2012 International Conference on Future Electrical Power and Energy Systems

Lecture Notes in Information Technology, Vol.9

Comparison and Analysis of theTwo Methods for Determination of

Sulphur Content in the Heavy Oil
Gang Chen1,a,Wei Su2,b
1

Electric Power Research Inst. of Guangdong Power Grid Corp., Guangzhou, Guangdong, China
2

No.8Shuijungang,Dongfengdong Road, Guangzhou, Guangdong, China.

a

chengang027@126.com; bjxhwsu@163.com

Key words: Heavy oil; sulfur; comparison; analysis

Abstract: In this paper, the principles for the determination of the sulfur content in the heavy oil are
described and the two methods are compared. Under the set test conditions, we carried out the
determination on the same kind of standard oil with two methods. The F test showed that there is no
significant difference in the precision and accuracy of the two methods.
1. Introduction
In the power generation, heavy oil is usually used for ignition of the coal machines and the fuel of the
oil engine. The sulfur element in the heavy oil will produce low-temperature corrosion of equipment
and the combustion exhaust gas S O 2 will be discharged to the air to form acid rain, causing damage
to the enrolments. Therefore, an accurate determination of the sulfur content in heavy oil is of great
significance of the power generation. Since the operating procedures of the cartridge method are very
complicated with poor repeatability and practicality. In this paper, we determine the sulfur content in
the imported standard oil by the coulometric titration method and the fluorescence method; and
compare their differences with the statistical methods[1].
2. Principle
2.1 Coulometric titration method
2.1.1 Principle for determination
The coal samples are burnt in the oxygen flow under the catalyst. The sulfur in coal will form the
sulfur oxides, which will be absorbed by the KI solution to electrolyze the I 2 in the KI solution.
Calculate the content of total sulfur in the coal according to the quantity of electricity consumed [2].
According to the electric quantity consumed for the generation of iodine through electrolysis, the
mass fraction of sulfur in heavy oil is calculated according to the Faraday's law of electrolysis.
Electric quantity (Coulomb) 16 f 100
s=
%
96500(Coulomb) w
w--- mass of samples; mg f--- correction coefficient
2.1.2 Reaction formula:
Coal +O 2 S O 2 +C O 2 +NO x +H 2 O+Cl 2 +SO 3 +
Before the sulfur oxides enter the electrolytic cell, the following dynamic equilibrium exists in the
indicator electrodes [3] .
In the anode: 2I - 2e I 2 ;
2Br - 2e Br 2
978-1-61275-005-7/10/$25.00 2012 IERI

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ICFEPES2012

After the sulfur oxides enter the electrolytic cell, the following reactions will occur:
I 2 + H 2 SO 3 + H 2 O H 2 SO 4 +2H + ++2 I
Br 2 + H 2 SO 3 + H 2 O H 2 SO 4 +2 H + +2Br
2.2 Fluorescence method (Energy dispersive X-ray fluorescence spectrometry)
2.2.1 Principle
The samples are placed at the beams emitted from the X-ray. The excitation energy can be obtained
from the radioactive sources or the X-ray tubes. Then the intensity of the sulfur K characteristic
spectral line with the energy of 2.3kev is measured and compare the cumulative intensity with the
intensity of the standard products, and thus obtain the sulfur content expressed by the mass
percentage concentration.
3. Instruments and reagents
3.1 Instruments and reagents for the Coulometric titration method Instrument and reagents
ZCS - I Intelligent measuring sulfur analyzer (Analytical Instrument Factory of Xuzhou).
Reagents: potassium iodide (A.R.). Potassium bromide (A.R.), tungsten trioxide (C.R.), quartz
sand (C.R.). Molecular sieve (5A), glacial acetic acid (C.R.), distilled water.
Imported standard oil: 501-095 (sulfur content of 1.07 0.03), Standard oil 502-026 (sulfur
content of 2.05 0.03).
3.2 Instruments and reagents for the fluorescence method
QuanX-type X-fluorescence spectroscopy, Wintrace workstations and analysis software (U.S.
Thermo Electron Corporation), Chernplex XRF sample cup (U.S. Chemplex IndustriesInc.), oil
standard samples with the mass fraction of 0.51%, 1.04%, 2.02% respectively (oil standard samples
from Tokyo Chemical Industry Co., Ltd).
4. Test Conditions
4.1 Test conditions of coulometric titration method
Table 1 List of measurement parameters for coulometric titration method
Combustion
temperature

Sampling size
(mg)

1150

20--30

Injection
way
Slow
injection

Catalyst

Air flow (ml.mm-1 )

Quartz sand

1000

4.2 Test conditions of fluorescence method

Table 2 List of measurement parameters for fluorescence method
Element

Tube voltage
/KV

Tube current
/mA

optical filter

Medium

Analysis time
/s

Sulfur

12

Automatic

No

Air

100

The sulfur content analysis in the oil samples is carried out with the standard curve method. The
standard curve is plotted according to the relationship between the sulfur content and the measured
X-ray fluorescence intensity.
4.3 Test conditions for sulfur standard curve analysis
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Table 3 List of sulfur standard curve parameters for fluorescence method

Item
Sulfur content
Intensity */cs-1

S %
1.04
599.2

0.51
319.6

2.02
1136.8

* The unit of intensity is the number of X-ray photons per second

Through the Unary Linear Regression method, the regression equation of oil sulfur content is
obtained as follows:
Y=0. 001 84X---0.073 88 (1)
Where, correlation coefficient of the curve r = 0. 99995, Y is the sulfur content of the sample,%, X
is the sample pulse intensity, c/s.
5. Test data
Table 4 statistical results of imported standard oil 501-095 determined by Coulometric method and
the fluorescence method
6. Data statistics and analysis
6.1 F test on the data
6.1.1 Carry out the test of homogeneity of variances, then judge whether there is significant
differences in precision between both.
Test of homogeneity of variances:
x =1.07; y =1.08; S 1 =0.02; S 2 =0.03

S 22
=2.25; by referring to the Table: F 0.05 99=3.18; because 2.25 <3.18, there is no
S12
significant difference in precision between both.
F=

6.1.2 Calculate the combined standard deviation and determine whether there is substantial bias
between the Coulometric method and the fluorescence method.
S=

(n 1) S12 + (n 1) S 22
=0.025
n1 + n2 2
x y

n1 n2

=0.896, by referring to the Table: F 0.975 (9)=2.262; because 0.896<2.262,

S
n1 + n2
there is no significant difference between the both methods.
So, the results of the sulphur content in the heavy oil obtained by the Coulometric method are
accurate.
t=

6.2 Analysis of Results:

6.2.1 The sulfur content in the heavy oil is determined by a kind of chemical method for the
Coulometric method. Its precision depends on control over the measurement conditions. For example,
the temperature of the sample ignition, the sampling weight, and the sample injection speed, selection
of the catalyst and air flow will produce a greater impact on the test results. If the above conditions
cannot be well controlled, it will cause the detonation of samples, excessive iodine in the electrolyte
easily, and lower the test results and even test fails.
6.2.2 The test time for a single sample with the Coulometric method is about 5 minutes.
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6.2.3 The instruments are relatively cheap for the Coulometric method. Most of the instruments are
made in china, so they are easy to buy and repair, suitable for most enterprises.
6.2.4 The sulfur content in the heavy oil is determined by a kind of physical method for the
Fluorescence method; its precision depends on the calibration curve of the standard oils. The
concentration scope of the samples determined should be close to the standard oil concentration. The
instruments are easy to operate with good reliability.
6.2.5 The test time for a single sample with the Fluorescence method is about 3 minutes.
6.2.6 The instruments are relatively expensive for the Fluorescence method. The instruments are
imported from abroad, not easy to repair. The consumption of the imported standard oil is very large,
and the purchase period is long, with high costs. It is suitable for the enterprises with good economic
conditions.
7. Conclusion

7.1 Although the determination principles for the Coulometric method and fluorescence method are
different, they both can be used to determine the sulfur content in heavy oil. They are easy to operate,
and quick to test.
7.2 Under the set test conditions, there is no significant difference in precision and accuracy between
both methods.
References

[1] Zhou ZY, Li YX, Chen YM. Coal Test Statistical Techniques [M]. Beijing: China Standard Press,
2007
[2] GB / T 214-2007. Determination of Total Sulfur in Coals [s]. Beijing, China Standard
Press, .2007
[3] Gao XX. Introduction to Electroanalytical Chemistry [M]. Beijing, Science Press. 1998
About the author: Chen Gang, Male, 44 year-old, Hubei Huanggang, Senior Engineer, he is engaged in fuel management
for many years and published many thesis. E-mail/:chengang027@126.com

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