Application

Note: 42101
Total Sulfur UV-F Analysis in Gas and
LPG samples

Key Words
• EGM
• Gas
• LPG
• Liquefied gas
• Total Sulfur
Introduction
Liquefied gases like LPG are often used for fuel purposes.
Sulfur found in fuels is one of the major causes of acid
rain and around the world many countries control the
sulfur content in fuels through laws to protect
the environment.
Petroleum and chemical refining processes often rely
on a catalyst. Most of these catalysts can be poisoned by
sulfur containing components. Process feeds, half-products
and finished products in these processes may be liquid
or gas.
To analyze the total content of sulfur in gas or
liquefied gas special care must be taken to introduce the
samples in a safe and reproducible manner. Thermo Fisher
Scientific has developed the new EGM II to introduce
either gas or liquefied gas into a combustion analyzer
safely and in a consistent manner.
Although this application note describes the Total
Sulfur analysis in gas and liquefied gas, the Thermo
Scientific EGM II can also be used for Total Chlorine
analysis or Total Nitrogen analysis.
Principle of operation
The Thermo Scientific EGM II is a semi-automatic sample
introduction accessory for gas and liquefied gas. The 10-
fold rotary valve holds two sample loops; one for gas and
one for liquefied gas. This feature enables the operator to
move between gas and liquefied gas at the flick of a switch
- without the need for tools. The volumes of the sample
loops are user definable, but typically 10 mL and 100 µL
respectively. In loading position the sample gas flows
through the sample loop to the vent. The loading sequence
is controlled by the EGM II; initiated either by pressing
the purge button or as a part of the injecting sequence.
Depending on the mode (set by the gas/liquids-switch) the
corresponding venting valve is opened and the sample gas
flows through the sample loop (figure 1).
After loading the sample loop the Thermo Scientific
EGM II is ready to inject the sample into the analyzer. By
turning the rotary valve (automatically) the carrier gas
forces the sample out of the loop towards the heater and
expansion vessel. This way the gas is stabilized for pressure
and temperature and if the sample is a liquefied gas it is
vaporized at the same time. From the expansion vessel the
sample gas is fed into the analyzer to be analyzed on Total
Sulfur, Total Nitrogen or Total Chlorine (figure 2).
 liquefied gas application the EGM II has been set-up to
inject 1, 2, 3, 4 and 5 times 100 µL liquefied Butane
containing 10 mole ppm Thiophene. These injections
correspond with 10, 20, 30, 40 and 50 ppm Sulfur.

Analysis
Each calibration point is measured 3 times to illustrate the
reproducibility. Table 1 and graph 1 show the means of
the data points for the calibration line of liquefied gas.
Table 2 and graph 2 show the mean of the data points for
the calibration line of gas. Graph 3 shows the detector
response of 4 injections of liquefied Butane and Graph 4
shows the detector response of 4 injections of COS.
Figure 1. Flow scheme of the EGM II. Rotary valve is in loading position CONC AREA RSD
(mole ppm) (mVs) (%)

10 7205 2.79
20 15004 2.42
30 22017 0.23
40 29262 0.54
50 35500 1.38
Table 1. Calibration data for liquefied gas

CONC AREA RSD

(mole ppm) (mVs) (%)
1000 31991 2.44
2000 63973 0.58
3000 93258 0.62
4000 120613 0.45
5000 147854 0.24
Figure 2. Flow scheme of the EGM II. Rotary valve is in injecting position
Table 2. Calibration data for gas

Sample preparation
For this application we have chosen Liquefied Butane Gas
containing 10 mole ppm of Thiophene using the liquefied
gas mode of the Thermo Scientific EGM II. For the gas
mode we have chosen 1000 mole ppm Carbonyl Sulfide
(COS) in nitrogen.

System settings
Thermo Scientific EGM II
Temperature: 90 °C (194 °F)
Argon flow: 20 ml/min at 2.5 bar (absolute)

Thermo Scientific Total Sulfur UV-F analyzer models:

TS 3000 and SphiNCX Graph 1. Calibration curve for liquid gas
Argon: 30 mL/min
Oxygen: 300 mL/min
Oxygen turbo: 100 mL/min

Calibration
By using the automated sampling sequencing of the
EGM II a calibration curve can be easily setup with just
one calibration gas. For example, when the sampling
sequence is set at 5 the EGM II injects 5 times 100 µL of
10 mole ppm Thiophene in butane. This corresponds with
50 mole ppm Sulfur in butane. The calibration of COS
was done accordingly.
For the gas application the EGM II has been set-up to
inject 1, 2, 3, 4 and 5 times 10 mL COS giving 1000,
2000, 3000, 4000, 5000 mole ppm Sulfur. For the Graph 2. Calibration curve for gas
 Discussions In addition to these
Multiple injections in one analysis of gas or liquefied gas offices, Thermo Fisher
can be used to set-up a calibration. The response of the Scientific maintains
analyzer as a function of the number of injections is linear a network of represen-
(for liquefied gas r2 = 0.9993 and for gas r2 = 0.9994), tative organizations
proving that the automated injection sequence of the throughout the world.
EGM II is a good alternative for setting up a calibration
curve using gases with different concentrations. The
relative standard deviation (RSD) for each calibration
point is lower than 3%, which illustrates the excellent
reproducibility of the EGM II.
Africa
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Conclusions Australia
Analysis of gases and liquefied gases requires strict and +61 2 8844 9500
precise control of pressure and temperature to enable Austria
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reproducible and reliable results. Experimental data show Belgium
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reproducible and reliable introduction procedure for gases Canada
Graph 3. Injection sequence of liquefied gas +1 800 530 8447
and liquefied gases.
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The EGM II is very easy to use with both sample +86 10 5850 3588
loops available at all times. Moving from gas to liquefied Denmark
samples is as easy as turning the switch; no tools are +45 70 23 62 60
required. Setting up a calibration curve for gases or Europe-Other
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liquefied gas normally requires gases with different France
concentrations of analytes. In practice this means a +33 1 60 92 48 00
number of heavy and difficult to handle gas bottles in the Germany
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laboratory and a significant investment in calibration
India
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EGM II one can set up a calibration line using only one Italy
calibration gas in a very easy way. The calibration lines +39 02 950 591
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are linear and the reproducibility is excellent. The Thermo +81 45 453 9100
Scientific EGM II saves the hassle and reduces the Latin America
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Graph 4. Injection sequence of gas Spain
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UK
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USA
Visit www.thermo.com/ceadealers +1 800 532 4752
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