Experiment Study of a Pilot FGD System by Ammonia

Scrubbing in a CFB Power Plant

Xu Hong, Yan Zhi-Yong, Hu Jian-Fei
Dept. of Thermal Power Engineering
China Jiliang University
Hangzhou, China
[email protected]

Abstract—A 3000Nm3/h pilot flue gas desulfurization experiment SO 2 +2NH 3 +H 2 O → (NH 4 ) 2SO3
system by ammonia scrubbing was established in a 35t/h (1)
SO 2 +(NH 4 ) 2SO3 +H 2 O → 2NH 4 HSO 3
circulating fluidized bed (CFB) power plant in Zhejiang
Province. Experiment results showed that the desulfurization NH 3 +NH 4 HSO3 → (NH 4 ) 2SO3
efficiency was above 90%, and SO2 emission concentration
satisfied the environment emission standard of China. Also, the
The technology has been applied in electric power plants
byproduct of desulfurization, aqueous ammonium bisulfite, can successfully by Marsulex Environmental Technologies (MET)
be utilized as middle chemical materials and its quality was in the U.S.A , NKK cooperation in Japan and Krupp Koppers
eligible to concerning chemical industry standard of China. The cooperation in German. The first commercial scale Ammonium
technological process of the flue gas ammonia scrubbing not only Sulfate Forced Oxidation FGD was built in the Great Plains
has high desulfurization efficiency but also recycles the valuable Synfuels Plant located in Dakota using MET[3]. It was
sulfur resources without secondary pollution. completed in 1996 and succeeded in allowing the plant to meet
state required sulfur dioxide regulations and producing a
Keywords-flue gas desulfurization(FGD); ammonia scrubbing; saleable grade of ammonium sulfate fertilizer. Combined
ammonium bisulfite (NH4HSO3); a CFB power plant AMASOX and NOX removal technology with ammonia was
used in the Krupp Koppers[5]. But ammonia FGD has hardly
I. INTRODUCTION been used in coal-fired power plants in China so far.
Sulfur and nitrogen oxides emitted from electric power In this paper, a pilot ammonia FGD apparatus was built in a
plants are the principle causes of acid rain in air pollution. 35t/h circulating fluidized bed power plant. Experiments were
They are known to be hazardous to people’s health and the completed to measure the desulfurization efficiencies and to
environment, and their emission into the atmosphere is strictly produce an aqueous solution containing dissolved ammonium
regulated by clean air statutes in all of the world. These gases bisulfite (NH4HSO3) as a byproduct. This byproduct can be
also form secondary particles in the atmosphere, contributing used as the middle chemical materials. Because it is different
to urban PM10 and PM2.5 problems and impairing visibility in from ammonium sulfate as a fertilizer, the apparatus and
the air. In China, most sulfur dioxide emissions are from coal procedures of the ammonia FGD have its own characteristics,
burning, since above 70% electricity source comes from coal- which has hardly been applied to thermal power plants.
fired power plants[1]. The situation is similar to the U.S.A [2]and
other countries. II. EXPERIMENTAL DEVICE AND PROCEDURE
Traditionally, ammonia-based scrubbing processes produce A 3000Nm3/h pilot flue gas desulfurization experiment
a more valuable byproduct of ammonium sulfate as a fertilizer system by ammonia scrubbing was designed and established in
in agriculture instead of discharging liquid pollutants into 35t/h circulating fluidized bed power plant. A series of
environment with high desulfurization efficiency[4]. In these experiments were carried out to confirm the process design and
processes, the scrubbing solution is accumulated in a tank operational parameters, which will provide basic data for
where the absorbed sulfur dioxide reacts with ammonia to form industrial application in the future.
ammonium sulfite and ammonium bisulfite, which are oxidized
in the presence of sufficient oxygen to form ammonium sulfate A. Description of experimental apparatus
and ammonium bisulfate. A portion of the ammonium sulfate Fig. 1 is a schematic representation of the flue gas ammonia
solution or ammonium sulfate crystals that form in the solution scrubbing apparatus. The total system is composed of pre-
can then be drawn off to yield the desired byproduct. scrubbing devices, desulfurization towers, deposited volumes
In wet ammonium FGD process, the main reactions are of byproduct solution and byproduct flirtation devices. The flue
showed in the following chemical formula. gas containing dust is cleaned by dynawave scrubber, then
entering a empty tower, where temperature of the flue gas
decreases from 105~110 ℃ to about 40 ℃ .The water after
scrubbing flows through the plate and frame filter press where

Natural Science Foundation of Zhejiang Province (Y5080087)

978-1-4244-4813-5/10/$25.00 ©2010 IEEE

filtrated sludgy is disposed, and cleaned water is pumped into cleansed gases continue to rise through a mist eliminator to the
dynawave scrubber recycling. atmosphere.
The main components is the ammonia-based scrubbing Ammonium bisulfite and sulfite solution in the tank of the
system. Two cascade towers of desulfurization are designed to first tower keep high concentration constantly through
achieve not only high SO2 removal efficiency but also aqueous accumulating reaction and adding ammonia. Some solution is
ammonium bisulfite byproduct. The first tower mainly acts as recycled into the spray ammonia scrubbing, while the other is
byproduct tank, in which part of SO2 gas is eliminated at the drawn off from the tank of the tower into the deposited
PH value of 5.2~5.4 and higher ammonium bisulfite container, where it is filtrated to achieve qualified byproduct.
concentration. The absorption solution will effluent from the The scrubbing solution in the tank of the second tower flows
system when accumulating to certain concentration. While the into the first one to remain liquid balance of the reaction
absorption solution in the second tower is controlled at higher solution.
PH value of 5.9~6.2 and lower concentrations, this operation
condition ensures the total high desulfurization efficiency. SO2 The flue gas from outlet of ESP contains fairly high SO2
concentration in the cleaned gases meets the emission concentration, which is 9572~14867 mg/m3, and relatively high
standards of air pollutants for thermal power plants. dust loading, which is 240~596 mg/Nm3, because sulfur and
ash constituent in the local coals is relatively high. TABLEⅠ
The deposited solution volumes are used to place ammonia shows the proximate and ultimate analysis and the low calorific
solution and the byproduct. Filtration devices will filter the value of the coals and flue gas constituents. In the experiment,
solution, eliminate the dust and ferri ion and achieve the the flue gas flux is about 3000Nm3/h and concentration of aqua
desired aqueous ammonium bisulfite solution. The quality of ammonia added in the spray tower is 25%. Operation
the byproduct needs to meet concerning chemical industry parameters of the two tower are desighed and showed in
standard. TABLEⅡin terms of total SO2 removal efficiency and the
byproduct quality request.
B. Experimental procedures
The initial flue gas is extracted from the stack at the outlet C. Experimental planning
of ESP and flows into the ammonia FGD pilot system by the The PH level of spray solution was adjusted to desired
pressured fan. Fly ash in the flue gas was most cleaned by value by adding 25% aqueous ammonia solution to both tanks
dynawave scrubber and the temperature decreases because of of the two towers. Detailed profiles of desulfurization
water evaporation. The flue gases containing acidic gases efficiency at different PH values can be gained by measuring
comprising sulfur dioxide then enter the two ammonia SO2 concentration with Testo335 gas analyzer at the inlet and
desulfurization towers sequently. An ammonium sulfite- outlet of the two towers respectively. Other parameters such as
containing solution contacts the flue gas and absorbs a portion L/G ratio and flue gas rate are changed in the desulfurization
of sulfur dioxide in the first tower and remaining sulfur dioxide experiments and a lot of valuable results are received.
in the flue gas is absorbed nearly completely by the scrubbing
solution in the second tower. With respect to quality of the aqueous ammonium bisulfite
byproduct, we concern about two important aspects. One is the
Spray wet ammonia scrubbing towers are applied in the concentration and constituent of ammonium bisulfite solution,
CFB power plant, where flues gas stream contacts with liquid
falls from spray nozzles counter-currently to collect SO2 gases.
The ammonia-based solution medium is recycled from the TABLE I. PROPERTIES OF COAL AND THE FLUE GAS
bottom of the tower to spray header. There are three banks of Proximate analysis (wt%) Coal 1 Coal 2
sprays in each tower to provide enough reaction time for the Moisture 2.36 3.24
gas-liquid contact. Intimate contact between the solution Volatile matter 4.17 6.49
medium and the flue gas rising through the tower results in
Fixed carbon 16.6 47.4
cleansing action, after which the contact solution and entrapped
Ash 76.9 42.87
gases are collected in the tank at the bottom of the tower. The
Ultimate analysis (wt%)
Carbon 16.4 40.88
The Cleaned Gas Hydrogen 0.69 1.14
Nitrogen 0.19 0.34
Mist Eliminator
Mist Eliminator Mist Eliminator Oxigen 0.19 8.9
Sulfur 3.26 2.63
Spray Snozzle Spray Snozzle
Heating value (kJ/kg) 5.52 17.18
Intial flue gas analysis (%) 1# boiler 2# boiler
Ammonia Tank Byproduct Tank O2 11.8 12
Initial Flue Gas
CO2 5.4 5.4
3
CO (mg/m ) 221 13
Dynawave Scrubber Empty Tower 3
No.1 Desulfurization Tower No.2 Desulfurization Tower NO (mg/m ) 188 110
3
SO2 (mg/m ) 12530 14086
Fig.1 A schematic representation of the flue gas ammonia scrubbing 3
Dust loading (mg/Nm ) 361.8 445.42
apparatus
 TABLE II. DESULFURIZATION EFFICIENCIES
100
No.1 Spray scrubber No.2 Spray scrubber
Total
tower tower
80 PH D. E.* % PH D. E.* % D. E.* %
desulfurization efficiency %

the first tower

the second tower
5.27 32.8 6.05 97.9 98.6
60
total
5.30 27.3 6.16 98.5 98.7

40 5.36 30 6.15 98.7 99.1

5.68 48.1 5.95 86.6 93.1

20
*. desulfurization efficiency. (D. E.)

gas-liquid contacting surface becomes greater, which results in

2100 2200 2300 2400 2500 2600 2700 2800 higher desulfurization efficiency. In our experiments, when
3
flue gas flux m /h L/G is from 8.5 to 15, the desulfurization efficiency increase
Fig.2 The desulfurization efficiency versus different flue gas flux from 90% to 100% (showed in Fig.3). The desulfurization
profile also shows most SO2 is absorbed in the second spray
which is limited to above 550~600g/L and tower, in which the desulfurization efficiency is between
NH4HSO3/(NH4)2SO3>10. The other is ferric ion content in the 86%~99.6%. However, the desulfurization efficiency in the
solution, which is required to be less than 2ppm. The ferric ion first tower scrubber is only about 27%.
concentrations in all tanks of the spray towers are sampled and B. The analysis of byproduct
measured with Atomic Absorption Spectrometer (AAS).
Millipore filter was employed to eliminate impurities and ferric 1) The concentrations of the byproduct ： The ammonia
ion in the solution to guarantee the byproduct meeting solution was added to the tank of No.1 tower scrubber at the
concerning chemical industry standard of China. rate of 10~15L/h, and 40~60L/h to the tank of No.2 tower.
The ammonium sulfate concentration in the solution is
III. RESULTS AND DISCUSSIONS comparatively high, because of the high oxygen content 12% in
the flue gas, which results in oxidization of ammonium
A. Parameters’ effects on the desulfurization efficiency bisulfite and sulfite. The constituents and concentrations of the
Influence of the main variables parameters, such as pH absorption solution in both spray towers during experiments
value, liquid to gas (L/G) ratio and flue gas rate on the are showed in TABLE Ⅲ.
desulfurization efficiency were analyzed in the ammonium-
based scrubbing experiments. TABLE III. THE CONSTITUENTS AND CONCENTRATION OF ABSORPTION
SOLUTION
1) The PH value: PH is the most important parameter to
Chief
affect desulfurization efficiency of the ammonium-based No.
constituents
Concentration, mol/L
scrubber. The designed PH value of the first spray tower is a
ABS 4.68 4.69 4.9 4.99 5.09 5.02
about 5.2 and the removal efficiency is 27.3%~48.1%, showed
b
in Table.Ⅱ, while the designed PH value of the second one is AS 0.39 0.32 0.59 0.67 0.41 0.49
about 6.0 and the efficiency is 86.6~98.7%. The total efficiency ABS/ AS 12 15 8.3 7.5 12.4 10.3
No.1
is 93.1~99.1%. SO2 concentration emitted from the Tower ABS+AS (g/L) 509 502 554 572 552 553
desulfurization system meets the emission control regulation
for thermal power plants. PH value 5.18 5.25 5.3 5.31 5.24 5.3
2) The flue gas rate: The gas rate indicates the flue Ammonium
0.84 1.11 0.87 0.83 1.08 1.01
residence time through the scrubbing tower. If the tower is 10m sulfate

high and the gas rate is 5.67~6.98m/s, the residence time is ABS 1.77 2.61 2.56 3.06 3.35 2.92
1.43~1.76s. The gas flow directly affects the SO2 mass AS 2.24 2.2 2.4 2.08 1.59 1.99
transfer/chemical reaction process, scrubber pressure drop and No.2 ABS+AS (g/L) 436 514 532 545 517 520
mist eliminator water removal[6]. Fig.2 shows the flue gas rates Tower
effect on desulfurization efficiencies. When the gas flow PH value 6.39 6.16 6.22 6.02 5.93 6.07
decreases from 2700m3/h to 2200m3/h, the desulfurization Ammonium
0.63 0.6 0.4 0.34 0.7 0.58
sulfate
efficiency increases from 78% to 99.5%. During the
a. Ammonium bisulfite. (ABS)
experiments the flux of spray liquid is consistent 45m3/h, and
b. Ammonium sulfite. (AS )
the PH value and other parameters keep relatively constant.
2) Ferric ion problem in the absorption solution: Some
3) The L/G ratio:When the spray liquid flow rate increases
heavy metals, such as iron, can undesirably effect the color of
under a constant flue gas rate, the L/G ratio increases, and the
 100
empty tower
80
the No.1 tower

ferri ion concentration mg/m3

desulfurization efficiency %

80 the No.2 tower

the first tower 60

60 the second tower
total

40 40

20
20

0
8 10 12 14 16
0
L/G ratio l/m
3
before filtration after filtration

Fig.3 The desulfurization efficiency versus the L/G ratio Fig.4 The ferri ion concentration in different towers before and after
filtrations

byproduct, further more, reducing product value. The solution to meet concerning chemical industry standard after subsequent
color of our byporducts is deep red, because the ferric ion treatments. It provides a new method to recycle utilizaton of
concentration in aqueous ammonium bisulfite is much higher the valuable sulfur resources contained in flue gas SO2.
than the chemical industry standard value, which is limited to
less than 2ppm. ACKNOWLEDGMENT
The tank solutions in the dynawave scrubber and three We acknowledge the support of Natural Science
spray towers were sampled, filtered and ferric ion Foundation of Zhejiang Province and really appreciate help of
concentration was analyzed with AAS. The ferric ion Zhejiang Huba Thermal Power Cooperation during field
concentration in the dynawave is remarkably high, which is experiments.
average 995mg/m3. Ferric ion content in the three towers
solution is showed in Fig.4 before filtration and after filtration.
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Since filtration can eliminate some fine fly ash paticles in the
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[3] Myles Dittus, Dale Johnson. DAKOTA GASIFICATION COMPANY
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