from
flue gas has technically and economically proven to be
a promising alternative to alkaline chemicals for power
plants located along the coast. A performance test on
an existing seawater flue gas desulfurization (FGD) sys-
tem employed at a 600-MWe power plant (utilizing coal
containing 0.62% sulfur) showed excellent desulfuriza-
tion efficiency, high reliability, as well as acceptable
environmental impacts. In comparison to a convention-
al wet limestone system, the seawater FGD system

72 April 2003 Environmental Progress (Vol.22, No.1)

offers a number of remarkable advantages, such as the
simplicity of the process, design, and operation
because no additional chemicals are needed, and no
solid wastes are produced. The quality of the seawater
effluent can be controlled through the oxidation and
neutralization processes.
Recently, a newly developed design for the absorp-
tion section of seawater FGD (i.e., combined pack-
ings/perforated plates) has shown increased cost effec-
tiveness and high sulfur dioxide removal.
ACKNOWLEDGMENTS
The authors are grateful to Natalie Nottage and Dr.
Thatchavee Leelawat for their critical comments on the
manuscript. They also thank the personnel involved in
this study at the Fujikasui Group for their assistance.
Finally, comments from the anonymous reviewers are
also greatly appreciated.
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