Effect of Amino-Desulphurization on the Concentration Retrieval of SO2

Chi Zhang, Baofeng Zhang

Bin Liu, Tao Zhou, Changku Sun*

School of Electrical Engineering

TJUT
Tianjin, China
ioe_omi@163.com

State Key Lab of Precision Measurement Technology and

Instruments
TJU
Tianjin, China
sunck@tju.edu.cn

AbstractAmino-Desulphurization technology has been widely

used to reduce the pollutant emission in coal-fired power plants.
However, excessive amino sprayed, not only results in the waste
of liquid amino, but also brings a great error of the
concentration retrieval of SO2 by Continuous Emission
Monitoring System(CEMS) based on Differential Optical
Absorption Spectroscopy(DOAS). To find an effective retrieving
method to determine the excessive ammonia, a least-square
algorithm simulation analysis on the effect of excessive ammonia
is proposed. And the method is used to analyze the on-site
spectrum data to improve the precision of the concentration
retrieval of SO2. The experimental result shows that the
downward trend of the concentration retrieval of SO2 is
recognized. It confirms that the excessive ammonia gas affects
the concentration retrieval of SO2 during aminodesulphurization process. And if the excessive ammonia is
considered, the change of concentration of SO2 before and after
the desulphurization can be fitted by least-square method, and
the accuracy of the retrieved concentration is improved.

retrieving method is effective to deal with the errors on

concentration retrieval of SO2 and NO.

Keywords-Amino-Desulphurization; Concentration Retrieval;

CEMS; DOAS

I.

II.

MONITORING OF STATIONARY SOURCES POLLUTION

A. Continuous Emission Monitoring System

Continuous emission monitoring system is used to monitor
the flue gas emitted by the boilers of civil or industrial plants
which use liquid or solid fossil fuel [1].
CEMS contains many subsystems monitoring several
different parameters of the flue gas. The principle of the gas
monitoring subsystem based on DOAS is shown in Figure 1.
UV source

Collimating lens

Transmitter

INTRODUCTION

With the development of Chinese industry, atmospheric

environmental problems attract more and more attentions.
Among them, monitoring of air pollutant SO2 and NO is a fatal
issue. Although CEMS based on DOAS has been used to
monitor the harmful gas successfully, it always incurs
measurement error when coal-fired power plants use aminodesulphurization system.
A power plant in Shandong Province, China, is chosen to
be the target. The CEMS used in this plant runs normally and
effectively in no-Amino-Desulphurization circumstance. When
amino-desulphurization was running, the concentration of SO2
measured by CEMS stayed at a level near 2000mg/m3, while
the concentration of SO2 measured by portable instrument
descended from 2000mg/m3 to 150mg/m3. The main reason for
this phenomenon is that NH3 is mixed into the flue gas caused
by excessive ammonia spraying.
To solve this problem, a least-square algorithm simulation
analysis is proposed. The simulation result proves that the
method can retrieve the concentration of SO2 and NO precisely
even when NH3 is mixed in the gas. And the method is tested
by on-site data analysis. The experimental result shows that the

Focusing lens

Measurement area

Fibre connector

Receiver
Fibre

Electrical signal
Spectrometer

Figure 1. Diagram of gas monitoring subsystem

The subsystem includes the light source, the collimating

lens, the sample pools, focusing lens, the fiber connector, the
base and so on. The UV-VIS beam emitted from the light
source transmits through the collimating lens to form a
uniform beam. After going through the sample pools on the
base, the beam accesses to the focusing lens and transferred to
the spectrometer by fiber. All the optical devices have a high
UV transmission ability. The optical path of the system is oneway path, which may reduce the unnecessary loss of the light
intensity in the transmission process [2].
B. Amino-Desulphurization of stationary sources
Amino-Desulphurization using liquid ammonia as
desulfurizer is an effective method to reduce the concentration
of SO2 in flue gas [3]. SO2 is eliminated during its reaction to
ammonia. The main reaction is described as follows:

*Prof. Changku Sun, Tianjin University

sunck@tju.edu.cn; fax 86 022 27404778

978-1-4244-2902-8/09/$25.00 2009 IEEE

Authorized licensed use limited to: Stefanos Diamantis. Downloaded on December 25, 2009 at 14:08 from IEEE Xplore. Restrictions apply.

2NH 3 + SO 2 + H 2 O ( NH 4 )2 SO3

SO 2 + ( NH 4 )2 SO3 + H 2 O 2NH 4 HSO3

(1)

NH 4 HSO3 + NH 3 ( NH 4 )2 SO3
The secondary reaction is:

( NH 4 )2 SO3 +

1
O 2 ( NH 4 )2 SO 4
2

(2)

Ammonia reacts to NO at the same time:

2NO+4NH 4 HSO3 N 2 +(NH 4 ) 2SO 4 +SO 2 +H 2 O

(3)

The desulphurization process using the spray method is as

follows. The flue gas is transferred into the bottom of the
desulphurization tower. There are two spray nozzles placed at
two different heights on the top of the desulphurization tower.
Regardless of the fact ammonia is gas or liquid, it will react to
the sulfur oxides and nitrogen oxides homogeneously. If the
content of the ammonia is appropriate, the utilization rate of
ammonia will be more than 90%. In this case, the
desulphurization efficiency can reach 90%, 80% for
denitrification. As the by-product of amino-desulphurization,
ammonium sulfate is the raw materials of fertilizer and
chemical industry, which can bring great economic value.
However, if the process is ineffective, it can cause the waste of
liquid ammonia.
C. DOAS Measurement Principles
In this study, the principle of CEMS is based on the DOAS
[4]. Differential optical absorption spectroscopy is an
absorption spectrum method of data-processing method. The
absorption spectrum of gas will be divided into quick and slow
varying. And the quick varying is used to determine the
measured concentration of the gas. The differential absorption
is the characteristics of the absorption related to structure and
elements of the gas molecules. So the differential absorption
spectrometry can eliminate the interference of other gas
components effectively. It also increases the sensitivity and
resolution, which can provide a wider measurement range of
gases.

Source

I0

Flue gas

Id

Receiver

Figure 2. Principle of DOAS

DOAS measurement based on the principle of the two

basic gas absorption laws, Lambert - Beer's law and absorption
summation law:
A = log

I0
= lc
Id

Asum = A1 + A2 + A3 + " + An =

(4)

1C1 + 2C2 + 3C3 + " + n Cn l

(5)

in which, A is the absorbance of the gas. I0 is the original light

intensity. Id is the light intensity acquired by the receiver. C is
the concentration of the measured gas. l is the thickness of the
measured path. is the absorption cross-section.
The slow varying cross-section B() is derived by fitting
in a low-order polynomial with cross-section ( ) . Then the
cross section can be divided into two parts:

( )= B ( ) + '( )

(6)

The same method is employed to deal with the absorption,

and then the concentration of the gas is determined:

C = ln I 0 ( ) / I ( ) '/( ' ( ) L )

(7)

According to Lambert - Beer's law and absorption

summation law, the absorbance of the gases Ai can be
calculated through spectra of reference and transmission:
N

'

A '(i ) = L j j (0 , 1 , ")
j =1

(8)

In (8), L and j are known. The gas contents j need to be

calculated. Then the original optical physical properties can be
converted into computer numerical calculation. The question is
how to give a certain value to j, making a balance to (8).
Some mature fitting methods are: least squares, wavelet
transform [5] and neural network [6]. If ammonia is not
sprayed in a proper amount or the temperature of the unit is not
in the region of best desulphurization efficiency during the
desulphurization process [3], excessive ammonia will be
mixed into the flue gas. According to the absorption crosssection, ammonia bears strong absorption characteristics at the
band of 200~230nm, which means that the concentration
retrieval of SO2 will be affected.
III.

LABORATORY ALGORITHM SIMULATION

In order to study the excessive ammonia effect on the

concentration retrieval of SO2, a least-square algorithm
simulation analysis in 200~230nm band is made in laboratory
condition. Cross-sections of SO2 and NH3 used in this study
are from the database of foreign higher-solution measurement
studies. And the cross-section of NO is from self-test data in
laboratory, because NO gas absorbs less in the deep purple
band by this measurement system. It is necessary to use the
instrument adaptation of self-test cross-section to ensure the
accuracy of the concentration retrieval.
First of all, differential absorption cross-sections of the
three types of gases are calculated, as is shown in Fig. 2. And
then the mixed differential absorption is fitted followed by the
given ratio of three types of gases. This simulation assumes
that the concentration of SO2 is 1000ppm, concentration of NO
is 400ppm, and that of NH3 is 300ppm. The given
concentrations are similar to the on-site data. The mixed
differential absorption is shown in Fig. 3. Taking the three

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differential absorption cross-sections as inputs and the fitted

differential absorption as outputs, the least-square method is
used to figure out the concentrations of these three gases.

Flue gas of the stationary sources at the scene is in a very

complex environment, the flue gas emissions usually vary with
the fuel composition. As a result, the on-site spectrum shows a
variety of characteristics absorption of unknown ingredients.
To validate excessive ammonia on SO2, assume that there are
only three types of flue gas: SO2, NO, NH3.

4
2
0
-2
-4
-6
200

205

210

215
Wavelength(nm)

220

225

Data number
Trend of Data

230

Concentration of SO 2
(PPM)

Differential Absorption

1000

Figure 3. The mixed differential absorption

-17

x 10
0.5
0

500
0

-500 1

-0.5
Absorption Cross-section(count)

In order to determine whether there is an excessive amount of

ammonia, which has an impact on the measurement, the
simulated algorithm is used to analyze the on-site data.

200

205

210

215

220

225

230

205

210

215

220

225

230

Data number

-18

9 13 17 21 25 29 33 37 41

x 10

Figure 5. Retrieved value of SO2

-2
200
-17

x 10
0.5

Data number
205

210

215
Wavelength(nm)

220

225

230

Figure 4. Differential absorption cross-sections

The simulation results are shown in Table 1:

TABLE I.
Gas

Trend of Data

60
40
20
0
-20 1

4 7 10 13 16 19 22 25 28 31 34 37 40 43

Data number

SIMULATION RESULTS

Figure 6. Retrieved value of NH3

Concentration(PPM)
Standard

Not Considering
ammonia

Considering
ammonia

SO2

1000.00

1002.44

996.52

NO

400.00

984.92

398.61

NH3

300.00

298.96

Data number
Trend of Data

600

Concentration of NO
(PPM)

200

Concentration of NH3
(PPM)

0
-0.5

500
400
300
200
100

Obviously, the concentration retrieval of SO2 and NO

without taking ammonia into account are larger. The main
reason is the absorption characteristic of ammonia is mixed
with the absorption characteristics of SO2 and NO. So the
calculated concentration of SO2 and NO is larger than the
actual values. On the other hand, when the absorption of
ammonia is considered, the error of concentration retrieval of
SO2 is about 0.003%. This simulation confirms that the effect
of excessive ammonia can be eliminated effectively by leastsquare method.
IV.

ON-SITE DATA ANALYSIS

-100 1
-200

9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43

Data number
Figure 7. Retrieved value of NO

A paradigm of single time-point spectrum including 15

data before desulphurization and 28 data after desulphurization
is acquired every 3 minutes. Considering flue gas in a complex
environment, such a single point of the spectrum waveform
will be affected by the environment easily, marking instability.
So the values retrieved are far from the actual values. The
fitted concentration of three gases is shown in Fig. 5 to Fig. 7.

The laboratory simulation confirms that the effect of

excessive ammonia can be judged by least-square algorithm.

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Concentration of SO2 (mg/m3)

The fitting results show that, the value of NH3 is zero

before desulphurization, which proves that ammonia does not
exist; with the start of the desulphurization, concentration of
ammonia is rising. It can be seen from the results that, when
ammonia is taken into account, the concentration of SO2 gas
shows a downward trend after the desulphurization. It shows
that the least-square fitting method is effective to eliminate the
effect of excessive ammonia.
As to some data, the retrieved concentration is below zero.
The reason is the results are derived from the direct
mathematical calculations. Minus retrieved concentration may
indicate the measured gas, at this time, is out of the measuring
path. Because DOAS takes the average concentration of the
gas from a single straight line, the concentrations are
changeable with temperature and pressure [7].
The original concentration measured by CEMS without
taking ammonia into account is shown with the concentration
measured by portable instruments produced by Kane
Company:

Concentration of SO2 (mg/m3)

Standard
Measured by CEMS

3000
2500
2000
1500
1000
500
0
1 3 5

7 9 11 13 15 17 19 21 23 25 27
Data number

Figure 8. Concentration of SO2 measured by CEMS

It should be noted that, this acquired standard value is

not synchronized with the spectra accurately. However, it still
can provide a trend to be contrast with the data measured by
CEMS. The concentrations retrieved by CEMS are calibrated
by the standard value measured by portable instruments.
After the calibration of instruments, the results are shown in
Fig .9.
The largest error appears in the 12th data, which is near
40.3%. And the average error is 21.4%. Errors can be
attributed to the variety and uncertainty of the intermediate
products of desulphurization. Effect of excessive ammonia is
the focus in this paper. In this paper, Least squares is applied
to confirm the composition and the model of the flue gas.
And these factors are what wavelet transform and neural
network methods depend on. An in-depth study of other
factors will be considered further.

3000

Standard

2500

Calibration

2000
1500
1000
500
0

1 3 5 7 9 11 13 15 17 19 21 23 25 27
Data number
Figure 9. Concentration of SO2 after calibration

CONCLUSION
Through the algorithm simulation and processing of on-site
spectral data, its confirmed that excessive ammonia made by
desulphurization and mixed with the flue gas, can bring errors
to the concentration retrieval of SO2. The least-square method
with ammonia taken into account can be used to reduce these
errors. And after calibration by the value of portable
instruments, the concentration measured by CEMS is set at an
average error of 21.4%. If the intermediate products of
desulphurization are studied further, concentration retrieved of
SO2 will be calibrated to be more accurate. Desulphurization
process will be correctly guided to implement economic
emission reduction, and thus the plant will achieve more
economic benefits.
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