1. business and industrial
2. energy
3. natural gas

micro Process Gas Chromatograph (PGC) analyses
with Sample Conditioning
by drs ing Tim Lenior
Analytical Solutions and Products BV
July, 17 2012
Analytical Solutions and Products BV
Contents:
1
Introduction to process analyses .......................................................................... 5
1.1
Micro Process Gas Chromatography (µPGC) ............................................................5
1.2
Research and theoretical aspects (2) .........................................................................6
1.2.1
1.2.2
1.2.3
1.2.4
1.2.5
1.2.6
1.3
Applications (8) (9) .....................................................................................................19
1.3.1
1.3.2
1.3.3
1.3.4
1.3.5
1.3.6
2
The essential steps in process analyses .................................................................27
Sample handling and integration back ground information .............................. 28
3.1.1
3.1.2
4
Further developments in sample handling (NeSSI™) (22)....................................................30
Integration of equipment in process plants a slim analyser package (aSAP) (9) ..................31
Discussions and Conclusions ............................................................................. 32
4.1
5
Natural gas & Liquified Natural Gas LNG ..............................................................................19
RGA, Cokes gas Analyses ....................................................................................................20
Sulfur analyses (9) (14) .........................................................................................................20
Syngas analyses (18) ............................................................................................................23
Biogas & Biomass analyses ..................................................................................................23
Environmental analyses (20) .................................................................................................24
From process sample to process control ........................................................... 26
2.1
3
µGC and narrow – medium bore columns ...............................................................................6
Micro-Injection (2) ..................................................................................................................12
The µTCD and the detection limit (4) (6) (2) ..........................................................................12
The minimum detectable amount (2) .....................................................................................15
The µGCs discussed and used for the LNG Probe tests ......................................................16
Description/explanation of the Agilent 490-GC µGC: ............................................................16
Further discussion for process analysis ..................................................................32
References ............................................................................................................. 34
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List of figures:
Figure 1: plate heights vs carrier gas velocity (2) ..........................................................................................6
Figure 2: analysis time vs column ID (2) .......................................................................................................7
Figure 3: plate hight equation & the van Deemter H vs u curve (2) ..............................................................8
Figure 4: efficiency packed vs. capillary column (2)......................................................................................9
Figure 5: plot of time H/u vs required plate number (5) ................................................................................9
Figure 6: carrier gas velocity u vs column ID (2) .........................................................................................10
Figure 7: PLOT Columns application Areas (2) ..........................................................................................10
Figure 8: adsorption and absorption GC (2) ................................................................................................11
Figure 9: thermal conductivity of gases (2) .................................................................................................12
Figure 10: Thermal Conductivity Detector (TCD), the Wheatstone Bridge configuration ...........................13
Figure 11: plot of minimum detectable concentration, Co, against column diameter dc , for n-C7 on a FID
and µTCD (6) ...............................................................................................................................................14
Figure 12: column diameter speed and detection limit (2) at the same injection volume (2) ......................15
Figure 14: Agilent 490-GC micro-gaschromatographic system ..................................................................16
Figure 13: Agilent 490-GC µGC system ......................................................................................................16
Figure 15: sample & inject on the chip injector ...........................................................................................17
Figure 16: etch pattern of the micro machined injector (7) .........................................................................17
Figure 17: portable Zone 2 uGC courtesy of ASaP BV ...............................................................................18
Figure 18: stationary process uGC for ATEX Zone 1. courtesy of ASaP BV ..............................................18
Figure 19 New LNG probe design ...............................................................................................................19
Figure 20: Cokes Gas Analyses ..................................................................................................................20
Figure 21: Lemon yellow Sulphur crystals ..................................................................................................20
Figure 22: Emissions of SO2 in 25 European countries in 2004 . ...............................................................21
Figure 25: Stability and step test for 3 to 0.5ppm H2S on a µTCD..............................................................22
Figure 23: Sulphur melts to a blood-red liquid. When burned, it emits a blue flame and forms SO2 from: S
+ O2 -> SO2..................................................................................................................................................22
Figure 24: 5.8ppmv H2S LOQ 0.5 ppmv on a µTCD ...................................................................................22
Figure 26: ASaP standalone Biogas Analyser ............................................................................................23
Figure 27: Column 4m CPSil5 CB ...............................................................................................................24
Figure 28: Column 10m WAX 52.................................................................................................................24
Figure 29: the steps from process sample to process control ....................................................................26
Figure 30: from process sample to process control, the P&ID ....................................................................27
Figure 31 Genie Retractable Probe Regulator Model GPR with integrated membrane (courtesy of Genie
inc.). .............................................................................................................................................................29
Figure 32: standardized building block for the NeSSI platform (courtesy of Circor Tech) ..........................30
Figure 33: a sample handling system on the NeSSI platform (courtesy Circor Tech) ...............................30
Figure 34: all steps from sample take-off to analysis integrated in one 3D probe (courtesy of EIF) ..........31
Figure 35: on pipeline installation including side platform ...........................................................................31
Figure 36: a Slim Analyser Package (aSAP), the back wall is transparent for illustration ..........................31
Figure 37 a µGC integrated into a Process (ATEX) certified µPGC and an aSAP analyser package .......32
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List of tables
Table 1: sample capacity and film thickness (2) .........................................................................................11
Table 2: thermal conductivities of some components and carrier gas He ..................................................18
Table 3: Repeatability for 1-3ppm H2S on a µTCD (17) ..............................................................................22
Table 4 Micro GC Column Modules ............................................................................................................25
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1
Introduction to process analyses
In a history overview of Gas Chromatography (GC) in the petrochemical industry (1) it was stated that,
after GC was introduced by James and Martin in 1952, GC was well established within the petrochemical
industry already in 1956. Since that time part of the GC has evolved from the laboratory into the process
environment. Analytical techniques and in particular GCs are used in process plants to determine product
quality & yield and GC is used as a guarding technique to protect essential process operations. Such as
the protection of catalyst in a reactor against contaminants. Industrial processes are operated by process
control systems. The process control system operates based on the measurement of physical properties
and composition of the product. The composition of the product is mainly determined in the laboratory.
Laboratory analyses are done within hours. Such measurement timeframe can have a negative impact on
the process plant’s throughput and product quality. An upset condition at the front may results in an offspec condition at the output when not quickly corrected. Therefore fast analyses are required. Some of
these analyses are performed on-line in the plant at different critical points in the process. This will speed
up the measurement and the operation of the plant, resulting in a better control of product specification.
Installing on-line analytical instruments will also minimize the errors that are introduced when taking
manual samples. Eventually on-line process analyses will result in the increase in the plant’s product yield
and in the return on investment of the analytical system. It is not a matter of how much an on-line
analytical system cost but how much money the implementation of an on-line process analyses can
make, by the product quality and yield improvement!
1.1
Micro Process Gas Chromatography (µPGC)
Micro Gas Chromatography (µGC) is a development that can be used for fast process analyses. µGCs
are fast due to the use of narrow and medium-bore columns. Second size and separation power of µGCs
allows it to be used for fast analysis and integration in a process plant. Moreover, for a number of
practical reasons it is an advantage to miniaturize the equipment for process analysis. Those practical
advantages are:
 close mounting to the sample take-off point
 lower amounts of sample gas needed
 lower transfer times of the samples
 shorter delay times for analyser results
 low energy and utility consumptions
 easier explosion proof (ATEX, CSA) integration
 increased reliability (24/7) operation
 increased precision and accuracy
Apart from the practical aspects of µGC technology this chapter will focus on the theoretical aspects of
µGC technology and in particular Micro Process Gas Chromatography (µPGC).
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1.2
Research and theoretical aspects (2)
In Chapter 1.1 the advantages of µGC technology was discussed, here the theoretical background about
the µGC technology will be discussed. This paragraph describes the background of narrow and medium
bore columns, micro-injector and micro thermal conductivity detector (µTCD).
1.2.1 µGC and narrow – medium bore columns
GC is a commonly used technique for compositional gas analysis. These measurements generally take
place in the laboratory. Analysis times of 10 minutes to one hour is normal. In a process environment
much faster analyses are required for the purpose of control of the subsequent processes. Analysis times
of 30 seconds to a few minutes are required for process analysis. The advantage of µGC are, besides the
reduction in size of the instrument, speed and their detection limits. µGC technology uses narrow to
medium bore capillary and micro packed columns. These columns in combination with an appropriate
detector results in faster analysis and lower detection limits. This was described by Thijssen et al (3) in
1987 and Cramers et al in 1999 (4). It is an improvement compared to conventional GC techniques.
Theory behind this describes (4) that the reduction of the characteristic diameter, being the inside of the
column diameter for open tubular columns and the particle size for packed columns, is the best approach
to increase the separation speed in gas chromatography (Figure 2). Hydrogen and Helium carrier are the
best choice for higher carrier gas velocities. Lowest plate height (HETP) is achieved for N2 in the
optimum for the carrier gas velocity but when increasing the carrier velocity through the column Helium
and Hydrogen give lower plate heights as can be seen in below figure.
Figure 1: plate heights vs carrier gas velocity (2)
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Reduction of the inside column diameter results in a reduction in analyses time as displayed in below
figure.
Figure 2: analysis time vs column ID (2)
A few reasons of the reduction of the total analysis time as described by (4) are:
1) Reduction of the characteristic diameter being the inside column diameter for open
tubular columns and the size of particles for packed columns is the best approach.
The equilibrium between mobile and stationary phase is faster for narrow bore columns
due to the relative distance for the molecules to get from the mobile to stationary phase.
2
Analysis time can be reduced proportional to characteristic particle diameter dp and
2
column diameter dc for respectively packed r capillary columns for p=1barg and linear
proportional to dp or dc for p>>1barg.
2) Also the film thickness is of some influence. In thin-film the Cs-term in the simplified Golay
equation (Figure 4) can be neglected.(e.g. df=0.4µm)
3) The influence of carrier gas type due to the diffusion coefficient and carrier gas viscosity
is 60% worse for He compared to H2 (smaller molecule H2 compared to He). H2 is
therefore the best choice. (for safety reasons He is often chosen in process analyses)
4) Temperature programming, higher temperature gives lower retention (10-15 C higher =2x
lower retention). Temperature programming should be ultra fast for narrow bore columns.
5) Multiple capillary columns : 919 coated capillaries ID40 um 1m length, high sample
capacity, fast due to the 919 parallel capillary columns. e.g. aromatics up to
o-xylene in 0.8 minutes.
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The van Deemter equation expresses the relation between the plate height (H) and the gas velocity
through the column (u).
Figure 3: plate hight equation & the van Deemter H vs u curve (2)





H = HETP (plate height)
A = eddy diffusion term
B = longitudinal diffusion term
u = linear gas velocity
C = resistance to mass transfer coefficient
The terms A, B and C will influence the plate height and eventually the separation efficiency Nth. For
narrow and medium bore columns in respect to wide bore or mega bore columns:




A is smaller due to relative smaller particles in packed columns.
B/u is smaller because the relative smaller travel distance of the molecules.
C is relative smaller due to the smaller relative distance of the molecules from the mobile to the
stationary phase.
For thin films the Cs term can be neglected and consequently the plate height will decrease
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For capillary columns the A term in the van Deemter equation, representing the column packing flow
pattern will disappear due to the absence of column particles.
Figure 4: efficiency packed vs. capillary column (2)
Ultra narrow bore columns with diameters < 100 µm are not advised, because they generate high
pressure drops and have very limited loading capacity.
An alternative way of presenting the van Deemter equation as proposed by (5) is the time equivalent to a
theoretical plate (TETP) as displayed in below figure. The curves for different particle size, or column
diameter are displayed in the figure and the required plate number in the shortest possible time can be
obtained.
Figure 5: plot of time H/u vs required plate number (5)
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Carrier gas flows through narrow- and medium bore columns are increased as the column diameter
decreases.
Figure 6: carrier gas velocity u vs column ID (2)
This has a positive effect on the longitudinal diffusion term B/u and negative effect on the C*u term. The
3
sample capacity is reduced proportional to d c for narrow bore open tubular columns (4) (with dc the
column diameter). Therefore the selection of columns with larger diameter (medium bore) will have a
positive effect on sample capacity and the minimum detectable quantity.
The columns used by Agilent as described in 1.2.6 consisted of a Pora PLOT Q (PPQ) column .Porous
Layer Open Tubular (PLOT) columns are open tubular columns coated with a layer of solid porous
material on the inside column wall.
Figure 7: PLOT Columns application Areas (2)
Porous polymers are prepared by the copolymerization of styrene and divinylbenzene or other related
monomers. The silicon chip column consists of etched channels with a size of 0.3mmx550mm packed
with carbon spheres of 1.3nm.
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Other columns used by Agilent as described in 1.2.6 consists of a non-polar CPSil5 liquid phase (df=5µm)
Also the sample capacity will increase with the column’s liquid phase film thickness (ref. Table 1).
Table 1: sample capacity and film thickness (2)
Sample capacity of capillary columns (in ng per component)
ID (mm)
0.15
0.25
0.32
0.53
0.12 μm
1 - 10
2 - 50
5 - 100
-
0.40 μm
3 – 30
6 - 150
15 - 400
-
1.2 μm
10 - 100
20- 500
50 - 1000
50 - 1200
2.0 μm
30 - 800
80 - 1500
100 - 2000
5.0 μm
200 - 5000
Chromatography is a physical method of separation in which the components to be separated are
distributed between two phases, one of which is stationary (stationary phase) while the other (the
mobile phase) moves in a definite direction. If the stationary phase is a liquid phase the analyte
molecules must dissolve in that liquid stationary phase and their separation is based on absorption . For
the PLOT and carbosphere column type, separation is based on the adsorption of analyte molecules on a
solid stationary phase.
Figure 8: adsorption and absorption GC (2)
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1.2.2 Micro-Injection (2)
To minimize the contribution of the input band-width (Agilentce) to total band-broadening, the injected
sample plug has to be narrow in comparison to the total chromatographic band broadening. In case of
faster analyses the residence time of the components in the column is reduced. This results in a reduced
chromatographic zone widening (i.e. the peak widths σw are reduced). Injection hence becomes more
critical. This is especially true for isothermal analyses. In temperature programmed separations zone
focusing will occur in the column inlet.
The theoretical value for the contribution of a plug injection to band-broadening (isothermal column
operation) is given by (6):
where w is the width of the injected plug. Extreme small injection band-widths (σi) are required for very
fast analyses on short narrow bore columns are approximately 1-3 ms (6). For the narrow bore option for
fast GC the injection band-width is critical. It is for this reason that the development of injection systems
compatible for narrow bore GC has received considerable attention in literature. For narrow and medium
bore columns, for the µGCs used in this paper, the injection time frame is between 10-100ms. In two of
the µGCs described in this paper a chip injector was used (explained in more detail in paragraph 1.2.6).
Decreasing the injector volume could result in discrimination in the injector due to differences in viscosity
of the sample components in the injector .
1.2.3 The µTCD and the detection limit (4) (6) (2)
The thermal conductivity detector (TCD) is a universal detector based on the measurement of the thermal
conductivity of a gas. The TCD measures the difference in heat conductivity between pure carrier gas and
carrier gas containing sample components.
The core of the TCD is a filament, a thin wire often made of tungsten, platinum or nickel. Since the
resistance of this filament is dependent on its temperature, a change in temperature will result in a
change in resistance. This change can be detected electronically.
The thermal conductivity of the carrier gas and the analyte influence the peak signal. If the conductivity of
the carrier gas is higher than that of the analyte, this results in a positive peak. The bigger the difference
in conductivity of analyte and carrier gas, the better the heat transfer and results.
Figure 9: thermal conductivity of gases (2)
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Detection principle:





A TCD usually has a double channel system. Pure carrier gas flows through one channel, the
carrier gas eluting from the column containing the sample components flows through the other
channel.
Electrically heated filaments in each channel are cooled by the carrier gas. The amount of heat
loss is a function of the thermal conductivity of the gas flowing through the cell.
Both resistance filaments are part of a Wheatstone bridge. The bridge is in equilibrium if the
composition of the gases is the same. The composition of the gas flowing through the reference
cell does not change.
A sample component passing the detector will change the composition of the gas. This results in
a change in conductivity which, in turn will distort the balance. The resulting signal will be passed
to the data recording system.
The detector has the highest sensitivity when the difference in thermal conductivity between the
carrier gas and the sample components is large. This is mostly the case with the lighter carrier
gases, such as hydrogen and helium (the exception is when He and H2 need to be measured).
Figure 10: Thermal Conductivity Detector (TCD), the Wheatstone Bridge configuration
The µTCD is a solid state detector (SSD) it consist of 4 silicon micro machined air bridges (two each
suspended in discrete parallel gas flow channels) coated with a metal filament, which, is heated. These
are arranged in a wheatstone bridge configuration. Its volume is only 200nl. Its dynamic linear response
spans 6 decades covering a concentration area from 1 ppmv to 100%v.
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The µTCD’s concentration limit can exceed that of the Flame Ionisation Detector (FID).
Figure 11: plot of minimum detectable concentration, Co, against column diameter dc , for n-C7 on a FID and
µTCD (6)
From this plot it follows that for column diameters below 135µm the application of the µTCD becomes
increasingly advantageous in comparison with the FID (6). Reduction of column diameter requires a
2
2
2
2
reduction of the total band-width (Agilentce) σt (σt = σi + σc + σd with i for injector, c for column and d
for detector). For the detector the band broadening depends on detector volume and flow. Reducing the
column diameter results in a reduction of the allowed detection volume.
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1.2.4 The minimum detectable amount (2)
The minimum detectable amount (Q0), i.e. the lowest quantity of solute that can be distinguished from the
noise, is given by:
Where Rn is the detector noise, S the detector sensitivity, σt is the total band-width and Fd the total flow
through the detector. The minimum detectable amount is favoured by a reduction of the inner diameter
(The minimum detectable amount is proportional to the column diameter, Leclercq and Cramers, 1998)
and basically by any other method that results in faster analysis. This is caused by the decrease of σ t
when the analysis time is reduced. The minimum detectable concentration on the other hand however, is
not always improved when methods for faster chromatography are implemented. The injection volume
might have to be reduced to avoid an excessive contribution of the injection to the overall peak width
resulting in higher detection limits. Whereas this effect is marginal for most of the options for faster
analysis, the minimum detectable concentration decreases dramatically when working with columns with
a reduced inner diameter. Narrow bore columns therefore are not suitable for trace analyses. Also
detectors have to be very sensitive to detect the low quantities eluting from a narrow bore column.
Figure 12: column diameter speed and detection limit (2) at the same injection volume (2)
The time constant of a detector (e.g. effects of resistance and capacitance in the detector electronics)
will contribute to peak broadening and noise. Increasing by digital filtering will reduce noise and will
have a positive effect on the detection limit (6). The peak width and time constant of a detector must be
matched. A relative too fast detector may introduce unwanted noise while a relative too slow detector
could result in peak deformation. For narrow bore columns the time constant for a detector should be
relative small (fast enough detector and electronics) in comparison to a detector for normal bore columns
in order to follow the fast chromatography.
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1.2.5 The µGCs discussed and used for the LNG Probe tests
The µGC further discussed as used process µGCs the Agilent µGC 490-GC
1.2.6 Description/explanation of the Agilent 490-GC µGC:
Agilent Inc. is a company supplying analytical laboratory equipment. One of their products is the 490-GC
th
µGC. It is the 4 generation of µGC products which was first developed in the 1970s. The µGCs consists
of an injector, column and a detector installed in different small temperature controlled compartments.
The unit uses precisely electronic pressure controlled carrier gas
to run the injected sample gas of interest through the analytical
column. The system can be configured of 1 – 4 channels. Each
channel consist of a carrier pressure controller and a module
which holds the injector, column and detector. Furthermore the
instrument consists of a set of electronics and a computer in order
to automatically control the different parts.
Figure 13: Agilent 490-GC µGC system
CHIP
INJECTOR
MICRO EGC
GC
COLUMN
MICRO TCD
Injector
TCD-detector
Sample in
Heated to110C
column in
Pre- column
Heated to110C
Reference
in
Analytical System
column
flow
µTCD
Analyticalcolumn
Carrier in
injector
-
Heated to180C
Reference
flow
heated
Sample out Backflush
vent
Carrier Bottle
or
bombe in fieldcase
Figure 14: Agilent 490-GC micro-gaschromatographic system
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In the column, which is isothermally controlled, the injected sample gas is separated into its individual
components based on their order of boiling point (non-polar columns), polarity (polar-columns), or
molecular size (mol-sieves columns). The columns used are narrow (0.15mm) and medium bore columns
(0.32mm). As displayed in the above diagram the analytical system also features a pre-column. This precolumn provides the functionality to pre-separate the sample. This is done to allow only the components
of interest to flow into the analytical column, thus speeding up the system. But also to prevent the
analytical column to be contaminated with the components of non interest. e.g. the protection of a molsieves column from the components CO2 and H2O. Those components would drastically decrease the
separation of the other permanent gasses as N2, O2 and Ar. CO2 and H2O will fill up the pores of the
material and will consequently decrease the separation power of the total column since the molecules of
Ar, O2 and N2 cannot penetrate the pores anymore and will flow un-retained through the column without
separation. Other µGC manufactures use different approaches to overcome this problem (e.g. by
temperature programming).
Figure 15: sample & inject on the chip injector
Figure 16: etch pattern of the micro machined injector (7)
The carrier gas helium is often chosen. Helium is second best after H2 for high speed analysis (HETP
lowest at high speeds) but has the advantage being nonflammable. It is a non-flammable inert gas which
will transport the separated and measured components through the analytical column. At the outlet of the
column the carrier gas, together with the separated components, will elute into a micro thermal
conductivity detector (µTCD) detector . At this stage the components are measured, based on their
difference in thermal conductivity with respect to the carrier gas (again He is second best after H2 in
conductivity), and quantified measuring their area as it is digitized. The µTCD is a universal detector and
will therefore measure all eluted components. The µTCD (ref. paragraph 1.2.3 for theoretical aspects) has
a volume of 200nl and a limited quantity of detection of one to a few parts per million (ppm). The system
can be equipped with a second detector in series with the µTCD to analyse the components to a relatively
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much lower limit of quantification (LOQ). However, this detector is a selective detector and is limited in
determining all components. A combination of the two detectors may produce the required detection
results. This detector will be used and further explained in paragraph Fout! Verwijzingsbron niet
gevonden..
Table 2: thermal conductivities of some components and carrier gas He
Thermal conductivities λ @ 1.013 bar, 0°C
Component λ [mW/mK]
Helium
142.64
CH4
32.81
CO2
14.65
H2S
12.98
delta λ vs He
0
109.83
127.99
129.66
Integration on a process instrumentation platform:
Two examples of the integration of the Agilent µGC in a portable Zone 2 and Stationary Zone 1 cabinet
for on-line installation is displayed below.
Figure 17: portable Zone 2 uGC courtesy of
ASaP BV
Figure 18: stationary process uGC
for ATEX Zone 1. courtesy of ASaP
BV
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1.3
Applications (8) (9)
A number of applications can be addressed as interesting in the area of Process Gaschromatography.
Where speed and complexibility is an advantage over conventional equipment. The process environment
uses a broad range of analytical equipment and in particular the Gaschromatograph. Due to its general
employability and compositional analyses it is a preferred technique in this area. As described in chapter
1.1 the uGC has advantages for use in a process environment. These are some examples how and
where they are used.
1.3.1 Natural gas & Liquified Natural Gas LNG
Natural gas is bought and sold as a bulk commodity with price based on its energy content. It is very
important to accurately determine the heating value/calorific value of natural gas as well as quantify
individual components of the streams. The Agilent Micro GC Natural Gas Analyzer (NGA) is a 2 channel,
multi-dimensional system based on the 490 Micro GC. Each channel includes a micro-machinedcapillary
column, and thermal conductivity detector enabling very fast analysis cycle times (typically less than 60
seconds). (ISO 6976 (10), ASTM D3588, GPA 2286 and GPA 2172)
Natural gas is a major source of energy, but many towns and cities that need the energy are located far
from the gas fields. Transporting gas by pipeline can be costly and impractical. Shell (11) creates LNG by
cooling the gas to a liquid at around -160ºC, which they can then ship out, safely and efficiently.
LNG is a clear, colourless, non-toxic liquid that can be transported and stored more easily than natural
gas because it occupies up to 600 times less space.
When LNG reaches its destination, it is returned to a gas at regasification facilities. It is then piped to
homes, businesses and industries.
Shell (11) helped pioneer the LNG sector, providing the technology for the world's first commercial
liquefaction plant at Arzew, Algeria, in 1964. Since then, Shell (11) has continued to improve the
technology behind LNG.
(12) Next to metering of the flow, composition analysis of LNG contributes to the correct fiscal accounting
of LNG movements. The basic function of the sampler is to take a representative sample from liquid
natural gas and vaporize this integrally for analysis by (micro-)GC (or other
analytical equipment) or to fill a sample cylinder for transport to the lab with
subsequent lab analysis. The requirements are fixed in (13). Having
followed this standard there still is a too large uncertainty in the analysis
results, even when the sampling is restricted in this standard to periods
where the LNG transfer is at a stable (maximum) rate.
The analysis’ performance itself is not questioned; it is the sampling method
that causes the deviation. The main problem in sampling is the sample
transport in the liquid phase from take-off to vaporisation step and a total
instant vaporisation of the LNG to the gas phase to prevent discrimination
of the sample. In present new design the vaporizer is integrated in the
sample probe and as such has no external liquid sample transport.
Moreover, a maximum of sub cooling (as specified in the a.m. ISO) is
provided. Tests on the new design sampler showed immediate, accurate
analysis on start of the loading. The measured relative standard deviation
of the results was better than 0.17%RSD based on a composition of CH4,
C2H6 and C3H8.
Figure 19 New LNG probe design
Impurities in Natural gas are present in low concentrations (i.e. H2S, COS H2O, MeOH). Pipeline
specifications dictate the maximum amounts allowed. The control and protect the levels present analysis
is required.
On the other hand since Natural gas is odourless small quantities of thiols (mercaptanes) derivatives are
added to the gas.
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Precision, speed and low ppm quantification is required of the substance and composition of the Natural
gas. In the referred applications this is achieved by uGC analyses. The analyses and the calculation of
the heat values are fast to acquire as much information as possible and protect the process from
impurities. The µPGC is able to deliver such speed and precision. Heat values are calculated according
the above mentioned standards
Reference:
ref: Agilent Technology application notes 5991-0275EN, 5990-8250EN, 5990-8528EN, 5990-8750EN (14)
& Analytical Solutions and Products BV: (9)
1.3.2 RGA, Cokes gas Analyses
The source and composition of refinery gases varies considerably. Measuring gas composition precisely
and accurately is a significant challenge in refinery operations. The Agilent Micro GC Refinery Gas
Analyzer (RGA) is a 4 channel, multi-dimensional system based on the 490 Micro GC. Each channel
includes a micro-machined injector, capillary column, and thermal conductivity detector optimized for
specific RGA analytes, with total analysis cycle time of less than three minutes. The small system volume
means the sample capacity is reduced in comparison to standard GC RGA systems and is more suitable
for sample streams with low sample component concentration such as typical refinery gas streams and
impurities in bulk ethylene.
In Cokes gas the application is similar but more impurities may exist is the process gas. One example is
given here. The analysis of Naphthalene and H2S:
Reference:
Figure 20: Cokes Gas Analyses
Agilent Technologies application note(s): SI-02233, SI-02235
Analytical Solutions and Products BV: (9)
1.3.3 Sulfur analyses (9) (14)
The analyses of sulphur containing components in the different industrial gasses is
a widely used measurement in the industrial environment. Sulphur is present in
raw energy products when extracted from its sources for processing. Crude oils,
raw coal and natural gas sources all contain sulphur in different concentrations
and structure. Before crude oils are distilled in refineries or when coal is converted
for the use of fuels, the sulphur is first removed from the raw feed streams. H2S
and in a lesser degree organic sulphur is formed during these conversion and
treating steps. When natural gas is extracted from their sources the gas is treated
Figure 21: Lemon
yellow Sulphur crystals
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in gas treating plants before use as an energy source in industries or households. The H 2S, COS and
other organic sulphur in the gas are removed from the raw material. The importance of the removal of
sulphur from the mentioned (energy) sources can be found in a number of reasons as the toxicity,
corrosion and environmental pollution that will be caused by sulphur containing components.
The methods for the measurement of H2S, COS and other organic sulphur are very broad. The analytical
methods used is first dependent on the range and composition of the gas. Second the analytical
technology available at the time of choice plays a role in the selection. Over the last decades new
analytical techniques are developed and have become available for the measurement of the sulphur
containing components.
The emission of sulphur will be in the form of sulphur oxides after burning as SO2 or SO3 indicated as
SOx. The emission of the sulphur oxides among other pollutants is restricted in Europe. The European
Union states: To maintain or improve the quality of ambient air, the European Union has established limit
values for concentrations of sulphur dioxide, nitrogen dioxide and nitrogen oxides, particulate matter and
lead, as well as alert thresholds for concentrations of sulphur dioxide and nitrogen oxide, in ambient air.
The alert threshold laid down in Directive 1999/30/EC is 500 µg/m³ measured over three consecutive
2
hours at locations representative of air quality over at least 100 km or an entire zone or agglomeration,
whichever is the smaller (15).
The emitted SO2 by only the 25 European countries’ industries was approximately 5,114,779 ton in 2004
(2004 data (16)), the power and refinery industry are the largest producers of SO 2.
Figure 22: Emissions of SO2 in 25 European countries in 2004 .
Therefore industrial companies have to restrict the amount of H2S and
other sulphur containing components exhausted to the incinerators and
vented as SO2 to the atmosphere. To control the emissions of the
components analytical measurements are necessary. When regulations
from governments limit the amount of pollutants, there must a way to
measure and control this. This literature thesis will focus on the literature about the analyses of sulphur
containing components and in particular SO2, H2S and COS in Flue gas, Fuel gas and Natural gas in a
industrial environment.
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Figure 23: Sulphur melts to a
blood-red liquid. When burned,
it emits a blue flame and forms
SO2 from: S + O2 -> SO2
New developments over the last decade allow the detection of sulphur using new detectors. The
detection of SO2, H2S, COS and CH3SH in a range from 500ppbv to 5ppmv in hydrocarbon gasses could
be achieved using a µGC in combination with the micro-Thermal Conductivity Detector (µTCD) and a
Pora PLOT U column quantification limits of 0.5 ppm H2S in Natural Gas could be achieved with a 2-8%
repeatability in the 1-3ppm H2S range.
Figure 24: 5.8ppmv H2S LOQ 0.5 ppmv on a µTCD
Table 3: Repeatability for 1-3ppm H2S on a µTCD (17)
H2S Conc
3ppm
2ppm
1ppm
%RSD
2-3%
3-4%
8%
Figure 25: Stability and step test for 3 to 0.5ppm H2S on a µTCD
Reference Analytical Solutions and Products BV: (9) (14)
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1.3.4 Syngas analyses (18)
Gas To Liquids (GTL) conversion is an umbrella term for a group of technologies that can create liquid
synthetic fuels from a variety of feed stocks like natural gas, biomass and coal. The basic technology was
developed in Germany in the 1920s and is known as the Fischer-Tropsch process after its inventors. In
essence it uses catalytic reactions to synthesize complex hydrocarbons from simpler organic chemicals.
This process can create identical liquids from a variety of feed stocks, although the technical challenges
are greater for biomass and coal.
The Shell middle distillate synthesis process (SMDS) process (19):
The Shell middle distillate synthesis process (SMDS) is a proven technology to convert hydrocarbon gas
to liquid fuels. The SMDS process uses natural gas as a feedstock. Natural gas produced at remote
locations where it is not directly used or necessary for direct energy consumption (in most cases the gas
is simply burned off, or “flared.”) is ideal for the conversion into heavy paraffin’s by the SMDS process. It
is transferred into ultra clean products. The main use is clean fuels and in particular gasoil (diesel). The
produced fuels are free from sulfur and aromatics. But other products produced are FDA-approved, foodgrade waxes (the waxes are used in chewing gum, cosmetics and medicines).
Impurity analyses (9)
The described process uses large amounts of high value cobalt (Co) or iron (Fe) catalyst. Low
concentration contaminant like the before mentioned HCN poison, will deactivate the catalyst. Therefore
expensive absorbers are used to prevent any of the contaminants from reaching the process vessels in
which the catalyst is stored. The absorbers, which are also installed in high-volume vessels, are
expensive pieces of process equipment. The µPGC analytical technique described in this paper is an
economic solution for this problem. It is a small and relatively inexpensive piece of equipment that can be
installed at various points in the process to monitor the contaminants.
Reference:
Agilent Technologies application notes: 5990-7054EN
Analytical Solutions and Products (9)
1.3.5 Biogas & Biomass analyses
Biogas, a renewable and sustainable energy source, is produced through biological processes like
anaerobic fermentation or digestion of organic material. The main components of biogas are methane
(CH4) and carbon dioxide (CO2), with some other permanent gases, hydrogen (H2) and hydrogen sulfide
(H2S). The exact composition of the biogas is related to the origin of the organic material. To increase its
caloric values, it can be necessary to remove some CO2 or blend it with other hydrocarbon streams.
To tie into the existing natural gas network the gas must
comply with the required specification and should not
disturb the composition in the pipeline.
Biomass has been recognized as a potential renewable
and sustainable energy source. The Delft University of
Technology researches the gasification of woody and
agricultural biomass in a Circulating Fluidized Bed Reactor.
The Agilent 490 Micro GC is used to characterize the
product gas using a COX column for the permanent gases
and a CP-Sil 5CB for the BTX compounds.
Speed and precision is required in order to reach this goal.
µPGC is able to do such required analysis.
Analytical Solutions and Products BV
Figure 26: ASaP standalone Biogas Analyser
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Reference: Agilent Technologies application note(s):
5990-8069EN, 5990-7054EN, 5990-8529EN, SI-02215, 5990-9508EN Analysis of Biogas, 5990-9517EN.
Analytical Solutions and Products (9)
1.3.6 Environmental analyses (20)
For this analyses of the contaminants in a soil sample by means of a steam injection. Steam injection is
used with the objective: soil decontamination.
The sample contains contaminants in high concentrations of ambient air and moisture (gas phase).
The sample is drawn from a ground location and handled by a processing plant.
Figure 27: Column 4m CPSil5 CB
Figure 28: Column 10m WAX 52
Low and precise analyses are required to control and report the soil cleaning process. µPGC is able to do
such required analysis
Reference:
Agilent Technologies application note(s): 5990-8361EN, BTEX 5990-9527EN.
Analytical Solutions and Products (9)
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Column/Phase
Type
Target Components
Molsieve 5•
Permanent gases, methane, CO, NO,etc. (H.R. for O2-Ar baseline separation). Optional Retention Time
Stability (RTS) configuration.
Hayesep A
Hydrocarbons C1-C3, N2, CO2, air, volatile solvents
CP-Sil 5 & 8 CB
Hydrocarbons C3-C10, aromatics, organic solvents
CP-Sil 19 CB
Hydrocarbons C4-C10, high boiling solvents, BTX
CP-WAX 52 CB
Polar higher boiling solvents
PLOT Al2O3/KCl
Light hydrocarbons C1-C5 saturated and un-saturated.
CP-PoraPLOT U
Hydrocarbons C1-C6, Freons, Anesthetics, H2S, CO2, SO2, volatile solvents
CP-PoraPLOT Q
Hydrocarbons C1-C6, Freons, Anesthetics, H2S, CO2, SO2, volatile solvents
CP-COx
CO, CO2, H2, Air, CH4
THT column
THT and C3-C6+ in Natural Gas Matrix
TBM column
TBM and C3-C6+ in Natural Gas Matrix
CP-PoraPLOT
Specially tested for H2S in natural gas (10 to 50 ppm)
MES column
Unique column specially tested for MES in natural gas (1 ppm)
Table 4 Micro GC Column Modules
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2
From process sample to process control
Often the focus is on the analyses itself while 90% of failures with process analyses occurs in the sample
handling and treatment. When fast analyses are introduced the speed of sample handling should be
adjusted accordingly. On-line process analyses requires a number of essential steps to make it
successful. It covers the steps from the process sample take off to the transfer of the results to the
process control system, which, in its turn operates the plant to the correct sample quality and yield.
The steps from process sample to process control are:
1.
2.
3.
4.
5.
6.
7.
The sample take-off from the process pipe/vessel
The sample pre-conditioning
The sample transport
The sample conditioning and handling including calibration
The sample analysis
The sample data processing, and finally
The feedback of the results to the process control system
Process
Plant
Product
Process Plant
Control
Sample
Transport
Sample
Transport
Sample
Transport
Pre-Conditioning
SampleConditioning
Results
SampleAnalysis
Process Computer
Process Pipe
Take Off Probe
Figure 29: the steps from process sample to process control
Generally in plant operations manual samples are taken from the process for laboratory analyses.These
sample are taken by the operators of the plant. The operator fills a sample bottle with the product and
brings it to the lab for further analysis. In some cases the samples are taken semi-automatic. Like a
sample bombe with a piston assembly, to control the sample pressure in the bottle, is automatically filled
using a process valve. These procedures introduce errors in the sample, e.g.:





The sample may be exposed to air with the consequence of oxidation and humidification of
the sample.
In case of a sample in the liquid phase a gas phase may arise when the pressure drops.
In case of a sample in the gas phase a liquid phase may arise when the temperature drops.
Especially in the last two examples, impurities may drop out and the sample composition may
end up different from the actual sample.
Sample flush times may differ from person to person with the risk of differences in sample
composition due to insufficient flushing.
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On-line analyses uses automatic sample handling. This excludes the human error and samples are taken
under repeatable circumstances. Still errors may occur with the sample handling when strict rules are not
followed. The design of the sample handling will be of influence to the sample transport time (lag time)
and eventually the total analyses time, which, is the sum of the sample transport and analyses time. The
automation of the process analyses will eventually result in cost reduction and yield improvement of
production plants due to better control of sample handling and analyses. One of the examples is the
extensive cost reduction in a catalyst protection by process analyses. Another example is the automated
analyses of important gas transport lines where toxic components and energy transfer is monitored and
reported. Below figure displays the process and instrumentation diagram (P&ID) of a process analyses
system. It displays the essential components for process analysis in detail.
Figure 30: from process sample to process control, the P&ID
2.1
The essential steps in process analyses
The essential steps in process analyses start at the sample take-off point. For this purpose a sample
take-off probe is used and mounted to the process pipe to draw a representative sample from the process
on 20%-80% in the cross section of the pipe.
Then the pressure and temperature are conditioned in the pre-conditioning system as close as possible to
the take off point. This is done at the take-off point in order to get a representative sample, to avoid the
use of high pressure sample lines and to make the system faster. Next the sample is transported to the
sample handling and conditioning system by heated and/or insulated sample lines. This to avoid
condensation and freezing of the sample in the lines. Also heating will minimize wall adsorption effects of
low sample component quantities. In some cases the sample line wall is in addition treated and coated for
this purpose.
The functions of a sample handling and conditioning system are (21):
 to condition the sample so it is compatible with the analyser and its application. The sample
conditioning includes operations as flushing, cleaning, condensing, pressure and temperature
adjusting.
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


for stream switching, so the analyser can be used on more than one stream.
to provide for proper introduction of a calibration standard.
to transport the sample from the analyser to the desired point of rejection. Included are venting
arrangements, waste disposal systems, and methods for returning the sample to the process
where necessary, without adversely affecting analyser operation.
All materials used are chosen with minimum effects from corrosion, adsorption or reaction with the
sample.
The analytical equipment forms the heart of the system. More than the laboratory analyses, process
analyses focuses on speed and reliability. The analyser must run unattended and continuous without
intervention of the operator. When the results indicate an off-set condition of the particular process, the
operator must be able to rely on the trueness of the results. In the impurity detection of a catalyst, a false
zero indication is an even worse scenario and can result in a life threatening situation. A good example is
the explosion that happened in an Air Separation Unit (ASU) at Shell’s Gas To Liquid (GTL) process in
Bintulu on December 1997. Detailed investigations revealed that the explosion was not caused by any
part of the plant itself, but by smoke particles from local forest fires building up in the liquefied oxygen in
the ASU. Fast (process) analyses of the hydrocarbons in the oxygen could have detected the threatening
situation and prevented the accident.
Therefore tools must be available on the analytical equipment to confirm the correctness of the
measurement. Statistical control carts are used to monitor the performance of the analytical equipment
over time. Instead of calibrating the instrument on time base it is subjected to a control sample tested
against warning and control limits for decision of corrective action.
From the large number of analytical techniques available for process analyses some methods used for
online compositional process analyses can be listed as follows:
1. Chromatography
a. Micro Gas Chromatography
b. Gas Chromatography
2. (Laser-) Spectroscopy
a. Photo-(acoustic laser) spectroscopy
b. Cavity ring down spectroscopy
3. Mass-spectrometry
a. Ion mobility spectroscopy
b. Field Asymmetric Ion Mobility Spectrometry
Finally results are transferred to the process control system using a standard industrial communications
TM
TM
protocol like Modbus or Fieldbus . Reason for such standard is the diversity in instrumentation used in
a plant. In general the protocols must be able to accurately transfer the data and inform the operator
about the condition of the instrument. Generally analytical instruments are equipped with redundant
communications outputs to ensure data pass to the control system in case one of the outputs fail or one
of the communication routes are blocked.
The result transfer may also include the tools for a process operator to start for example a so called
benchmark analysis to confirm the correctness of the measurement of the analytical equipment.
3
Sample handling and integration back ground information
Sample handling is often forgotten to be one of the most important aspects for process analysis. While in
laboratory environment the sample handling is a well addressed issue (2) in process analysis the focus is
commonly on the analysis itself. A number of developments in the area of process analysis sampling will
be addressed here.
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First a conventional process sample handling system consists of a sample take-off and preconditioning
system, sample transport and sample conditioning and calibration system. These are basic blocks
needed to built a sample handling system. The particular parameters that need to be controlled are
pressure, flow and temperature, clean-up of the sample by filtration, liquid separation and calibration. For
example when a system is build to analyse environmental samples the pressure is normally atmospheric
and a pump is needed to pull the sample through the system, then liquids are taken out of the system
using a cooler in combination with a peristaltic pump, after which temperature is slightly elevated above
the dew point to prevent any gasses to condense during transport and further treatment. One important
aspect here is not to drop-out any of the components of interest during the liquids drop-out step.
Another example where the sample is taken from a process at a high pressure. Normally the pressures at
the process pipe, particular in natural gas transport, are relative high (50-100 barg). To be able to analyse
the sample with an analyser, which is generally done at a few bar gauge, the sample first needs to be
reduced in pressure. Doing that a pressure drop will result in a temperature drop due to the Joule
Thompson effect (also called a throttling process). This results in unwanted effects like freezing at the
sample take-off point. The sample handling device to neutralize this effect is a vaporizing regulator. This
device is often installed at the sample take-off point as close as possible to the sample probe. A new
development is a probe which uses the process fluid energy in conjunction with an internal heat transfer
device to heat the pressure regulator installed at the bottom in the probe to neutralize the temperature
drop effect (see Figure 31)
Figure 31 Genie Retractable Probe
Regulator Model GPR with integrated
membrane (courtesy of Genie inc.).
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3.1.1
Further developments in sample handling (NeSSI™) (22)
A new development in sample handling is the NeSSI platform which reduces conventional sample
handling systems to a standardized miniaturized platform. The NeSSI initiative was begun to simplify the
tasks, and reduce the overall costs, associated with engineering, installing and maintaining chemical
process analytical systems. NeSSI is an acronym for New Sampling/Sensor Initiative. The specific
objectives of NeSSI are:
 to increase process analytical system reliability,
 through the use of increased automation,
 shrink the physical size, sample and energy use by means of miniaturization,
 decrease sample flush times by analyser and sample handling integration,
 promote the creation and use of industry standards for process analytical systems,
 and help create the infrastructure needed to support the use of the emerging class of robust and
selective micro-Analytical sensors.
Figure 32: standardized building block for the NeSSI platform (courtesy of Circor Tech)
The sample handling building blocks are standardized resulting in simplified engineering and construction
of the sample handling system. The components are interchangeable which reduces the cost and
maintainability.
Figure 33: a sample handling system on the NeSSI platform (courtesy Circor Tech)
The sample volume Vsample in
is reduced to a minimum on this platform.
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A number of other analytical devices/sensors are available on this platform; e.g. a photometer, a moisture
sensor, a viscosity meter and an oxygen sensor. An interesting development from EIF is the Astute 3D
Probe. Here the integration reaches an ultimate level, the sample take-off probe, sample preconditioning,
and sample analysis are all integrated in one device.
Figure 34: all steps from sample take-off to analysis integrated in one 3D probe (courtesy of EIF)
3.1.2
Integration of equipment in process plants a slim analyser package (aSAP) (9)
Another new development of further integration of equipment with its sample handling in a process plant
and the increase of sampling speed has been developed by ASaP BV the Netherlands. It consists of a
flexible cabinet called a Slim Analyser Package (aSAP) with integrated sample handling and .
For the analyser(s) and maintenance personnel a weather protective enclosure is provided. The
construction of the enclosure is such that by opening both enclosure doors are at an angle of 90, a
weather protective area is created for maintenance personnel. Both doors will be fixed at 90 by special
plastic breaking rods. In case of an emergency maintenance personnel can walk/fall through the doors
which will open to 180. This concept called will enclose the requested analyser(s) and its sample
handling system and utilities.
Direct on top of the pipeline installation is possible with this
setup. It will also reduce overall installation and
engineering costs. Below example shows the integration
Figure 36: a Slim Analyser Package (aSAP),
the back wall is transparent for illustration
Figure 35: on pipeline installation including side platform
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steps of a µGC into a Process (ATEX) certified µPGC and an aSAP analyser package.
Analytical
Channel
µGC Casing
Process
micro GC
Figure 37 a µGC integrated into a Process (ATEX)
certified µPGC and an aSAP analyser package
Analytical Shelter
4
Discussions and Conclusions
Micro Gas Chromatography (µGC) is an interesting development for process analyses. For reasons of:
 The high speed of the analysis.
 The small size, high robustness and reliability of the instrument.
 The low consumption of utilities (power and carrier) and sample.
 The advantage towards EMC and ATEX certification and integration.
 The modular design for the ease of adaption of laboratory applications.
The µGCs selected was Agilent 490-GC µGC. The selection was based on how well the µGC could be
used in process analyses.
The reason for the selection can be summarized as follows:
 The application frame is extensive and applications can be selected and extended by
adding/combining modules with different columns. A feature to flush out components is available.
 The uGC has heated injectors, sample lines and inlets with a temperature up to 110°C to handle
high boiling point samples in the gas phase. The sample inject volume is variable and can be
reconfigured in seconds.
 The uGC has µTCDs which allows for a wide dynamic range (ppmv – vol%) and universal
detection of components.
 ATEX/CSA certification (for explosion safe operation) and environmental protection is available.
 Long term hardware field tests are performed and confirm suitability for process installation.
 Unattended operation and tools to confirm the correctness of the µGC are available.
 The manufacturer Agilent Technologies made a choice to make the instrument suitable for
process analyses.
4.1
Further discussion for process analysis
Due to the fast process analyses the µGCs require special features like special software and hardware
tools, fast sample handling and features to prevent the analytical column from unwanted impurities and
high boiling point components.
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The Agilent 490-GC µGC uses a back-flush system. The integrated software for standalone operation
with an industrial standard communications output like Modbus and a ATEX Zone1 and 2 certification (9)
results in a µGC fit for process analysis. The optional Differential Mobility Detector (DMD) is an interesting
development for selective impurity measurement.
The µGC has a repeatability <0.5%RSD based on normalized data with day-night influences included.
Finally it must be emphasized that an advantage for the µGC is the speed of analysis (0,5-1,5 minutes)
the low utilities and power consumption and low sample waste. It size allows for integration and
installation direct on the process pipe. Modular design allows maintenance on a plug and play basis.
Future developments on the µGCs should include features for:
 liquid injection for liquid (petro)chemical & bio-chemical applications
 multi method and multi stream operation
 remote communications and
 expand the detector range for low concentration and selective detection of impurities
 column switching
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5
References
1. Blomberg, Jan. Multidimentional GC-based separations for the oil and petrochemical industry.
Amsterdam : s.n., 2002. ISBN 90-9016065-5.
2. Schoenmakers, Peter, et al. Chromedia. Chromedia. [Online] 02 01, 2008. [Cited: 02 01, 2009.]
http://www.chromedia.org.
3. Theoretical Aspects and Practical Potentials of Rapid Gas Analysis in Capillary Gas Chromatography.
Thijssen, Robert, Hoed, Nico van den and Kreveld, M. Emile van. 1007-1015, Amsterdam : Anal.
Chem., 1987, Vol. 59.
4. Cramers, Carel A., et al. High-speed gas chromatography: an overview of various concepts. Journal
of chromatography A. 856, 1999, Vol. 856(1999).
5. Some reflections on speed and efficiency of modern chromatographic methods. Poppe, H. A, 778 321, Amsterdam : Elsevier, 1997.
6. Es, Andrew van. High speed narrow bore capillary gas chromatograpy. Heidelberg : Huthig Buch
verlag GmbH, 1992. ISBN 377852027X.
7. High Speed Portable Gas Chromatography. Bruns, Mark. W. 1994.
8. Technologies, Agilent. Scanview. Agilent technologies Scanview. [Online] 07 29, 2012. [Cited: 07 29,
2012.] http://www.chem.agilent.com/enus/search/library/Pages/CompoundSearch.aspx?a=scope:%22Library%22+lngcontenttype:%22applicatio
n%22.
9. Analytical Solutions and Products B.V. ASaP Producten and Application Notes. ASAP Producten.
[Online] 10 01, 2007. [Cited: 12 03, 2011.] http://www.asap.nl.
10. STANDARDIZATION, NEN INTERNATIONAL ORGANIZATION FOR. Ref. No. ISO 6976:1995(E) &
Cor.2:1997(E). Natural gas — Calculation of calorific values, density, relative density and Wobbe index
from composition. Switzerland : NEN, 1995, 1997. Vol. 1997.
11. Solutions, Shell Global. What is LNG? http://www.shell.com/. [Online] Shell Global Solutions, 07 24,
2012. [Cited: 07 24, 2012.]
http://www.shell.com/home/content/future_energy/meeting_demand/natural_gas/lng/what_is_lng/.
12. Doeschgate, ir Henk Ten and Lenior, drs ing Tim. LNG Sampler with sample conditioning and
micro Process Gaschromatograph. Amsterdam : ASaP BV & Doesco, 2012.
13. NEN. ISO 8943: 2007. LNG Sampling. Switserland : NEN, 2007. Vol. 2007.
14. Lenior, Tim. Literature Thesis Tim Lenior Analytical Sciences Aug 2009 ver1. Amsterdam : VU
University, 2009.
15. Agency, European Environment. Annual European Community LRTAP Convention emission
inventory report 1990–2006. Copenhagen : European Environment Agency, 2008. ISBN 978-92-9167366-7.
16. Register, EPER: the European Pollutant Emission. EPER Review Report 2004. Copenhagen K,
Denmark : European Commission, 2007.
17. Adrichem, Arno van. H2S Testdata. Rotterdam : Exxon Mobil, 2009.
18. Gas-to-Liquids. EP Technology. no.1, 2008, Vol. 2008, 1.
19. Meyers, Robert A. HANDBOOK OF PETROLEUM REFINING PROCESSES Third edition. s.l. :
McGraw-Hill, 2004.
20. Tim Lenior and Hans-Peter Smid, Asap, the Netherlands. Remko van Loon , Agilent
Technologies, Inc, the Netherlands. Analysis of Acetone, n-Hexane, MIBK,MNBK and MIBC Using the
Agilent 490 micro GC. Amsterdam : Dura Vermeer, ASaP BV, Agilent Technologies Inc, 2011.
21. Wealleans, Fred. THE SIX FUNCTIONS OF ANY SAMPLING SYSTEM. Milton Keynes : PASS,
2002.
22. New Sampling/Sensor Initiative (NeSSI™). New Sampling/Sensor Initiative (NeSSI™). [Online] 05 01,
2009. [Cited: 05 01, 2009.] http://www.cpac.washington.edu/NeSSI/NeSSI.htm.
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Fast Analysis of Natural Gas Using
the Agilent 490 Micro GC Natural
Gas Analyzer
Application Note
Micro Gas Chromatography, Hydrocarbon Processing,
Natural Gas Analysis
Author
Remko van Loon,
Agilent Technologies,
Middelburg, the Netherlands
Abstract
During production and distribution of natural gas it is of high importance to
determine its composition and calorific value because natural gas is bought and
sold on its energy content. This application note shows the use of the Agilent 490
Micro GC Natural Gas Analyzer for the analysis of natural gas and the calculation of
its heating value. With the 490 Micro GC, Agilent provides ideal solutions for
laboratory, on-line and field use.
Introduction
Natural Gas Analyzer setup
Natural gas mainly consists of methane and variable levels of
other hydrocarbons and permanent gases such as oxygen,
nitrogen, and carbon dioxide. Different sources of natural gas
usually have similar composition but vary in concentration.
Based on the 490 Micro GC, four Natural Gas Analyzers are
available, depending on the composition of the natural gas
and the compounds of interest. The configurations and
analysis characteristics for all analyzers are shown in Table 1.
Additional information for the configurations can be found in
Natural Gas Analyzer Data Sheet [1].
Natural gas is traded on its energy content and therefore the
analysis of the chemical composition and calorific value is of
high importance for all stakeholders. That is where the
490 Micro GC based Natural Gas Analyzer can play a
significant role.
The Natural Gas Analyzers are equipped with heated injectors
and sample lines, both set to 110 °C in the analyzer method,
to eliminate any cold spots and prevent possible condensation
of moisture, and to ensure the integrity of the sample is
maintained throughout the sample flow path.
The 490 Micro GC Natural Gas Analyzers are shipped as a
total solution; the analyzers are factory tuned, for optimal
separation, and come with final test data, a complete method,
a user manual, and a check-out sample. Easy-to-use software
is available for the calculation of all required physical
properties, such as heating value and Wobbe index, conform
official methods from the American Society of Testing and
Materials (ASTM), Gas Processors Association (GPA) and
International Standards Organization (ISO).
Table 1.
Table 1 shows multiple column channels are equipped with a
back flush to vent option. To protect the CP-Molsieve 5A
stationary phase and maintain the separation efficiency of the
molecular sieve column, it is necessary to back flush carbon
dioxide, moisture, and higher hydrocarbons. Moisture and
carbon dioxide tend to adsorb quickly to the molecular sieve
stationary phase change its chromatographic properties. This
can result in retention shifts and loss of separation. Higher
hydrocarbons will eventually elute, but will cause higher
detector noise levels and would lead to reduced sensitivity;
the back flush to vent functionality on the Molsieve 5A
column channel prevents this from happening. On the
PoraPLOT U and HayeSep A channels, the higher
hydrocarbons, C4 and higher, are back flushed to vent. This
prevents these late eluting components from interfering in the
next analysis.
Agilent 490 Micro GC Natural Gas Analyzers Overview.
Analyzer
characteristics
Natural Gas
Analyzer A
Natural Gas
Analyzer A Extended
Natural Gas
Analyzer B
Natural Gas
Analyzer B Extended
Micro GC cabinet
Dual with 2 channels
Quad with 3 channels
Dual with 2 channels
Quad with 3 channels
Column channels installed
HayeSep A
HayeSep A
PoraPLOT U
CP-MolSieve 5A
40 cm, without backflush
40 cm, with backflush
10 m, with backflush
10 m, with backflush and retention time
stability option
CP-Sil 5 CB
CP-Sil 5 CB
CP-Sil 5 CB
PoraPLOT U
6 m, without backflush
4 m, with backflush
6 m, without backflush
10 m, with backflush
Analysis
Hydrocarbons C1-C9
Carbon dioxide, Air
CP-Sil 5 CB
CP-Sil 5 CB
8 m, without backflush
6 m, without backflush
Hydrocarbons C1-C12
Carbon dioxide, Air
2
Hydrocarbons C1-C9
Carbon dioxide, Air,
Hydrogen sulfide
Hydrocarbons C1-C9
Carbon dioxide, Air,
Hydrogen sulfide
Permanent gases (N2, O2, He and H2)
The CP-Molsieve 5A is equipped with the retention time
stability (RTS) option. This RTS option consists of additional
in-line filters between the electronic gas control and the
column module to ensure moisture and carbon dioxide free
carrier gas. The use of the RTS option enables a more efficient
back flush of carbon dioxide. This enhances column lifetime
and, most importantly, leads to more stable retention times.
Fast Natural gas analysis using the Natural Gas
Analyzer A
The first channel in the Natural Gas Analyzer A is equipped
with a HaySep A column for separating methane from the
composite air peak (nitrogen and oxygen). Carbon dioxide,
ethane, and propane are analyzed on this column channel as
well. Figure 1 shows an example chromatogram for these
compounds.
The natural gas sample can be introduced to the 490 Micro
GC either pressurized (maximum limit 1 bar), through a Tedlar
sampling bag using the internal sampling pump, or by using
continuous flow sampling mode. When you need to analyze
multiple streams on a single analyzer or you want to connect
multiple calibration samples for automated calibration, the
use of a stream selector valve is recommended.
For the analysis of the hydrocarbons from propane to
n-nonane, a second column channel, equipped with a 6-meter
CP-Sil 5 CB column, is used. Figure 2a shows a chromatogram
on the 6-meter CP-Sil 5 CB for the separation until n-octane;
n-hexane elutes in less than 60 seconds and n-octane in just
over 3 minutes. Propane is analyzed on both HayeSep A and
CP-Sil 5 CB column enabling the use of propane as a bridge
component. The extended part of the chromatogram obtained
with a 6-meter CP-Sil 5 CB column, displayed in Figure 2b,
shows the analysis of hydrocarbons until n-nonane.
To expand the range of samples to Liquid Petroleum Gas
(LPG) and Liquefied Natural Gas (LNG), the Micro-Gasifier
provides controlled evaporation before the sample is
introduced into the gas chromatographic injector for analysis.
In addition, high-pressure gas samples can be reduced
without creating cold spots, which prevents
discrimination in the sample.
2
Conditions
Column temperature
Carrier gas
Injection time
Peak identification
60 °C
helium, 260 kPa
40 ms
1.
2.
3.
4.
5.
4
1
5
composite air peak
methane
carbon dioxide
ethane
propane
3
200 × Zoom
20 × Zoom
3
0
4
5
30
60
90
120
Seconds
Figure 1.
Chromatogram for nitrogen, carbon dioxide, and C1 – C3 hydrocarbons on a HayeSep A column.
3
Peak identification
Conditions
Column temperature 70 °C
Carrier gas
helium, 150 kPa
Injection time
40 ms
1
56
1.
2.
3.
4.
5.
6.
7.
8.
9.
7
8
9
propane
i-butane
n-butane
neo-pentane
i-pentane
n-pentane
n-hexane
n-heptane
n-octane
20 × Zoom
23
4
0
30
60
90
120
150
180
210
Seconds
Figure 2a. Chromatogram for C3 – C8 hydrocarbon using a 6-meter CP-Sil 5 CB column.
Peak identification
9. n-octane
10. n-nonane
10
9
100 × Zoom
160
220
280
340
400
Seconds
Figure 2b. Chromatogram for C8 – C9 hydrocarbons using a 6-meter CP-Sil 5 CB column.
Analysis up to n-dodecane with the Natural Gas
Analyzer A Extended
The extended version of the Natural Gas Analyzer A is used
for the analysis of natural gas until n-dodecane. This extended
analyzer is equipped with three column channels. First, a
HayeSep A column channel is used for separation of
composite air peak from methane, carbon dioxide ethane, and
propane. This channel is equipped with back flush
functionality ensuring that butanes and later eluting
hydrocarbons are back flushed to vent. Figure 3 shows an
example for the HayeSep A channel, propane is eluting in less
than 2 minutes.
4
2
Conditions
Column temperature
Carrier gas
Injection time
Backflush time
4
Peak identification
90 °C
helium, 340 kPa
20 ms
120 s
1.
2.
3.
4.
5.
3
composite air peak
methane
carbon dioxide
ethane
propane
5
1
20 × Zoom
3
0
100 × Zoom
4
5
30
60
90
120
Seconds
Figure 3.
Chromatogram for HayeSep A column with backflush.
The second channel, equipped with a 4-meter CP-Sil 5 CB
column with back flush functionality, is used to analyze C3 to
C5 hydrocarbons; the chromatogram is shown in Figure 4.
N-hexane and higher hydrocarbons are back flushed to vent.
2
Conditions
Column temperature
Carrier gas
Injection time
Backflush time
3
4
5
Peak identification
60 °C
helium, 150 kPa
40 ms
12 s
1.
2.
3.
4.
5.
6.
6
1
20 × Zoom
0
Figure 4.
10
Seconds
20
30
Chromatogram for C3 to C5 hydrocarbons on a 4-meter CP-Sil 5 CB.
5
propane
i-butane
n-butane
neo-pentane
i-pentane
n-pentane
and the sample inlet of the Micro GC have an UltiMetal
deactivation layer, which results in an inert sample flow path
and excellent peak shape ensuring correct analysis of
hydrogen sulfide even at ppm level.
A third column channel, equipped with a 8-meter CP-Sil 5 CB
column, is used to analyze the higher hydrocarbons from
n-hexane to dodecane; n-Dodecane elutes in approximately
240 seconds. A natural gas sample sample until n-decane,
demonstrated in Figure 5a, is analyzed in less than 2 minutes.
Figure 5b displays a hydrocarbon gas mixture from n-hexane
until n-docecane, typical analysis time is 240 seconds.
Hydrocarbon analysis from propane until n-nonane for the
Natural Gas Analyzer B is done with a second channel
equipped with a 6-meter CP-Sil 5 CB. This column is identical
to the one used for the Natural Gas Analyzer A.
The chromatograms for this channel are displayed in
Figure 2a and 2b.
Analysis of natural gas including hydrogen sulfide
using the Natural Gas Analyzer B
When your natural gas analysis needs to include hydrogen
sulfide, the 490 Micro GC Natural Gas Analyzer B is the
analyzer of choice. This analyzer uses a PoraPLOT U column
channel for the separation of methane from the composite air
peak (nitrogen and oxygen). This column is also used for the
analysis of carbon dioxide, ethane, and propane. The
chromatogram in Figure 6 shows an example of natural gas
on the PoraPLOT U column; total analysis is done in
approximately 60 seconds. For the analysis of hydrogen
sulfide, the stainless steel tubing in the PoraPLOT U channel
Conditions
Column temperature 150 °C
Carrier gas
helium, 200 kPa
Injection time
40 ms
4
5
1
5 × Zoom
2
3
0
30
4
5
60
90
120
Seconds
Figure 5a. Analysis of natural gas on an 8-meter CP-Sil 5 CB.
Peak identification
2
1
1.
2.
3.
4.
5.
6.
7.
3
4
5
n-hexane
n-heptane
n-octane
n-nonane
n-decane
n-undecane
n-dodecane
7
6
0
60
120
Seconds
180
240
Figure 5b. Analysis C7 – C12 hydrocarbon mix on an 8-meter CP-Sil 5 CB.
6
Peak identification
1.
2.
3.
4.
5.
n-hexane
n-heptane
n-octane
n-nonane
n-decane
Conditions
Column temperature
Carrier gas
Injection time
Backflush time
2
4
Peak identification
60 °C
helium, 175 kPa
40 ms
17 s
1
5
6
1.
2.
3.
4.
5.
6.
composite air peak
methane
carbon dioxide
ethane
hydrogen sulfide
propane
3
10 × Zoom
100 × Zoom
3
4
6
5
15
30
45
60
75
Seconds
Figure 6.
Chromatogram for natural gas on the PoraPLOT U column channel.
When you need to analyze helium, neon, or hydrogen as well,
the use of argon instead of helium as carrier gas is required.
The bottom part of Figure 7 shows a chromatogram for the
molecular sieve column running with argon as carrier gas. To
have the flexibility to change the carrier gas for only the
molecular sieve column to argon, this channel is connected to
a separate carrier gas inlet at the rear of the micro GC.
Permanent gas analysis using Natural Gas
Analyzer B Extended
The Extended version of the 490 Micro GC Natural Gas
Analyzer B is equipped with an additional CP-MolSieve 5A
column channel for the analysis of permanent gases in your
natural gas sample. Helium carrier gas on this channel
enables the separation and quantification of oxygen and
nitrogen, an example is shown in Figure 7 (top part).
Peak identification
Sample 1
Helium carrier gas
Conditions
Column temperature
Carrier gas
Injection time
Backflush time
5
Sample 2
Argon carrier gas
Figure 7.
5 × Zoom
3
Conditions
Column temperature 80 °C
Carrier gas
argon,
200 kPa
Injection time
40 ms
Backflush time
11 s
0
6
4
80 °C
helium, 200 kPa
40 ms
11 s
15
1.
2.
3.
4.
5.
6.
helium
neon
hydrogen
oxygen
nitrogen
methane
6
1
2
5
4
20 × Zoom
30
Seconds
45
60
75
Chromatograms for the analysis of permanent gases on the CP-MolSieve 5A column channel.
7
Conclusion
Reporting tools for the physical properties
of natural gas
Micro GC Natural Gas Analyzer is a genuinely better solution
for analyzing your natural gas stream. Whether in the lab,
on-line/at-line, or in the field, the “Measure Anywhere”
Micro GC provides natural gas analysis in a matter of
seconds.
The results for all individual components are sent from the
chromatography data software of choice (EZChrom Elite,
OpenLAB EZChrom, or OpenLAB Chemstation) to optional
EZReporter software to calculate a wide range of physical
properties like, calorific value, relative density,
compressibility, and Wobbe index, see Figure 8 (left). These
key parameters are important to determine the commercial
value of the natural gas. EZReporter supports reports in
accordance with official methods ASTM D3588, ISO 6976, and
GPA 2172. The reports can be printed locally or exported to a
file for further use in a laboratory information management
system (LIMS).
The Natural Gas Analyzer A analyzer combined with a
HayeSep A and 6-meter CP-Sil 5 CB column channel is used
for the analysis of natural gas. This analyzer will separate
methane from air and can analyze up to n-nonane. Carbon
dioxide is also analyzed. Total analysis time depends on the
hydrocarbons in the sample; up to n-heptane is done in
approximately 90 seconds, n-nonane elutes just under
400 seconds.
The software includes functionality to select raw analysis
amounts and calculated key parameters for monitoring and
historical trend analysis. Upper and lower warning limits can
be given to these monitor parameters to better visualize the
results from your natural gas stream. Some examples are
given in Figure 8 (middle and right).
Figure 8.
When you want to analyze until n-dodecane in natural gas,
the Natural Gas Analyzer A Extended is required. The 6-meter
CP-Sil 5 CB column channel is replaced by two different CPSil 5 CB channels. A short CP-Sil 5 CB (4-meter) will analyze
from propane to the pentanes; hexane and higher will be back
flushed to vent. The second CP-Sil 5 CB channel, with an
8-meter column, is used for analysis of hexane up to
n-dodecane.
EZReporter, sample results with calculated physical properties (left), parameter monitoring (middle), and trend analysis (right).
8
The Natural Gas Analyzer B, equipped with a PoraPLOT U
and a 6-meter CP-Sil 5 CB CB column channel, provides fast
analysis of natural gas, from the separation of air and
methane, carbon dioxide, and hydrocarbons up to n-nonane.
This analyzer setup is designed for the analysis of hydrogen
sulfide. The stainless steel sample inlet of the systsm is
deactivated using an UltiMetal treatment resulting in
excellent peak shape for hydrogen sulfide.
If more detailed analysis of the permanent gases in the
natural gas sample is required, the extended version of the
Natural Gas Analyzer B is the system of choice. This analyzer
is equipped with an additional CP-MolSieve 5A column
enabling the separation of oxygen and nitrogen, using helium
as carrier gas. When this analyzer uses argon as carrier gas,
helium and hydrogen can be detected as well.
The 490 Micro GC Natural Gas Analyzers are factory tuned,
including the appropriate settings for the back flush times.
The Agilent Natural Gas Analyzers are shipped with final test
data, optimized analytical method, Natural Gas Analyzer User
Manual, and a check out sample kit to have all information
available upon installation.
The analyzer hardware together with your chromatography
data system (CDS) of choice provides an easy-to-use and
powerful system. The EZReporter software is linked to
Agilent CDS, resulting in automatic calorific value/BTU
calculations and reports according to American Society of
Testing and Materials (ASTM D3588), Gas Processors
Association (GPA 2172), and International Standards
Organization (ISO 6976).
For more information about the 490 micro GC Natural Gas
Analyzer or other Micro GC solutions, visit our website at
www.agilent.com/chem/microgc.
References
1. 5991-0301EN; Agilent 490 Micro GC Natural Gas
Analyzers; Data Sheet; April 2012.
For More Information
These data represent typical results. For more information on
our products and services, visit our Web site at
www.agilent.com/chem.
9
www.agilent.com/chem/microgc
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2012
Printed in the USA
April 16 2012
5991-0275EN
Analysis of Tetrahydrothiophene (THT)
in Natural Gas using the
Agilent 490 Micro GC
Application Note
Micro Gas Chromatography, Natural Gas Analysis, Sulfur Compound
Analysis
Author
Remko van Loon
Agilent Technologies
Middelburg
The Netherlands
Introduction
This application note shows the analysis of Tetrahydrothiophene (THT) in a Natural
Gas matrix using the Agilent 490 Micro GC. THT consists of a five-membered ring
containing a sulfur atom and four carbon atoms. THT is used as an odorant in
Natural Gas, because of its smell.
The chromatogram clearly shows the separation of THT from the other compounds
in the Natural Gas sample. The dimensions for the column channel used, a
CP-Sil 19 CB for THT, are optimized for this application. Moreover, this column
channel is factory tested to ensure the separation between THT and Nonane.
The advantage of the Agilent 490 Micro GC, in combination with the CP-Sil 19 CB
column channel, is the ease-of-use and the speed of analysis. Tetrahydrothiophene
eluetes around 40 sec and the total analysis time is less than 90 sec.
The Agilent 490 Micro GC is a rugged, compact, and portable lab-quality gas analysis platform. When the composition of gas mixtures is critical, count on this fifth
generation micro gas chromatography.
Instrumentation
Instrument
Agilent 490 Micro GC (G3581A)
Column channel
CP-Sil 19 CB for THT
Column temperature
90 °C
Carrier gas
Helium, 200 kPa
Injection time
255 msec
Injector temperature
110 °C
Sampling time
30 sec
S
For More Information
These data represent typical results. For more information on
our products and services, visit our Web site at
www.agilent.com/chem.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2011
Printed in the USA
June 29, 2011
5990-8528EN
Analysis of tert-Butyl Mercaptan in
Natural Gas on a CP-Sil 13 CB Using the
Agilent 490 Micro GC
Application Note
Micro Gas Chromatography, Hydrocarbon processing, Natural Gas
Analysis
Author
Remko van Loon
Agilent Technologies Inc.
Middelburg, The Netherlands
Introduction
This application note shows the analysis of tertiary-butyl mercaptan (TBM) in a
natural gas matrix using the Agilent 490 Micro GC. The dimensions and instrument
conditions for the column channel used in this application note, a CP-Sil 13 CB,
clearly shows the separation of TBM from the other compounds in the natural gas
sample.
The advantage of the Agilent 490 Micro GC, in combination with the CP-Sil 13 CB
column channel, is the ease of use and the speed of analysis. Tertiary-butyl
mercaptan elutes just before 60 seconds and the total analysis time is only
100 seconds.
The Agilent 490 Micro GC is a rugged, compact and portable lab-quality gas analysis
platform. When the composition of gas mixtures is critical, count on this fifth
generation micro gas chromatography.
SH
H3C
C
CH3
CH3
tert-Butyl Mercaptan
15 x Zoom
tert-Butyl Mercaptan
20
40
60
80
100
seconds
Instrumentation
Instrument
Agilent 490 Micro GC (G3581A)
Column channel
CP-Sil 13 CB for TBM
Column temperature
40°C
Carrier gas
Helium, 250 kPa
Injection time
255 msec
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Matrix
Information, descriptions, and specifications in this
publication are subject to change without notice.
Sample information
Natural gas
www.agilent.com
Tert-butyl mercaptan (TBM) 4 ppm
For More Information
These data represent typical results. For more information on
our products and services, visit our Web site at
www.agilent.com.
© Agilent Technologies, Inc., 2011
Printed in the USA
May 27, 2011
5990-8250EN
Analysis of Methyl Ethyl Sulfide (MES)
in Natural Gas using the
Agilent 490 Micro GC
Application Note
Authors
Mohamed Bajja and Remko van Loon,
Micro Gas Chromatography, Natural Gas Analysis, Sulpher Compound
Analysis
Agilent Technologies, Inc.
Middelburg,
The Netherlands
Introduction
This application note shows the analysis of Methyl Ethyl Sulfide (MES) in natural gas
using the Agilent 490 Micro GC. Methyl Ethyl Sulfide is an organosulfur compound
with a characteristic odor, and therefore used in some countries as an odorant for
natural gas.
This Micro GC column channel is equipped with a special dedicated column, MES in
natural gas, for the separation of MES from the other compounds in natural gas.
Moreover, this column channel is factory tested to ensure the separation between
n-Decane and MES.
If you want to the ability to measure anywhere and get the results you need in seconds, the Agilent 490 Micro GC is the ideal solution. With its rugged, compact, laboratory quality gas analysis platform, the 490 Micro GC generates more data in less
time for faster, and better, business decisions.
Instrumentation
Sample information
Instrument
Agilent 490 Micro GC (G3581A)
n-Decane
11 ppm
Column channel
MES in natural gas
Methyl Ethyl Sulfide (MES)
14 ppm
Column temperature
90 °C
Carrier gas
Helium, 70 kPa
Injection time
255 msec
Injector temperature
110 °C
Sampling time
30 sec
Matrix
S
n-Decane
H3C
CH3
Methyl Ethyl Sulfide (MES)
60
90
120
Seconds
For More Information
These data represent typical results. For more information on
our products and services, visit our Web site at
www.agilent.com/chem.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2011
Printed in the USA
August 26, 2011
5990-8750EN
Analysis of Biogas Using the Agilent 490
Micro GC Biogas Analyzer
Application Note
Micro Gas Chromatography, Hydrocarbon Processing, Renewable
Energy, Biogas Analysis
Author
Abstract
Remko van Loon
Biogas is considered a renewable and sustainable energy source and therefore is of
Agilent Technologies, Inc.
great interest worldwide. This application note shows the analysis of biogas, and
Middelburg, the Netherlands
related samples, using the Agilent 490 Micro GC Biogas Analyzer. Depending on the
biogas composition two configurations are available; the Agilent 490 Micro GC Biogas
Analyzer for pure biogas analysis and the Agilent 490 Micro GC Biogas Analyzer
Extended when biogas is mixed with other hydrocarbon streams, such as natural gas
or liquefied petroleum gas (LPG).
Introduction
Biogas is a gas mixture produced through biological processes; from anaerobic
fermentation or digestion of organic material such as biomass, manure or sewage,
municipal waste and energy crops. The composition of biogas is related to the origin
of the organic material; the main components of biogas are methane and carbon
dioxide, with some other permanent gases, hydrogen and hydrogen sulfide.
Biogas has a role in modern waste management and can fuel any type of heat
engine to generate either mechanical or electrical power. To increase its caloric
values it is sometimes necessary to remove some of the carbon dioxide or blend it
with other hydrocarbon streams. Biogas can be compressed, much like liquefied
natural gas, and used to power motor vehicles. For this purpose, it is essential to
remove hydrogen sulfide if present. Biogas is a renewable fuel, and so it qualifies for
renewable energy subsidies in some parts of the world.
The increased interest in biogas has resulted in a growing demand for fast and
efficient analysis technology to determine its composition. The Agilent Micro GC
Biogas Analyzers can play a significant role in achieving this goal.
The Agilent 490 Micro GC Biogas Analyzers are shipped as a
total solution; the analyzers are factory tuned, for optimal
separation, and come with final test data, analytical method
parameters, a user manual and a check-out sample.
Biogas Analyzer setup and conditions
Based on the Agilent 490 Micro GC, two Biogas Analyzers are
available; the configuration required for biogas analysis
depends on the sample composition.
For pure biogas analysis, including permanent gases and
hydrogen sulfide, the Agilent 490 Micro GC Biogas Analyzer
(p/n G3582A#110) is recommended, even ethane and
propane can be analyzed with this setup. This Biogas
Analyzer consists of a dual channel cabinet including a
10-meter CP-Molsieve 5A with argon as a carrier gas, providing excellent sensitivity and linearity for hydrogen, and a
10-meter CP-PoraPLOT U column channel with helium as
carrier gas.
Figure 1.
Agilent 490 Micro GC Biogas Analyzers.
Both Biogas Analyzers are equipped with heated sample line
and injectors to eliminate any cold spot and prevent possible
condensation of moisture, to ensure the integrity of the
sample is maintained throughout the sample flow path. Both
CP-Molsieve 5A and CP-PoraPLOT U columns have a backflush to vent option, moreover the CP-Molsieve 5A is
equipped with the retention time stability (RTS) option. This
RTS option consists of additional in-line filters between the
electronic gas control and the column module to ensure moisture and carbon dioxide free carrier gas. Moreover the use of
the RTS option enables a more efficient backflush of carbon
dioxide. This enhances column lifetime and, most importantly,
leads to more stable retention times.
When biogas is mixed with other hydrocarbon streams such
as natural gas or liquefied petroleum gas (LPG), the sample
contains higher boiling hydrocarbons. To analyze these hydrocarbons the Agilent 490 Micro GC Biogas Analyzer Extended
is the analyzer of choice. This Biogas Analyzer Extended
(p/n G3582A#111) is a quad channel cabinet Micro GC
including three column channels; a 10-meter CP-Molsieve
column on argon as carrier gas, a 10-meter CP-PoraPLOT U
column and an additional 6-meter CP-Sil 5 CB column on
helium as carrier gas for the analysis of higher boiling hydrocarbons. Figure 1 shows the quad and dual cabinet housing
for the Agilent 490 Micro GC Biogas Analyzers.
Table 1 gives an overview of typical conditions used for the
Biogas Analyzers.
Table 1.
490 Micro GC Biogas Analyzer Instrument Conditions
CP-Molsieve 5A, 10 m
CP-PoraPLOT U, 10 m
CP-Sil 5 CB, 6 m
Column temperature
80 °C
80 °C
60 °C
Carrier gas
argon, 200 kPa
helium, 150 kPa
helium, 150 kPa
Injector temperature
110 °C
110 °C
110 °C
Injection time
40 ms
40 ms
40 ms
1
11
14
no backflush
Detector sensitivity
auto
auto
auto
Invert signal
yes
no
no
Sample line temperature
110 °C
Sampling time
30 seconds
Backflush time
1
Note Backflush time is column channel dependent and should be fine tuned for each new column.
2
The sample can be introduced to the Agilent 490 Micro GC
Biogas Analyzer either pressurized (maximum limit 1 bar),
through a Tedlar sampling bag using the internal sampling
pump, or by using a continuous flow sampling mode. When
the sample pressure exceeds the 1 bar limit, for example with
a liquefied natural gas or liquefied petroleum gas, the
pressure should be reduced. The use of the Agilent MicroGasifier, a heated pressure reducer, is recommended here.
As biogas and related samples may contain larger amounts of
carbon dioxide, moisture, and higher hydrocarbons it is
necessary to backflush these components to maintain the
separation effiency of the Molsieve 5A column. Moisture and
carbon dioxide tend to adsorb quickly to the Molsieve 5A stationary phase and change its chromatographic properties.
This would result, over time, in retention shifts and loss of
separation. Higher hydrocarbons will eventually elute, but will
cause higher detector noise levels and lead to reduced
sensitivity. The backflush to vent functionality on the
Molsieve 5A column channel prevents this from happening.
Results and Discussion
The first column channel, a CP-Molsieve 5A, is used to
analyze the permanent gases, including hydrogen, oxygen,
nitrogen, methane, and carbon monoxide. Figure 2 shows a
chromatogram for this column channel.
Table 2 shows excellent repeatability figures for both
retention time, below RSD 0.05 %, and peak area below
RSD 0.1 %, for the compounds analyzed on the Molsieve
column channel.
Hydrogen
Methane
Carbon
monoxide
Nitrogen
Oxygen
Zoom
0
30
60
90
Seconds
Figure 2.
Chromatogram for permanent gases on the CP-Molsieve 5A column channel.
3
120
Table 2.
Run no.
Repeatability Figures for Retention Time and Peak Area on the CP-Molsieve Column
Hydrogen
Rt (sec)
Oxygen
Rt (sec)
Nitrogen
Rt (sec)
Methane
area
Hydrogen
area
Oxygen
area
Nitrogen
area
Methane
area
1
23.23
30.46
42.31
55.85
5852426
1594746
4855956
15750694
2
23.22
30.46
42.31
55.85
5852402
1594913
4856189
15752646
3
23.22
30.45
42.30
55.85
5849806
1594074
4853402
15749892
4
23.22
30.45
42.30
55.85
5857044
1596055
4859671
15769519
5
23.22
30.46
42.31
55.86
5853222
1595289
4856426
15762840
6
23.23
30.46
42.30
55.85
5847437
1593546
4853332
15742096
7
23.22
30.45
42.30
55.85
5855831
1596512
4860136
15768153
8
23.23
30.46
42.31
55.86
5846434
1594241
4854710
15745279
9
23.22
30.46
42.30
55.85
5860122
1597659
4864955
15785858
10
23.22
30.45
42.30
55.85
5852819
1595989
4860359
15768762
Average
23.22
30.46
42.30
55.85
5852754
1595302
4857514
15759574
Std. dev.
0.0048
0.005
0.005
0.004
4210
1258
3691
13699
RSD (%)
0.021
0.017
0.012
0.008
0.072
0.079
0.076
0.087
For pure biogas, carbon dioxide and hydrogen sulfide are
analyzed on a CP-PoraPLOT U column channel. When biogas
is mixed with other hydrocarbon streams, ethane and propane
can also be analyzed on this channel. Baseline separation of
carbon dioxide, ethane, hydrogen sulfide, and propane is
obtained, shown in Figure 2. Higher hydrocarbons present in
the sample are backflushed to vent; which prevents late
eluting components from interfering in the next analysis.
Carbon dioxide
Ethane
Hydrogen sulfide
Zoom
Propane
Hydrogen sulfide
10
20
30
40
50
Seconds
Figure 3.
Chromatogram for carbon dioxide, hydrogen sulfide, ethane, and propane on the CP-PoraPLOT U channel.
4
60
The stainless steel tubing in the CP-PoraPLOT U channel and
the sample inlet of the Micro GC have an UltiMetal deactivation layer, which results in an inert sample flow path and
better performance for hydrogen sulfide analysis. Results presented in Table 3 shows very good repeatability figures for
hydrogen sulfide and the other compounds (carbon dioxide,
ethane, and n-propane) analyzed on the CP-PoraPLOT U channel. Relative standard deviation (RSD %) below 0.02 % for
retention time and below 0.15 % based on area illustrates the
system’s suitability for this type of analysis. Moreover the
UltiMetal deactivated sample inlet tubing provides an
excellent peak shape for hydrogen sulfide, see Figure 3.
Table 3.
The CP-Molsieve and CP-PoraPLOT U channel,
chromatograms as shown in Figure 3, are part of both the
Biogas and Extended Biogas Analyzer.
Retention Time and Peak Area Repeatability Results for the CP-PoraPLOT U Column
Run no.
Carbon
dioxide
Rt (sec)
Ethane
Rt (sec)
Hydrogen
sulfide
Rt (sec)
n-Propane
Rt (sec)
Carbon
dioxide
area
Ethane
area
Hydrogen
sulfide
area
n-Propane
area
1
24.56
26.87
34.11
44.80
3240882
2662227
320047
2175181
2
24.56
26.88
34.12
44.80
3239148
2660569
319969
2178315
3
24.56
26.87
34.12
44.80
3240617
2662025
320273
2181300
4
24.56
26.87
34.11
44.79
3239973
2661327
320031
2180366
5
24.56
26.87
34.11
44.79
3239006
2661163
319909
2178141
6
24.56
26.87
34.11
44.80
3240134
2661385
319833
2174648
7
24.55
26.87
34.11
44.79
3239972
2661379
320000
2173550
8
24.55
26.87
34.11
44.79
3238407
2660348
319721
2177678
9
24.56
26.87
34.11
44.79
3238332
2660512
320024
2179891
10
24.55
26.87
34.11
44.79
3237012
2659615
319789
2176390
Average
24.56
26.87
34.11
44.79
3239348
2661055
319960
2177546
Std. dev.
0.0048
0.0032
0.0042
0.0052
1197
797
157
2578
RSD (%)
0.020
0.012
0.012
0.012
0.037
0.030
0.049
0.12
5
Propane
i-Butane
n-Butane
neo-Pentane
n-Heptane
i- Pentane
n-Pentane
Zoom
n-Hexane
0
Figure 4.
30
60
Seconds
Chromatogram on the CP-Sil 5 CB, separating the hydrocarbons from butanes to n-heptane.
In Figure 4, the chromatogram illustrates the separation and
quantification of the higher boiling hydrocarbons as part of
the Extended Biogas Analyzer setup; the column used is a
CP-Sil 5 CB. This additional channel expands the application
range of biogas analysis to blends with natural gas or
liquefied petroleum gas (LPG). In this particular case, the
biogas was mixed with natural gas.
Table 4a.
120
90
Tables 4a and 4b show repeatability on the CP-Sil 5 CB
channel for the hydrocarbons. The repeatability data of
approximately 0.05% for retention times and below the 0.2%
mark for peak area can be considered as excellent. Even the
partially separated neo-pentane shows a good peak area
repeatability performance.
Retention Time Reproducibility Data for the CP-Sil 5 CB Channel
Run no.
i-Butane
Rt (sec)
n-Butane
Rt (sec)
neo-Pentane
Rt (sec)
n-Pentane
Rt (sec)
i-Pentane
Rt (sec)
n-Hexane
t (sec)
n-Heptane
Rt (sec)
1
18.10
20.43
21.75
28.58
32.52
59.67
120.66
2
18.10
20.43
21.75
28.58
32.52
59.67
120.69
3
18.10
20.42
21.74
28.58
32.51
59.66
120.70
4
18.10
20.42
21.74
28.57
32.51
59.66
120.71
5
18.09
20.42
21.74
28.57
32.50
59.64
120.72
6
18.09
20.42
21.74
28.57
32.50
59.64
120.72
7
18.09
20.41
21.73
28.56
32.49
59.63
120.72
8
18.08
20.41
21.72
28.55
32.48
59.61
120.73
9
18.08
20.40
21.72
28.55
32.48
59.60
120.72
10
18.08
20.40
21.72
28.54
32.47
59.59
120.74
Average
18.09
20.42
21.74
28.57
32.50
59.64
120.71
Std. dev.
0.0088
0.0107
0.0118
0.014
0.018
0.029
0.023
RSD (%)
0.048
0.053
0.054
0.050
0.054
0.049
0.019
6
Table 4b.
Reproducibility Data, Based on Peak Area, for the CP-Sil 5 CB Column
Run no.
i-Butane
area
n-Butane
area
neo-Pentane
area
n-Pentane
area
i-Pentane
area
n-Hexane
area
n-Heptane
area
1
7014680
7186850
1265110
2702141
2781533
1552255
133755
2
7018181
7190966
1264813
2703703
2783345
1553847
133682
3
7018469
7187273
1269047
2704327
2783935
1554441
133642
4
7017302
7188209
1269045
2705176
2784640
1554809
133920
5
7017858
7190794
1264914
2705022
2784520
1554963
133951
6
7024447
7196790
1265962
2707439
2787091
1556518
133959
7
7025658
7196118
1269229
2708459
2787981
1557169
133959
8
7019982
7188645
1270146
2706467
2785715
1555951
133880
9
7018355
7189383
1267352
2706536
2785636
1556096
134091
10
7018173
7190297
1266144
2706696
2785947
1555806
134130
Average
7019311
7190533
1267176
2705597
2785034
1555186
133897
Std. dev.
3315
3418
2043
1888
1865
1439
162
RSD (%)
0.047
0.048
0.16
0.070
0.067
0.093
0.12
When butanes and higher hydrocarbons need to be analyzed,
the Agilent 490 Micro GC Biogas Analyzer Extended is
recommended. This analyzer, suited for analysis of biogas
mixed with other hydrocarbon streams such as natural gas or
LPG, is equipped with an additional CP-Sil 5 CB column
channel.
Conclusion
The Agilent 490 Micro GC Biogas Analyzer type required
depends on biogas sample type. Regular biogas contains
methane, carbon dioxide, nitrogen, and sometimes some
hydrogen, hydrogen sulfide, and carbon monoxide. For this
type of sample, the 490 Micro GC Biogas Analyzer is perfectly
suited.
All results clearly illustrate that both analyzer configurations
are perfectly capable of analyzing biogas and related sample
streams. Typical repeatability figures show RSD’s around
0.05 % for retention time and RSD’s less than 0.2 % for peak
area, while the factory specification for peak area repeatability
is specified on 0.5% RSD (based on 1 % concentration level
propane).
The first column channel, configured with a CP-Molsieve 5A
column with argon as carrier gas, will separate and analyze
hydrogen, oxygen, nitrogen, methane, and carbon monoxide.
Moisture and carbon dioxide, as well as higher hydrocarbons
present in the sample, are backflushed to vent, ensuring
trouble free operation, perfect repeatability, and a long
column lifetime without the need for extensive conditioning
procedures. Moreover, this column channel is equipped with
a Retention Time Stability option (RTS) to ensure stable
retention time on the CP-Molsieve 5A column over time.
The Agilent 490 Micro GC Biogas Analyzers are factory tuned,
including the appropriate settings for the backflush times for
the CP-MolSieve 5A and CP-PoraPLOT U columns. The Agilent
Biogas Analyzers are shipped with final test data, optimized
analytical method, Biogas Analyzer User Manual, and a check
out sample kit to have all information available at installation.
The second channel, equipped with a CP-PoraPLOT U column,
analyzes carbon dioxide and hydrogen sulfide as part of the
biogas sample. This column can even be used when ethane
and propane are present in the sample. The sample inlet of
the Micro GC and the CP-PoraPLOT U channel are treated
with an UltiMetal deactivation process to guaranty good
performance for hydrogen sulfide analysis.
For More Information
These data represent typical results. For more information on
our products and services, visit our Web site at
www.agilent.com/chem/microgc.
7
www.agilent.com/chem/microgc
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2011
Printed in the USA
November 22, 2011
5990-9508EN
Agilent 490 Micro GC Biogas
Analyzers
Data Sheet
Key benefits
• Complete Solution
The Agilent 490 Micro GC Biogas Analyzers are shipped as
a total solution. The analyzers are factory tuned and come
with final test data, analytical method parameters,
analyzer user manual and a check-out sample.
• Optimized Configuration
The Biogas Analyzers provide the results and ruggedness
you demand in the laboratory or in the field for the analysis
of biogas and related sample streams. Agilent provides a
single part number Biogas and Extended Biogas Analyzer
depending on the nature of the sample.
• Ready-to-Go
Start-up is easy; the analyzer ships fully loaded with a
method and is ready-to-go upon installation.
Introduction
Biogas is produced through biological processes such as
anaerobic fermentation or digestion of organic material. The
main components of biogas are methane and carbon dioxide,
with some other permanent gases, hydrogen and hydrogen
sulfide. The exact composition of the biogas is related to the
origin of the organic material.
• Easy to Operate
Agilent’s 490 Micro GC is designed to achieve the best
possible results. In addition, this system does not require a
high degree of operator skills to be used successfully.
Biogas is considered a renewable and sustainable energy
source; it can fuel any type of heat engine to generate either
mechanical or electrical power. To increase its caloric values,
it is sometimes necessary to remove some of the carbon
dioxide or blend it with other hydrocarbon streams.
• The Speed You Need
Micro GC is all about fast chromatography. Precise gas
analysis in seconds rather than minutes provides improved
product quality and more exact product valuation.
The increasing interest in biogas results in a growing demand
for fast and efficient analysis technology to determine its
composition. That is where the Agilent 490 Micro GC Biogas
Analyzers can play a significant role.
• Fast Delivery
The Agilent Biogas Analyzers are shipped from stock
ensuring short delivery times.
Choose the right Biogas Analyzer for your
needs
Channel 1 – Permanent gases
Hydrogen
Depending on the composition of your biogas sample, Agilent
has two 490 Micro GC based Biogas Analyzer configurations
available.
Methane
Carbon monoxide
For pure biogas analysis, including permanent gases and
hydrogen sulfide, the Agilent 490 Micro GC Biogas Analyzer
is recommended; even ethane and propane can be can be
analyzed with this analyzer setup. This Biogas Analyzer
consists of a dual channel cabinet including a 10-meter
CP-Molsieve 5A with argon as carrier gas, providing excellent
sensitivity and linearity for hydrogen, and a 10-meter
CP-PoraPLOT U column channel with helium carrier gas.
Nitrogen
Oxygen
Zoom
0
When biogas is mixed with other hydrocarbon streams such
as natural gas or liquefied petroleum gas (LPG), the sample
contains higher boiling hydrocarbons. To analyze these
hydrocarbons, the Agilent 490 Micro GC Biogas Analyzer
Extended is the analyzer of choice. This Extended Biogas
Analyzer is a quad channel cabinet Micro GC including three
column channels; a 10-meter CP-Molsieve column on argon
as carrier gas, a 10-meter CP-PoraPLOT U column, and an
additional 6-meter CP-Sil 5 CB column on helium as carrier
gas.
30
60
Seconds
90
120
Channel 2 – CO2, C2, H2S, and C3
Carbon dioxide
Ethane
Hydrogen sulfide
Zoom
Both Biogas Analyzers are equipped with heated sample
lines and injectors to eliminate any cold spot and prevent
possible condensation of moisture, to ensure the integrity of
the sample is maintained throughout the sample flow path.
10
20
30
Propane
40
50
60
Seconds
The CP-Molsieve 5A and CP-PoraPLOT U columns are
equipped with backflush to vent functionality. For the
Molsieve column, this backflush to vent is required to maintain the separation effiency as biogas and related samples
may contain larger amounts of carbon dioxide, moisture, and
higher boiling hydrocarbons. Moisture and carbon dioxide
tend to adsorb quickly to the Molsieve 5A stationary phase
and change its chromatographic properties. This would
results, over time, in retention shifts and loss of separation.
Higher hydrocarbons will eventually elute, but will cause
higher detector noise levels and would lead to reduced sensitivity. The backflush to vent functionality on the Molsieve 5A
and PoraPLOT U column channel prevents this from
happening.
Channel 3 – C4 – C7 hydrocarbons
i-Butane
n-Butane
neo-Pentane
i-Pentane
n-Heptane
n-Pentane
Zoom
n-Hexane
0
30
60
Seconds
Moreover the CP-Molsieve 5A is equipped with the retention
time stability (RTS) option. This RTS option consists of additional in-line filters between the electronic gas control and
the column module to ensure moisture and carbon dioxide
free carrier gas. Moreover the use of the RTS option enables
a more efficient backflush of carbon dioxide. This enhances
column lifetime and, most importantly, leads to more stable
retention times.
2
90
120
Technical specification
Analyzer characteristics
Agilent 490 Micro GC Biogas Analyzer
Agilent 490 Micro GC Biogas Analyzer Extended
Micro GC cabinet
Dual
Quad
Number of column channels
2
3
CP-MolSieve 5A column channel

with backflush and
retention time stability (RTS)
 with backflush and
retention time stability (RTS)
CP-PoraPLOT U column channel

with backflush

CP-Sil 5 CB column channel
–

All channels equipped with heated injectors (up to 110 °C)


Dual Carrier gas; Argon on Molsieve 5A, Helium on other
channels


Sample inlet UltiMetal treated


Heated sample line (up to 110 °C)


O2/ N2 separation


CO and CO2 analysis


H2S analysis


CH4, C2, and C3 hydrocarbon analysis


C4, C5, C6, and C7 hydrocarbon analysis
–

Sample type
biogas
biogas and biogas mixed with other hydrocarbon
streams (natural gas or LPG)1
Typical peak area repeatability (RSD%)
< 0.5 %
< 0.5 %
Analysis time
< 120 seconds
< 150 seconds
with backflush
Note 1: To introduce of a Liquefied Natural Gas (LNG) or Liquefied Petroleum Gas (LPG) sample on the Micro GC, the use of the Micro-Gasifier is required.
Accessories
The table below gives an overview of the most important
Agilent 490 Micro GC Biogas Analyzer compatible accessories.
Contact your local Agilent office for more details and
accessories.
Product description
Compatible with
Part number
Portable field case for a dual channel cabinet and dual carrier gases
Agilent 490 Micro GC Biogas Analyzer
CP490242
Portable field case for a quad channel cabinet and dual carrier gases
Agilent 490 Micro GC Biogas Analyzer Extended
CP490252
Micro-Gasifier
Both Biogas Analyzers
G7623A#001
Genie filter
Both Biogas Analyzers
Multiple p/n’s
3
Dimensions and weight
Height
Width
Depth
Weight
Product description
inch
cm
inch
cm
inch
cm
lb
kg
Agilent 490 Micro GC Biogas Analyzer
11
28
6.5
16
12
30
14
6
Agilent 490 Micro GC Biogas Analyzer Extended
11
28
6.5
16
21.5
55
22
10
Micro GC Power Supply
1.8
4.5
3.4
8.5
6.7
17
3.3
1.5
Ordering information
The Agilent Biogas Analyzers can be purchased by ordering
the main part number G3582A and an option number per
analyzer type; option numbers for the Biogas Analyzers are
displayed below.
Product description
Part number
Agilent 490 Micro GC Analyzer
G3582A
Agilent 490 Micro GC Biogas Analyzer
G3582A#110
Agilent 490 Micro GC Biogas Analyzer Extended
G3582A#111
www.agilent.com/chem/microgc
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change without notice.
© Agilent Technologies, Inc., 2011
Published in USA,
November 29, 2011
5990-9517EN
Analysis of Biogas with the
490 Micro GC Gas Chromatograph
Application Note
Authors
Introduction
Coen Duvekot
Agilent Technologies, Inc.
Biogas is a gas mixture produced by biological processes, from the anaerobic
fermentation of organic material such as biomass, manure or sewage, municipal
waste, green waste and energy crops. Swamp gas is a naturally produced biogas.
The main components of biogas are methane and carbon dioxide, with some carbon
monoxide and hydrogen. Biogas can be used as biofuel, as a low-cost fuel for any
heating purpose. It also has a role in modern waste management to run any type of
heat engine, to generate either mechanical or electrical power. To increase caloric
values it might be necessary to remove some of the carbon dioxide. Biogas can be
compressed, much like liquified natural gas, and used to power motor vehicles. For
this purpose it is necessary to remove hydrogen sulfide. Biogas is a renewable fuel,
and so it qualifies for renewable energy subsidies in some parts of the world. Due
to the increasing interest in biogas, there is a growing demand for fast and efficient
analysis technology. That is where the new generation micro GC from Agilent, the
490 Micro GC, can play a significant role.
Instrumentation
As biogas and related samples
may contain large amounts of CO2,
water and higher hydrocarbons it
was necessary to back flush these
components. Water and CO2, in
particular, adsorb to the stationary
phase and change chromatographic
properties. Higher hydrocarbons
eventually elute but cause higher noise
and thus reduced sensitivity.
Depending on the type of biogas to
be analyzed, two configurations are
available. If the sample contains only
permanent gases and the hydrocarbons
methane, ethane and propane, a
dual channel GC is ideal. If higher
hydrocarbons are also present in the
sample, a third channel is needed and
therefore the quad version of the microGC is recommended.
An indication of changed
chromatographic properties is
a drift in retention time. Table 2
shows repeatability figures on the
CP-Molsieve channel. Repeatability
figures of retention time and quantity
are presented.
490 Micro GC Gas Chromatograph
Dual channel:
• Channel 1, CP-Molsieve column
• Channel 2, CP-PoraPLOT U column
Quad equipped with three channels:
• Channel 1, CP-Molsieve column
• Channel 2, CP-PoraPLOT U column
• Channel 3, CP-Sil 5 CB column
GC control and data handling software:
Galaxie Chromatography Data System
Conditions
Table 1. GC conditions
Inj Time
(ms)
Inj Temp
(° C)
Column Temp
(° C)
Carrier Gas
Pressure
(kPa)
Back Flush
(sec)
Ch1
40
80
80
Ar
150
9
Ch2
100
80
100
He
100
10
Ch3
100
80
60
He
150
-
Results and Discussion
The sample can be introduced to
the 490 Micro GC either pressurized
(reduced to max 1 bar) via a Tedlar
sampling bag, or by using continuous
flow. In this case the sample was
pressurized, see Figure 1.
4
1
2
0.4
KEY
1. H2
2. O2
3. N2
4. CH4
3
min
Figure 1. Permanent gases on the CP-Molsieve
channel
2
2
Table 2. Repeatability figures for the
CP-Molsieve channel
Run #
Tr (min)
Hydrogen
Tr (min)
Oxygen
Tr (min)
Nitrogen
Tr (min)
Methane
QTY (%)
Hydrogen
QTY (%)
Oxygen
QTY (%)
Nitrogen
QTY (%)
Methane
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
0.5095
0.5097
0.509
0.5095
0.5095
0.5095
0.5097
0.5092
0.5095
0.5098
0.5093
0.5092
0.5092
0.5097
0.5092
0.6858
0.6858
0.6852
0.6857
0.6858
0.6858
0.686
0.6853
0.6858
0.6862
0.6855
0.6855
0.6855
0.686
0.6853
0.9618
0.962
0.961
0.9617
0.9622
0.962
0.9622
0.9617
0.962
0.9623
0.9617
0.9615
0.9617
0.9622
0.9615
1.2745
1.2748
1.2727
1.2743
1.2748
1.2743
1.2748
1.2735
1.2745
1.2753
1.2736
1.2735
1.2737
1.2752
1.2735
1.0253
1.0222
1.0375
1.0239
1.0292
1.0329
1.0306
1.0365
1.0278
1.0252
1.0347
1.0398
1.0368
1.0264
1.0361
2.0183
2.012
2.0272
2.0155
2.0197
2.0258
2.0254
2.0303
2.0188
2.0165
2.0277
2.0358
2.032
2.0143
2.0294
8.0511
8.057
8.0874
8.0307
8.0516
8.0664
8.0589
8.0875
8.0446
8.0182
8.0754
8.099
8.0797
8.0082
8.0688
84.5107
82.945
88.3207
83.2869
85.4475
86.787
85.2073
88.3182
85.3981
83.0202
87.3976
88.1668
87.1916
82.8409
87.3486
Average
Std Dev
RSD %
0.5094
0.0002
0.05%
0.6857
0.0003
0.04%
0.9618
0.0003
0.04%
1.2742
0.0007
0.06%
1.0310
0.0057
0.55%
2.0232
0.0073
0.36%
8.0569
0.0274
0.34%
85.7458
2.0592
2.40%
The very low relative standard deviation
(RSD%) figures in Table 2 clearly show
that the CP-Molsieve channel was
working with very good repeatability.
There was no drift in retention time and
the analysis results for quantity were
also very repeatable.
1
3
5
KEY
1. Composite air peak
2. CO2
3. Ethane
4. H2S
5. Propane
2
Figure 2 shows the chromatogram of
the CP-PoraPLOT U channel. Separation
of carbon dioxide, ethane, hydrogen
sulfide and propane was achieved.
Baseline separation of all components
of interest was obtained. Higher
hydrocarbons were back flushed to
vent, which prevented later eluting
components from disturbing the next
analysis. The results presented in Table
3 show very good repeatability figures
for the CP-PoraPLOT U channel. RSD%
below 0.1% for retention times and
quantification illustrate the system’s
suitability for this type of analysis.
4
0.3
min
Figure 2. CO2, H2S, ethane and propane on the
CP-PoraPLOT U channel
3
1
Table 3. Repeatability figures of the
CP-PoraPLOT U channel
Run #
Tr (min)
Air Peak
Tr (min)
CO2
Tr (min)
Ethane
Tr (min)
Propane
QTY (%)
CO2
QTY (%)
Ethane
QTY (%)
Propane
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
0.4115
0.4113
0.4117
0.4117
0.4115
0.4115
0.4115
0.4113
0.4115
0.4115
0.4115
0.4115
0.4113
0.4113
0.4118
0.4522
0.452
0.4525
0.4525
0.4522
0.4523
0.4522
0.4522
0.4522
0.4522
0.4522
0.4522
0.4522
0.452
0.4525
0.4833
0.4832
0.4837
0.4837
0.4833
0.4835
0.4835
0.4833
0.4833
0.4833
0.4833
0.4833
0.4833
0.4832
0.4837
0.6808
0.6807
0.6815
0.6813
0.6808
0.681
0.6808
0.6808
0.6808
0.6808
0.6808
0.6807
0.6807
0.6807
0.6815
1.9866
1.988
1.9921
1.99
1.9921
1.991
1.9896
1.9908
1.9927
1.9912
1.9933
1.9927
1.9908
1.9928
1.9919
4.0032
4.0048
4.0121
4.0073
4.011
4.0089
4.0059
4.0073
4.011
4.0069
4.0113
4.0103
4.0062
4.0096
4.0076
2.9955
2.9967
3.0015
2.9985
3.0014
2.9992
2.9973
2.9986
3.0027
2.9984
3.0018
3.0008
2.9978
2.9994
2.9992
Finally, Figure 3 is a chromatogram of
the separation and determination of
the (higher) hydrocarbons. The column
used was a CP-Sil 5 CB. This extra
channel expanded the application range
of biogas analysis to blends with C3
and or C4 LPGs.
2
1
3
4
KEY
1. H2S
2. Propane
3. iso-Butane
4. n-Butane
5. iso-Pentane
6. n-Pentane
7. n-Hexane
5
6
0.2
7
min
1.6
Figure 3. Higher hydrocarbons on the CP-Sil 5 CB channel
Table 4 shows the repeatability figures
of the CP-Sil 5 CB channel. Again,
very good repeatability figures were
obtained. Relative standard deviation
was well below 0.05% for retention
times and below 0.15% for quantitative
measurements.
4
Table 4. Repeatability figures of the CP-Sil 5 CB
channel
Run #
Tr (min)
Air Peak
Tr (min)
Ethane
Tr (min)
Propane
Tr (min)
iso-Butane
Tr (min)
n-Butane
QTY (%)
Ethane
QTY (%)
Propane
QTY (%)
iso-Butane
QTY (%)
n-Butane
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
0.3025
0.3023
0.3023
0.3023
0.3022
0.3023
0.3023
0.3022
0.3023
0.3023
0.3023
0.3023
0.3022
0.3022
0.3022
0.3333
0.3333
0.3333
0.3332
0.3332
0.3332
0.3332
0.3332
0.3332
0.3332
0.3332
0.3332
0.333
0.333
0.333
0.3833
0.3833
0.3832
0.3832
0.383
0.3832
0.3832
0.383
0.3832
0.3832
0.3832
0.3832
0.383
0.383
0.383
0.455
0.455
0.455
0.4548
0.4547
0.4547
0.4548
0.4547
0.4548
0.4548
0.4548
0.4548
0.4547
0.4547
0.4547
0.5107
0.5105
0.5105
0.5103
0.5102
0.5102
0.5103
0.5102
0.5103
0.5103
0.5103
0.5103
0.5102
0.5102
0.5102
4.0108
4.0092
4.0139
4.0116
4.0129
4.0096
4.0102
4.0126
4.0119
4.0098
4.0112
4.0091
4.0128
4.0099
4.0098
3.0222
3.0179
3.0171
3.0136
3.0131
3.0111
3.0095
3.0104
3.009
3.009
3.0092
3.0078
3.0101
3.0083
3.0083
0.501
0.501
0.5007
0.5009
0.5007
0.5007
0.5006
0.5009
0.5007
0.5009
0.5011
0.5008
0.5014
0.501
0.5009
0.5005
0.5004
0.5002
0.5003
0.5004
0.5003
0.5002
0.5004
0.5003
0.5003
0.5005
0.5
0.5007
0.5003
0.5002
Average
Std Dev
RSD %
0.3023
0.0001
0.03%
0.3332
0.0001
0.03%
0.3831
0.0001
0.03%
0.4548
0.0001
0.02%
0.5103
0.0001
0.03%
4.0110
0.0015
0.04%
3.0118
0.0042
0.14%
0.5009
0.0002
0.04%
0.5003
0.0002
0.03%
490 Micro GC Configuration for
Biogas depends on Sample Type
Regular biogas contains methane,
oxygen, nitrogen, carbon dioxide,
hydrogen sulfide, and sometimes some
hydrogen and carbon monoxide. For
this type of sample a two channel
490 Micro GC is perfectly suited.
Channel 1, configured with a
CP-Molsieve column, will separate
and analyze hydrogen, oxygen,
nitrogen, methane and carbon
monoxide. Channel 2, equipped with a
CP-PoraPLOT U column, will analyze
carbon dioxide and hydrogen sulfide.
This configuration can even be used if
ethane and propane are present in the
sample. If, however, C4+ hydrocarbons
also have to be analyzed, a third CP-Sil
5 CB channel is required, together with
the 490 Micro GC QUAD.
Conclusion
All results clearly showed that the
system configuration was perfectly
capable of analyzing biogas.
The CP-Molsieve channel separated
and analyzed permanent gases such
as hydrogen, oxygen, nitrogen and
methane. With some changes in
chromatographic parameters even
carbon monoxide can be analyzed on
this channel. Higher hydrocarbons,
as well as moisture and carbon
dioxide, were back flushed to vent
ensuring trouble free operation, perfect
repeatability and a long column lifetime.
www.agilent.com/chem
This information is subject to change without notice.
© Agilent Technologies, Inc. 2010
Published in UK, August 19, 2010
SI-02215
Using the Agilent 490 Micro GC for the
Monitoring of a Circulating Fluidized Bed
Biomass Gasifier
Application Note
Micro Gas Chromatography, Reaction/Production Monitoring,
Renewable Energy
Author
Abstract
Marcin Siedlecki
Biomass has been recognized as a potential renewable and sustainable energy
Energy Technology Section
source. The Delft University of Technology researches the gasification of woody and
Process and Energy Department
agricultural biomass in a Circulating Fluidized Bed Reactor. The Agilent 490 Micro GC
Delft University of Technology
is used to characterize the product gas using a COX column for the permanent gases
Delft, The Netherlands
and a CP-Sil 5CB for the BTX compounds.
Remko van Loon
Introduction
Agilent Technologies, Inc.
Middelburg, The Netherlands
There is a growing interest in sustainable heat and power generation using biomass.
A possible way to use the biomass is through thermal conversion processes; combustion and gasification are the most well-known examples. The Process and Energy
Department of the Delft University of Technology researched the gasification of
woody and agricultural biomass in a Circulating Fluidized Bed. The product gas consists roughly of 5–15% Carbon monoxide, 10–15% Hydrogen, 3–5% Methane,
10–20% Carbon dioxide, 5–10% Nitrogen, and 40–70% Water, also (poly)aromatic
compounds, minor inorganic species, and particles are present in the gas.
This product gas can be subsequently upgraded to Syngas (a mixture of Hydrogen,
Carbon monoxide, Carbon dioxide and eventually water vapor). After applying the
water-gas shift reaction (CO + H2O & CO2 + H2), Syngas could be used as a hydrogen-rich fuel gas for Fuel Cells. Other applications of Syngas are Fisher Tropsch
processes (Gas to Liquid fuels), platform chemicals (like furfural), or the combustion
in a gas turbine to generate heat and power. For the characterization of the product
gas, the Agilent 490 Micro GC was used.
Experimental
Fluidization media and woody or agricultural biomass are fed
into the Circulating Fluidized Bed Reactor, where the biomass
is gasified at around 850 °C. The sample is taken from the
product gas stream using a heated probe. Particles present in
the sample are removed by the dust filter. Water vapor is
stripped from the sample using two condensers. Figure 1
gives an overview of the sampling and sample conditioning
setup. An external gas pump provides a continuous sample
gas flow to the Agilent Micro GC. Every 3 min, the
Micro GC starts an analytical run and analyses the gas
sample on both column channels.
The Agilent 490 Micro GC used for the analysis of the
product gas is equipped with a 1 m COX column channel for
permanent gas analysis and a 4 m CP-Sil 5 CB column
channel for the analysis of Benzene, Toluene and the Xylenes.
The Micro GC conditions for both channels are displayed in
Table 1.
Table 1.
Reactor, sampling and sample conditioning setup.
Agilent 490 Micro GC Instrument Conditions
Column temperature
Carrier gas
Injector temperature
Injection time
Detector sensitivity
Sample line temperature
Sampling mode
Sampling time
Figure 2.
Figure 1.
1 m COX
4 m CP-Sil 5 CB
100 °C
Argon, 200 kPa
110 °C
20 ms
Auto
110 °C
Continuous flow
10 s
100 °C
Argon, 150 kPa
110 °C
40 ms
High
Results and Discussion
The COX column shows an excellent separation for the
permanent gases, as shown in Figure 2.
Permanent gases on the COX column.
2
Although the COX column does not separate oxygen and
nitrogen, it is very suitable for the analysis of permanent
gases including carbon dioxide. In the case of gasification, the
product gas sample does not contain oxygen. When the
sample contains both oxygen and nitrogen, and these gases
need to be quantified separately, the use of a MolSieve5A
column channel instead of the COX column channel is
required. The COX column can be equipped with a back flush
to vent. This option makes it possible to back flush later eluting compounds to reduce analysis time and to prolong column
lifetime.
formed. Figures 3 and 4 show an excellent calibration curve
for Methane and Carbon monoxide. For a linear regression,
the R-Squared for these compounds is nearly perfect.
The BTX compounds are analyzed on a CP-Sil 5 CB column
channel. The chromatogram in Figure 5 shows that all compounds are eluted in less than 90 sec. On the CP-Sil 5 CB
column type it is not possible to separate meta- and
para-Xylene. These compounds are reported in a single result.
For all BTX compounds, a 4-level calibration is performed.
Figure 6 shows an example of Benzene. R-squared (linear
regression) for Benzene is 0.9969.
For each component a multi-level calibration (4 levels) is perMethane
900
Carbon Monoxide
800
R2=0.9999
800
700
600
600
500
500
Area
Area
R2=0.9998
700
400
400
300
300
200
200
100
100
0
0
0
5
10
Concentration (vol %)
Figure 3.
Calibration curve for methane.
Figure 5.
BTX analysis on the CP-Sil 5 CB column.
0
15
Figure 4.
3
10
20
30
Concentration (vol %)
Calibration curve for Carbon monoxide.
40
50
Benzene
500,000
R2=0.9969
450,000
400,000
350,000
Delft University of Technology. The main advantages of the
490 Micro GC analyzer are its reliability, short analysis times,
ease of use (both hardware and software), and a certain
degree of flexibility. The modular setup of the 490 Micro GC
makes it possible to exchange the column modules if other
gas components need to be analyzed.
Area
300,000
The Agilent 490 Micro GC is a rugged, compact and portable
lab-quality gas analysis platform. When the composition of
gas mixtures is critical, count on this fifth generation micro
gas chromatograph.
250,000
200,000
150,000
100,000
50,000
0
0
Figure 6.
2
4
6
Concentration (vol %)
8
10
Calibration curve for Benzene.
Conclusion
The data presented in this application note clearly shows that
the Agilent 490 Micro GC equipped with two column channels
was capable of monitoring the product gas from the
Circulating Fluidized Bed biomass gasifier. Within
180 sec the permanent gases were analyzed using a
COX column channel. The BTX analysis was performed on a
CP-Sil 5CB column channel with an analysis time of less than
90 sec.
The Agilent 490 Micro GC is considered a key apparatus for
the quantification of the main product gas components in the
gasification test rig at the Process & Energy Laboratory at
References
1. M.Siedlecki, R. Nieuwstraten, E. Simone, W. de Jong and
A.H.M. Verkooijen; Delft University of Technology; ‘Effect
of Magnesite as Bed Material in a 100 kWth SteamOxygen Blown Circulating Fluidized-Bed Biomass Gasifier
on Gas Composition and Tar Formation’; 2009.
2. Application note 5990-7054EN; Simone DarphornHooijschuur and Marijn van Harmelen, Avantium
Technologies; Remko van Loon and Coen Duvekot, Agilent
Technologies; ‘Permanent Gases on a COX Module Using
an Agilent 490 Micro GC’; 2010.
For More Information
These data represent typical results. For more information on
our products and services, visit our Web site at
www.agilent.com/chem.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2011
Printed in the USA
June 2, 2011
5990-8069EN
BIOGAS Analyser
BIOGAS analyser
Specifications Model 490-GC
Configuration: one plug- and-play GC
channel
Detection Limits

WCOT columns: 1ppm

Micro-packed columns: 10ppm
Operating Range

Concentration: 1ppm to 100%
level
6

Linear dynamic range: 10
Power Requirements
Injector
Repeatability:
Communication



Control:


SERVICE MERGES QUALITY
Analytical Solutions and Products B.V.
Distelweg 80m ● Amsterdam
P.O. box 37146 ● 1030 AC ● Amsterdam
Tel. +31 (0)20 49 24 748 ● E-mail info@asap4u.nl
Fax. +31 (0)20 33 72 798 ● homepage www.asap4u.nl
TCD Detector


control for the BIO gas channel with
its separate pneumatics, injector,
column and detector.
Control of max two stream. One
process stream and one calibration
stream
Micro-machined injector with no
moving parts
Injection volume:1µl to 10µl,
software selectable
Optional heated injector: 30°C to
110°C, including heated transfer line
Environmental Requirements
Column Oven



Temperature range: 30°C to 180°C,
isothermal
Optional backflush capability
All capillary columns available
Control/Data Handling Software



<0.5% RSD for propane at 1
mol % level for WCOT columns
at constant temperature and
pressure
Standard packag Pro Software
Regulatory compliance and reports:
meet requirements, particularly for
the natural gas and petrochemical
industries
Special packages: ISOCAL and BTU
for natural (BIO) gas properties,
such as calorific value and relative
density, meet ISO 6976, GPA 2171,
and ASTM D 3588 standards
Sample gas
Flow
Minimum 12
Carrier gas
Argon
Helium
Hydrogen
Nitrogen
16
16
16
16


Humidity (relative): 0% to 95%
non-condensing
Temperature 0°C to 30°C in a
controlled atmosphere







Main power: 12 VAC
Opt: 100-240 VAC 50-60 Hz
Power consumption: 130 Watt
Ethernet TCP/IP with static IP
address
RS-232
Optional: Com port for external
devices, selectable RS-232 or
RS-485
Optional: fibre optic modem
Optional: gsm/gprs modem
Optional: wireless TCP/IP
Optional: 4-20 mA outputs
Optional: digital outputs
Dimensions and Weight
Hazardous Area Classification





Enclosure material Aluminium
280 mm (W) x 150 mm (D) x
300 mm (H)
Weight: 5.2 kg
Pressure
Connection
ml/min
0-1
barG 1/8" OD
1/16" OD
ml/min
ml/min
ml/min
ml/min



5,5±0,1
5,5±0,1
5,5±0,1
5,5±0,1
barG
barG
barG
barG
1/8"
1/8"
1/8"
1/8"
OD
OD
OD
OD
ATEX Zone 2
II 3G Ex nA IIC T3
1
Grade / Purity
-
4.8 / 99,998%
4.8 / 99,998%
4.8 / 99,998%
4.8 / 99,998%
Dewpoint
Non condensing
0 - 110°C
< -30°C
< -30°C
< -30°C
< -30°C
BIOGAS Analyser
Analytical Solutions and Products B.V.
Distelweg 80m ● Amsterdam
P.O. box 37146 ● 1030 AC ● Amsterdam
Tel. +31 (0)20 49 24 748 ● E-mail info@asap4u.nl
Fax. +31 (0)20 33 72 798 ● homepage www.asap4u.nl
CO2 analyser Infrared Smart gas sensor
Measuring principle:
Measurement range:
Gas supply:
Gas line connectors:
Flow rate:
Dimensions:
Warm-up time:
Non Dispersive Infra-Red (NDIR), dual wavelength
0-100 % CO2 in CH4
flow through cell
3 mm internal, 5 mm outer diameter
0.2 to 0.8 l/min (constant)
Length (model dependent) x 28 mm x 42 mm (L x W x H)
< 2 minutes (start up time)
< 30 minutes (full specification)
SERVICE MERGES QUALITY
(2)
Measuring response
Response time (t90):
Digital resolution (@ zero):
Detection Limit (3s):
Repeatability:
(4)
Linearity error :
(5)
Long term stability (zero) :
5)
Long term stability (span) ( :
(1)
Appr. 15 s (@ 0.5 l/min)
(1)
1 ppm / 0.1 % LEL / 0.01 Vol.-% / 0.1 Vol.-%
(3)
≤ 1 % FS (typically)
≤ +/- 1 % FS(3)
(3)
≤ +/- 2 % FS
(3)
≤ +/- 2 % FS over 12 month period
(3)
≤ +/- 2 % FS over 12 month period
(6)
Influencing variable
Temp. dependence (zero):
Temp. dependence (span):
Pressure dependence (zero):
Pressure dependence (span):
≤ +/- 0.1 % FS per °C
(3)
≤ +/- 0.2 % FS per °C
(1)
0.1 % to 0.2 % value per hPa
Electrical inputs and outputs
Supply voltage:
Supply current:
Power consumption:
6 V DC +/- 5 %
70 mA average, max. 140 mA
< 1 Watt
Outputs
Digital output signal:
Calibration:
Modbus ASCII via UART
zero and span by SW
Climatic conditions
Operating temperature:
Storage temperature:
Air pressure:
Humidity:
-10 °C to 40 °C
-20 °C to 60 °C
800 to 1200 hPa
0 % to 95 % rel. humidity (not condensing)
1)
(3)
Dependent on the gas and the measurement range
2) Relating to sample gas pressure 1013 hPa absolute, 0.5 l/min gas flow and 25°C ambient and gas
temperature
3) FS = Full scale
4) Stated linearity error excludes calibration gas tolerance of ± 2 %
5) For dry and clean test gas at 25°C and 1013hPa absolute - depending on the operating and ambient
conditions values may differ
6) Relating to calibration conditions (see final check)
Fast Refinery Gas Analysis Using the
490 Micro GC QUAD
Application Note
Authors
Introduction
Coen Duvekot
Agilent Technologies, Inc.
There is a large variation in the composition and source of refinery gases. Therefore,
the precise and accurate analysis of these gases is a significant challenge in today’s
refineries. Typical sources include fluid coking overheads, ethylene, propylene,
fuel gas, stack gas, off gas, etc. The physical stream ranges from gas to highly
pressurized gas or liquid.
Very fast refinery gas analysis (RGA) is possible with the portable 490 Micro GC
QUAD. This note describes the use of the 490 Micro GC for RGA, with results
obtained in about two minutes.
Instrumentation
Refinery Gas standard
490 Micro GC QUAD
• Channel 1: Molsieve with back flush
• Channel 2: CP-PoraPlot U with back
flush
• Channel 3: Aluminium oxide with
back flush
• Channel 4: CP-Sil 5 CB
The Molsieve channel and the
aluminium oxide channel are equipped
with extra in-line filters between the
manifold and the column module to
ensure moisture and carbon-dioxidefree carrier gas. This enhances column
lifetime and, most importantly, leads to
stable retention times.
GC control and data handling software:
Galaxie Chromatography Software.
Component
Amt (%)
Peak #
Component
Amt (%)
2
4
5
6
7
8
9
10
11
12
13
14
Helium
Nitrogen
Methane
Carbon monoxide
Carbon dioxide
Ethylene
Ethane
Acetylene
Hydrogen sulfide
Propane
Propylene
iso-Butane
Bal
5.1
24.9
1.0
0.5
24.9
5.0
1.0
1.01
5.0
5.0
0.5
15
16
17
18
19
20
21
22
23
24
25
Propadiene
n-Butane
tr-2-Butylene
1-Butylene
iso-Butylene
cis-2-Butylene
iso-Pentane
Methyl acetylene
n-Pentane
1, 3-Butadiene
n-Hexane
0.62
1.0
0.5
0.5
1.01
0.5
0.5
1.0
0.2
1.0
0.2
Channel 1
Channel 2
Channel 3
Channel 4
10 m
Molsieve
10 m
CP-PoraPLOT U
10 m
Al2O3/KCL
8m
CP-Sil 5 CB
Injector Temp (°C)
110
110
110
110
Column Temp (°C)
80
100
100
80
Carrier Gas
Argon
Helium
Helium
Helium
Column Head Pressure (kPa)
150
205
70
205
Injection Time (ms)
40
10
10
100
Back Flush Time (s)
11
7.1
33
N/A
Conditions
Table 2. Chromatographic conditions
Materials and Reagents
Channel 1, equipped with a Molsieve
column, separates and analyzes the
permanent gases except for carbon
dioxide. Channel 2, with a CP-PoraPLOT
U column, separates and analyzes
the C2 gases and hydrogen sulfide.
The C3 and C4 hydrocarbons are
analyzed on the third channel with
an Al2O3 column. Finally, the higher
hydrocarbons are analyzed on the
fourth channel, with a CP-Sil 5 CB
column.
Peak
#
6
Results and Discussion
6
Figures 1 and 2 show chromatograms
of the Molsieve channel 1.
Table 1. Peak identification and composition of
gas standards
2
2
4
4
80
80
5
Gas Standard
Peak
#
Component
1
3
4
5
6
Hydrogen
Oxygen
Nitrogen
Methane
Carbon monoxide
Sec
Sec105
105
5
Amt (%)
44
11
25
Bal
25
22
25
25
66
Sec
Sec
120120
Figure 2. Refinery gas on the Molsieve column,
channel 1
33
Sec
120
120
Figure 1. Standard gas on the Molsieve column,
channel 1
2
Hydrogen or helium, oxygen, nitrogen
methane and carbon monoxide were
separated and analyzed. Later eluting
components were back flushed to vent.
88
77
99
10
10
11
11
10
10
20
20
Sec
30
30
Sec. 40
40
Figure 3. Refinery gas on the CP-PoraPLOT U
column, channel 2
Stable retention times are key factors
for good chromatographic results.
Repeatability results derived from Table
3 and Figure 5 for retention times are
superb with RSDs around 0.1% and no
drift.
On the CP-PoraPLOT U channel
(channel 2), the C2 hydrocarbons,
hydrogen sulfide and carbon dioxide
were separated and analyzed. The
channel was equipped with a back
flush later eluting components to
vent.
12
12 13
13
1616
19
19
15
10
10 14 15
14
40
40
171718
18
60
60
Figure 4. Refinery gas on the aluminium oxide
column, channel 3
On channel 2 the C3 and C4 saturated
and unsaturated hydrocarbons were
separated and analyzed. This channel
was also equipped with back flush
in order to prevent the later eluting
hydrocarbons from entering the
analytical column. This prevented
the later eluting components from
interfering with the next analysis
causing “ghost” peaks and/or baseline
drift and higher noise. Furthermore,
this channel was equipped with
extra filters in the carrier gas lines,
effectively protecting the analytical
column from traces of moisture and
carbon dioxide that could influence
the chromatographic properties of the
stationary phase in the long term.
2121
20
20
80
80
Sec
2424
22
22
2323
100
100
3
Sec.
120
120
Tr (min)
Tr (min)
22
tr-2-Butylene
1-Butylene
iso-Butylene
cis-2-Butylene
iso-Pentane
Methyl acetylene
2,3-Butadiene
1.5
1.5
1
0
0
5
5
10
10
20
15
Run # 15
25
20
25
30
Run #30
Figure 5. Repeatability figures for the aluminium oxide channel, channel 3
Table 3. Repeatability figures for the aluminium oxide channel
Run #
Tr (min)
tr-2-Butylene
Tr (min)
1-Butylene
Tr (min)
iso-Butylene
Tr (min)
cis-2-Butylene
Tr (min)
iso-Pentane
Tr (min)
Methyl acetylene
Tr (min)
2, 3-Butadiene
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
1.2672
1.266
1.2657
1.2647
1.2647
1.265
1.2648
1.2653
1.2653
1.2647
1.265
1.2667
1.2658
1.2655
1.2655
1.2658
1.2653
1.2657
1.2657
1.2655
1.2663
1.2667
1.2672
1.2667
1.2675
1.2678
1.2683
1.2685
1.2682
1.2685
1.2963
1.2952
1.2948
1.2938
1.2937
1.2942
1.2938
1.2943
1.2943
1.2938
1.294
1.2958
1.2948
1.2945
1.2947
1.295
1.2945
1.2948
1.2947
1.2947
1.2953
1.2958
1.2963
1.2958
1.2967
1.2968
1.2975
1.2975
1.2973
1.2977
1.366
1.3647
1.3643
1.3632
1.3633
1.3633
1.3632
1.364
1.3638
1.3633
1.3633
1.3653
1.3643
1.3638
1.364
1.3645
1.3638
1.3642
1.3642
1.364
1.3648
1.3653
1.366
1.3655
1.3662
1.3667
1.367
1.3673
1.3668
1.3673
1.4447
1.4437
1.443
1.442
1.442
1.4423
1.442
1.4427
1.4423
1.442
1.4422
1.444
1.4432
1.4427
1.4428
1.4432
1.4425
1.443
1.443
1.4428
1.4435
1.4443
1.4448
1.4443
1.445
1.4455
1.446
1.4462
1.446
1.4462
1.7797
1.7772
1.7768
1.7755
1.7758
1.7757
1.7753
1.7763
1.776
1.7753
1.7752
1.778
1.7768
1.7762
1.7763
1.7768
1.776
1.7765
1.7765
1.7762
1.7775
1.7782
1.7793
1.7782
1.7788
1.7798
1.7807
1.7803
1.7802
1.781
1.934
1.9322
1.9323
1.931
1.931
1.9315
1.9303
1.931
1.9308
1.9305
1.9303
1.9337
1.9322
1.9322
1.9322
1.9325
1.9315
1.9322
1.9312
1.932
1.9328
1.934
1.9353
1.9338
1.9343
1.9357
1.936
1.936
1.9367
1.9367
2.0155
2.0122
2.0115
2.0097
2.0102
2.0102
2.0092
2.0105
2.0108
2.0095
2.0098
2.0128
2.0117
2.0108
2.011
2.0115
2.0107
2.011
2.0108
2.0108
2.012
2.0133
2.0145
2.013
2.0138
2.015
2.0162
2.0158
2.016
2.0163
Average
Std Dev
Rsd %
1.2662
0.0012
0.10%
1.2953
0.0012
0.09%
1.3648
0.0013
0.10%
1.4436
0.0014
0.10%
1.7774
0.0018
0.10%
1.9329
0.0020
0.10%
2.0122
0.0022
0.11%
4
Table 4. Reproducibility figures
Day
tr-2-Butylene
1-Butylene
iso-Butylene
cis-2-Butylene
iso-Pentane
Methyl acetylene
2, 3-Butadiene
1
2
3
4
8
9
10
1.2695
1.2678
1.2668
1.2665
1.2697
1.2681
1.2667
1.2988
1.2970
1.2958
1.2956
1.2989
1.2973
1.2957
1.3687
1.3668
1.3654
1.3652
1.3689
1.3671
1.3655
1.4481
1.4458
1.4443
1.4439
1.4483
1.4462
1.4443
1.7849
1.7815
1.7787
1.7781
1.7854
1.7821
1.7785
1.9406
1.9370
1.9339
1.9333
1.9405
1.9367
1.9345
2.0216
2.0173
2.0137
2.0130
2.0222
2.0180
2.0139
Average
St. dev.
RSD
1.2679
0.0013
0.10%
1.2970
0.0014
0.11%
1.3668
0.0015
0.11%
1.4458
0.0018
0.13%
1.7813
0.0031
0.17%
1.9366
0.0030
0.15%
2.0171
0.0037
0.19%
Table 4 and Figure 6 show the effects
over several days. RSDs are only
slightly higher when compared to
the “results-per-day” which is to be
expected. However, the results are very
good, demonstrating the suitability
of the Al2O3 channel for this type of
analysis.
Figure 6 shows no drift in retention
time of components analyzed on the
Al2O3 channel over ten days.
Figure 7 shows a chromatogram of
refinery gas on the CP-Sil 5 CB channel.
In this case the higher hydrocarbons
C5+ were analyzed.
Tr (min)
RSDs below 0.2% are shown in Table
4. During the ten day laboratory
experiments no drift in retention times
were observed, as can be seen in
Figure 6.
2.0
2.0
Tr (min)
tr-2-Butylene
1-Butylene
iso-Butylene
cis-2-Butylene
iso-Pentane
Methyl acetylene
2,3-Butadiene
1.5
1.5
1.0
1.0
00
55
10
10
Analysis Day
Analysis Day
Figure 6. Reproducibility of the aluminium oxide channel, channel 3
5
21
21
2323
2525
15
15
20
20
25
25
30
30
35
35
Sec
40
40
45
45
50
50
55
55
Sec.60
60
Figure 7. Refinery gas on the CP-Sil 5 CB
column, channel 4
Conclusion
The 490 Micro GC QUAD was
successfully used for the analysis of
refinery gas. The permanent gases
helium, hydrogen, oxygen, nitrogen,
methane and carbon monoxide were
analyzed on the Molsieve channel.
The C2 hydrocarbons, carbon dioxide
and hydrogen sulfide were analyzed
on the second channel equipped with
a CP-PoraPLOT U column. On the third
channel, with an aluminium oxide
column, the C3 and C4 hydrocarbons
were analyzed. This channel was
equipped with extra in-line filters to
ensure moisture and carbon-dioxidefree carrier gas. This significantly
enhanced column lifetime and ensured
long-term stable retention times.
Finally, the fourth channel, equipped
with a CP-Sil 5 CB column, analyzed the
C5+ hydrocarbons.
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This information is subject to change without notice.
© Agilent Technologies, Inc. 2010
Published in UK, August 03, 2010
SI-02233
Mine Gas Analysis Using the
490 Micro GC
Application Note
Authors
Introduction
Darren Brady
Safety in Mines Testing and Research
Station (SIMTARS)
Department for Natural Resources
and Mines, Queensland Government,
Australia
This note describes the use of the 490 Micro GC for the analyses of mine gas, and
especially carbon monoxide at low level, detection of which is essential for the
safety of mine workers. Three independent GC channels analyze the sample in less
than two minutes, including permanent gases and C1-C2 hydrocarbons.
Instrumentation
490 Micro GC
• Channel 1: Molsieve
Conditions
Table 1. Chromatographic conditions
• Channel 2: Molsieve
Channel 1
Channel 2
Channel 3
• Channel 3: CP-PoraPlot Q
10 m Molsieve
10 m Molsieve
10 m
CP-PoraPLOT Q
Injector Temp (°C)
50
50
50
Column Temp (°C)
100
70
70
Carrier Gas
Argon
Helium
Helium
Column Head Pressure, Static (kPa)
150
150
150
Injection Time (ms)
100
100
100
Back Flush Time (s)
Not present
5.65
Not present
Detector Sensitivity
Medium
Extra high
High
Materials and Methods
The 490 Micro GC analysis uses argon
on Molsieve channel 1. This was
done to measure hydrogen, helium
and all other permanent gases in
one channel. Using argon as carrier
gas gives an excellent response for
hydrogen and helium but a reduced
sensitivity for the permanent gases
compared to using hydrogen/
helium as carrier gas. The Limit of
Quantification (LOQ) is approximately
50 to 100 ppm for oxygen, nitrogen
and CO. Using nitrogen as carrier gas
detects no nitrogen, and almost no
oxygen or carbon monoxide. Very low
concentrations of oxygen and nitrogen
(ppm level) can be measured on the
carbon monoxide Molsieve channel 2.
Low carbon monoxide levels were
detected on Molsieve channel 2, with
no interference from bulk methane.
The mixture to test low levels of CO
was 2 ppm CO in methane. To detect
low CO in bulk methane two settings
are crucial. First, the use of back flush
enables the elimination of peak tailing
interference of the bulk methane
during the elution of CO. Secondly,
the detector was set in the extra high
sensitivity mode. However, as a result
of using this mode, auto ranging of
the detector was set off and high
concentrations of components could
not be measured, since the signal was
cut off. CO2, ethane and ethylene were
measured on channel 3 using a CPPoraPLOT Q column.
Results and Discussion
4
Separations are shown in the figures,
with Figure 1 indicating the effect
of using the detector in extra high
sensitivity mode. Figure 3 demonstrates
the ability of the 490 Micro GC to detect
trace levels of carbon monoxide in the
presence of bulk methane.
5, approx 200 ppm
70
120
120
70
Figure 2. Carbon monoxide on channel 2
Peak identification
Rt (s)
1. Hydrogen
27
2. Oxygen
37
3. Nitrogen
48
4. Methane
66
5. Carbon monoxide
111
6. Carbon dioxide
24
7. Ethylene
30
8. Ethane 34
3
Methane bulk at >99%
Carbon monoxide at ppm level
70
70
Figure 3. Low ppm carbon monoxide sample in
methane, channel 2
4
Signal is
cut off
2
1
20
100
20
100
Figure 1. Permanent gases on channel 1
2
120120
6
7
8
20
20
40
40
Figure 4. Carbon dioxide, ethane and ethylene
on channel 3
Conclusion
The 490 Micro GC successfully
analyzed a sample of mine gas.
The excellent performance of the
instrument was shown by its capability
to detect very low levels of potentially
lethal carbon monoxide, even in the
presence of bulk methane.
www.agilent.com/chem
This information is subject to change without notice.
© Agilent Technologies, Inc. 2010
Published in UK, August 16, 2010
SI-02235
Fast On-Site Mine Safety Analysis by
the Agilent 490 Micro GC
Application Note
Micro Gas Chromatography, Mine gas analysis, Mine safety
Authors
Darren Brady
Safety in Mines Testing and Research
Station (SIMTARS)/Queensland
Government
Goodna, Australia
Remko van Loon
Agilent Technologies, Inc.
Middelburg, the Netherlands
Abstract
Numerous mine disasters with loss of many lives continue to occur today. This fact
dramatically emphasizes the importance of fast and accurate determination of the
mine atmosphere for an early warning of hazards in day-to-day mine operations or
after an accident has happened. This application note describes a method for fast
on-site analysis of mine gases in less than 100 seconds using the Agilent 490 Micro
GC equipped with four independent column channels.
Introduction
Micro GC setup and conditions
The 490 Micro GC (p/n G3581A) used for the analysis of mine
gas consists of a quad cabinet (Figure 1), and is equipped
with four column independent column channels. Each column
channel is a complete, miniaturized GC with electronic carrier
gas control, micro-machined injector, narrow-bore analytical
column, and micro-thermal conductivity detector (µTCD).
We all can recall the news bulletins reporting a mine accident
and, in some cases, the many lives that are lost. Therefore, to
have an early warning for multiple safety reasons, fast
analysis of the mine atmosphere is extremely important for
day-to-day mining activities. Moreover, a complete overview
of the gases in the mine, after an accident, is essential to
determine if the mine is safe for a rescue team to enter.
First, it is necessary to check for explosive gases in a mine
environment. During the formation of coal beds, some gases,
mainly methane and some ethane and hydrogen were trapped
in the coal. When these coal beds are mined, the gases are
released. Methane and other explosive gases, when mixed in
certain ratios with oxygen from the air, are highly explosive.
To prevent explosion hazards, it is necessary to monitor
flammable gases such as methane, hydrogen, and the
C2 hydrocarbons.
A second reason for mine gas analysis is that the absence of
carbon monoxide and the right oxygen and carbon dioxide
levels in the mine atmosphere are critical for the safety of the
mine workers and rescue teams.
Third, analyzing the gases in the mine can predict spontaneous combustion or detect a fire in an early stage.
Spontaneous combustion could happen when internal heat,
produced by chemical reactions in the coal, is generated
faster than it can be lost to the surrounding environment.
Hydrogen and ethylene are formed when temperatures rise
above 100 °C. The presence of low concentrations of these
components gives an indication of fire or elevated temperatures in an early stage. This increases the chance of
successfully dealing with the problem.
Figure 1.
The Safety in Mines Testing and Research Station (SIMTARS),
based in Queensland Australia has been providing and
supporting gas monitoring systems based on gas
chromatographs to the mining industry for over 20 years and
offer their services, support, and training to mining companies
to reduce the risks of mine explosions and help them after a
mine disaster. For the three reasons given, SIMTARS is using
the Agilent 490 Micro GC to provide a complete, fast, and
on-site analysis of the gases collected from the underground
mine.
2
Agilent 490 Micro GC with quad channel cabinet housing.
The first channel installed, is equipped with a 10 meter
CP-MolSieve 5Å column, running on argon as carrier gas for
the analysis of helium, hydrogen, oxygen, and nitrogen.
Channels 2 and 3 are identical and, like the first channel, are
equipped with a 10 meter CP-MolSieve 5Å column. However,
these channels have the optional backflush functionality and
run on helium carrier gas, for the analysis of methane and
carbon monoxide. Ethane and ethylene are analyzed on a
fourth channel using a 10 meter a PoraPLOT U column.
Table 1 shows the analytical conditions for all channels.
Table 1.
Agilent EZChrom Chromatography Data Software is used for
data acquisition, and SIMTARS EZGas Professional software,
specifically written for the mining industry, is used for calibration and result generating. The analysis results are exported
to Segas Professional, a software package developed by
SIMTARS, for additional combustibility calculations,
combustion ratios and trend analysis.
Fast mine safety analysis in less than 100 seconds
The first column channel, equipped with a CP-Molsieve 5Å
column, is used to analyze permanent gases, including
helium, hydrogen, oxygen and nitrogen. Figure 2 shows a
chromatogram where the compounds of interest are well
separated.
Analytical Conditions for Quad Channel Micro GC
Channel 1
CP-Molsieve 5A 10 m
Channel 2
CP-Molsieve 5A 10 m
Channel 3
CP-Molsieve 5A 10 m
Channel 4
PoraPLOT U 10 m
Column temperature
80 °C
80 °C
80 °C
60 °C
Carrier gas
argon, 120 kPa
helium, 150 kPa
helium, 150 kPa
helium, 100 kPa
Injector temperature
50 °C
50 °C
50 °C
50 °C
Injection time
100 ms
110 ms
110 ms
90 ms
Back flush time
no backflush
10
10
no backflush
Detector sensitivity
auto
auto
auto
auto
Invert signal
yes
no
no
no
Sample line temperature
40 °C
Sampling time
70 seconds
Sample 1
Low ppm level
helium and hydrogen
Oxygen
Helium 15 ppm
Hydrogen
3.5 ppm
Hydrogen 194 ppm
Nitrogen
Sample 2
Medium ppm level
helium and hydrogen
Helium 96 ppm
50 × zoom
0
20
40
60
80
100
Seconds
Figure 2.
Chromatogram for helium, hydrogen, oxygen and nitrogen separation on the first column
channel.
3
The molecular sieve channel is running on argon as the
carrier gas, which enables the determination of low concentrations of helium and hydrogen. All other compounds will
have an increased detection limit by approximately a factor of
10, compared to helium, when argon is used as a carrier gas.
However, oxygen and nitrogen are present at percentage
levels in the mine atmosphere, which allows the use of argon
carrier gas for detection of these gases. Concentration results
for hydrogen, oxygen, and nitrogen are used by SIMTARS for
combustibility calculations.
The typical limit of detection for the µTCD, specified by
Agilent, is 1 ppm for early eluting components on a Wall
Coated Open Tubular (WCOT) column and 10 ppm on Porous
Layer Open Tubular (PLOT) and micro-packed column types.
The CP-MolSieve 5Å column is a PLOT type column, however
when it comes to carbon monoxide at low levels, the exact
concentration is of less importance for SIMTARS than the
trend. Even a slight increasing trend of the chromatogram’s
base line at the carbon monoxide retention time is monitored
for early indications of spontaneous combustion in the mine.
Helium, naturally available in our atmosphere at low ppm
concentrations, is analyzed on this channel as well. On a
molecular sieve column, helium and hydrogen elute close
together. Analysis of helium prevents it from being incorrectly
reported as hydrogen. This can result in the erroneous
conclusion that spontaneous combustion is occurring. From
time to time, helium is also used as a tracer gas to determine
gas movements in the underground mine.
This MolSieve 5Å channel is equipped with back flush
functionality to ensure moisture, carbon dioxide, and the
C2 hydrocarbons are backflushed to vent, to maintain the
separation efficiency of the molecular sieve column. Moisture
and carbon dioxide tend to adsorb quickly to the Molsieve 5Å
stationary phase changing its chromatographic properties.
This could result, over time, in retention shifts and loss of
separation.
Channel two also includes a 10 meter MolSieve 5Å, this time
with helium as the carrier gas. This channel is used for the
analysis of methane and carbon monoxide. Figure 3 shows a
chromatogram for two different samples, one containing a
medium level for carbon monoxide (~ 200 ppm) and the other
with a very low level of carbon monoxide. In this chromatogram, excellent separation and analysis of methane and
carbon monoxide in less than 100 seconds is obtained.
For SIMTARS, the analysis of methane for explosion risk
reasons and carbon monoxide for combustion identification
are of high importance, especially when the Micro GC is taken
into the field after a mine disaster. Therefore, this column
channel is duplicated to the third position of the instrument to
allow optimized operation for the analysis of each, and to
have a back up available at all times. When one column is
reconditioned, the other column can still be used for analysis.
Carbon monoxide 3 ppm
Methane
120 ppm
Sample 1
Low ppm level
carbon monoxide
10 x zoom
Methane 0.79%
Carbon monoxide
193 ppm
20
40
60
80
Sample 2
Medium ppm level
carbon monoxide
100
Seconds
Figure 3.
Chromatogram for methane and carbon monoxide on the second column channel.
4
The fourth channel, equipped with a 10 meter PoraPLOT U
column and helium as the carrier gas, is used to analyze
carbon dioxide, ethane, and ethylene. Figure 4 shows an
example for baseline separation of these three components.
Excellent repeatability for quantity and retention
time
Repeatability, reported as relative standard deviation, shows
excellent results for both concentration and retention time as
shown in Table 2. Typical values, based on quantity, are determined around 0.05% RSD for components that are present in
the sample at percentage levels and between 0.1 to 0.6% for
ppm level components. Retention time repeatability, for all
components of interest, is calculated at 0.015% or lower.
The right carbon dioxide level is of importance for the safety
of the mine workers and rescue personnel. Moreover, the
results for carbon dioxide and ethane as well, are used in the
combustibility calculations by SIMTARS. Ethylene, like
hydrogen, is formed when coal temperatures rise above
100 °C and, therefore, is used as an early warning for
spontaneous combustion or a fire.
Ethane 1.4 ppm
Ethylene
1.9 ppm
Sample 1
Low ppm level
ethane and
ethylene
Carbon
dioxide
Ethylene
113 ppm
Ethane
98 ppm
Sample 2
Medium ppm level
ethane and
ethylene
30 × zoom
30
40
50
60
Seconds
Figure 4.
Chromatogram for carbon dioxide, ethane and ethylene on the fourth column channel.
Table 2.
Typical Repeatability Figures (Population Size is 10) for the Agilent 490 Micro GC
Component
Column
channel
Concentration
average
Concentration
unit
Concentration
RSD (%)
Retention time
average (seconds)
Retention time
RSD (%)
Helium
1
102.8
ppm
0.10
35.22
0.015
Hydrogen
1
118.5
ppm
0.11
38.79
0.014
Oxygen
1
20.4
%
0.044
54.65
0.0088
Nitrogen
1
72.4
%
0.056
70.00
0.011
Methane
2 (and 3)
1.85
%
0.054
54.09
0.0087
Carbon monoxide
2 (and 3)
181.9
ppm
0.25
71.35
0.012
Carbon dioxide
4
1.91
%
0.040
43.92
0.014
Ethylene
4
110.8
ppm
0.61
48.01
0.013
Ethane
4
92.3
ppm
0.25
51.62
0.013
5
Conclusion
This application note clearly show that the 490 Micro GC is a
powerful tool for accurate mine safety analysis.
The major reason for SIMTARS using the 490 Micro GC is
that it provides a complete, fast and on-site analysis of the
mine gases collected from underground. Moreover, the 490
Micro GC detects compounds that are not covered by the
mine’s continuous monitoring system.
The 490 Micro GC analyzes mine environment samples in
less than 100 seconds resulting in multiple results per hour
for accurate trend analysis and thus better informed decision
making for the prevention of mine disasters.
In addition, the 490 Micro GC gives SIMTARS rapid and reliable results to determine, after a mine disaster, the status of
the underground environment before deciding to send in a
rescue teams.
For More Information
These data represent typical results. For more information on
our products and services, visit our Web site at
www.agilent.com/chem.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2012
Printed in the USA
June 6, 2012
5991-0438EN
Permanent Gases on a COX Module
Using a Agilent 490 Micro GC
Application Note
Micro Gas Chromatography
Authors
Abstract
Simone Darphorn-Hooijschuur and
This application note demonstrates the capabilities of the COX column with the
Marijn van Harmelen
Agilent 490 Micro GC, including separation of permanent gases and backflush
Avantium
possibilities to ensure extended column lifetimes.
Amsterdam
The Netherlands
Remko van Loon and Coen Duvekot
Agilent Technologies
Middelburg
The Netherlands
Introduction
Separation of permanent gases is usually performed on a Molsieve column. This
column offers the best separation for all permanent gases but also has some severe
drawbacks. Water and carbon dioxide do not elute from a Molsieve column under
regular GC conditions. A bake out at high temperatures (250 – 300 °C) is needed to
fully regenerate the column. Regeneration is very time consuming in a Micro GC
usually taking overnight or longer because the maximum temperature is 180 °C.
In addition, it is likely that regeneration from moisture does not occur at this
temperature.
If there is no need to separate oxygen and nitrogen, the COX column is a better
alternative. It delivers good separation of permanent gases, and carbon dioxide
elutes from the column. COX is an ideal alternative for a Molsieve column, offering
prolonged lifetime and instrument uptime.
Table 1.
Experimental
Instrumentation
An Agilent 490 Micro GC system with a COX column module
was used for these experiments. The COX column module
was equipped with a heated injector and an optinal precolumn with backflush.
Conditions
Column temperature
100 °C
Carrier gas
Argon, 100 kPa
Backflush to vent time
13 s
Injection time
80 ms
Injection temperature
110 °C
Sample line temperature
100 °C
Sampling time
30 s
Stabilization time
5s
Run time
200 s
Repeatability Figures Per Component on Peak Area
Run
He
H2
N2
CO
CH4
CO2
1
943213
16024030
20593423
1439534
1535598
1064007
2
947355
16092042
20685887
1444814
1538714
1062243
3
949818
16142635
20749728
1446996
1544418
1070193
4
949808
16167426
20781405
1449939
1542239
1066091
5
952725
16194789
20815739
1453498
1539162
1066940
6
952107
16206479
20826967
1456289
1543749
1063772
7
954648
16228802
20856620
1455219
1548126
1074325
8
954635
16249294
20879589
1456795
1547760
1079645
9
955454
16251565
20883920
1456611
1552320
1064839
10
955872
16250493
20901246
1473831
1547242
1065483
Average
951563.5
16180756
20797452
1453353
1543933
1067754
St. Dev
4053
75870
97930
9249
5122
5456
RSD%
0.43
0.47
0.47
0.64
0.33
0.51
Sample Information
Results and Discussion
Standard gas samples were used. Concentrations were in
% levels.
The above settings produce the chromatogram shown in
Figure 1, with repeatability data in Table 1.
The chromatogram shows a baseline separation of helium and
hydrogen. Oxygen and nitrogen eluted as a single peak but
separate from carbon monoxide and methane. Carbon dioxide
eluted perfectly.
2
3
Peak
Identification
1
He
2
H2
3
N2 + O2
4
CO
5
CH 4
6
CO 2
1
4
5
6
0
40
60
80
100
120
140
Sec
Figure 1.
Excellent baseline separation of a gas sample on a COX column.
2
160
180
200
Nitrogen
Ethane
Methane
No backflush
Water
CO2
Min
0
3
Water, ethane and higher hydrocarbons
are backflushed to vent.
Optimal tuned backflush
Oven: 120 °C
Carrier gas: helium, 200 kPa
Figure 2.
Backflush of water and ethane.
Other components such as water and higher hydrocarbons
were backflushed to vent.
Although the COX column does not separate oxygen and
nitrogen, it does separate hydrogen and helium. In addition,
carbon dioxide is analyzed and water elutes from the COX
column. Repeatability figures are good, ensuring reliable
analysis results.
If the backflush time is set at a high value then virtually all
the sample components enter the analytical column and
eventually elute. However, if higher hydrocarbons are present
the COX column is polluted because these components elute
late and can influence the succeeding analysis.
The COX module can be equipped with a precolumn. This
allows backflush of higher components and prolongs column
lifetime.
Figure 2 shows the elution of water and ethane if no backflush is applied. If the backflush time is optimally tuned,
water, ethane and higher hydrocarbons are backflushed to
vent and does not enter the analytical column.
The Agilent 490 Micro GC is a rugged, compact and portable
“lab-quality” gas analysis platform. When the composition of
gas mixtures is critical, this fifth generation Micro Gas
Chromatograph generates more data in less time for faster
and better performance.
Conclusion
For the analysis of permanent gases the COX column is a
good alternative to the commonly used Molsieve column.
For More Information
For more information on our products and services, visit our
Web site at www.agilent.com/chem.
3
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this
publication are subject to change without notice.
© Agilent Technologies, Inc., 2010
Printed in the USA
December 28, 2010
5990-7054EN
Analysis of Acetone, n-Hexane,
MIBK, MNBK, and MIBC Using the
Agilent 490 Micro GC
Application Note
Micro Gas Chromatography, Environmental Analysis
Authors
Introduction
Tim Lenior and Hans-Peter Smid, ASaP
This application note shows the analysis of Aceton, n-Hexane, Methyl iso-Butyl
Ketone (MIBK), Methyl iso-Butyl Carbinol (MIBC), and Methyl n-Butyl Ketone
(MNBK, 2-Hexanone) using the Agilent 490 Micro GC.
Amsterdam, the Netherlands
Remko van Loon
Agilent Technologies, Inc.
Middelburg, the Netherlands
To decontaminate a polluted soil environment, steam is injected into the ground.
The contaminants will evaporate from the soil and the steam is collected and
cleaned. The 490 Micro GC is used to monitor this decontamination process.
The initial soil sample, including the contaminants, is collected and handled by
a processing plant. This system, designed and build by Analytical Solutions and
Products (ASaP) in the Netherlands, separates the gas from the soil sample. The
final gas sample, containing the contaminations in ppm range, high concentration
of ambient air, and some moisture vapor, is analyzed by the 490 Micro GC. The
compounds of interest can be separated on both a CP-Sil 5 CB column channel and
a CP-Wax 52 CB column channel.
The Agilent 490 Micro GC is a rugged, compact and portable lab-quality gas
analysis platform. When the composition of gas mixtures is critical, count on this
fifth-generation micro gas chromatography.
Instrumentation
Sample information
For this analysis, an Agilent 490 Micro GC (p/n G3581A),
equipped with a CP-Sil 5 CB and CP-Wax 52 CB, is used to
analyze the compounds of interest.
CP-Sil 5 CB, 4m
CP-Wax 52 CB, 10m
(special)
Column temperature
60 °C
60 °C
Carrier gas
Helium, 200 kPa
Helium, 200 kPa
Injector temperature
60 °C
60 °C
Injection time
200 ms
200 ms
Sample line temperature
60 °C
60 °C
Nitrogen/Oxygen (Air)
Matrix
Acetone
64 ppm
n-Hexane
15 ppm
Methyl iso-Butyl Ketone (MIBK)
250 ppm
Methyl iso-Butyl Carbinol (MIBC)
73 ppm
Methyl n-Butyl Ketone (MNBK)
20 ppm
CP-Sil 5 CB
CP-Wax 52 CB
Methyl iso-Butyl
Ketone (MIBK)
Methyl iso-Butyl
Ketone (MIBK)
Water
Acetone
n-Hexane
Acetone
Water
Methyl iso-Butyl
Carbinol (MIBC)
n-Hexane
Methyl n-Butyl
Ketone (MNBK)
Methyl n-Butyl
Ketone (MNBK)
0
20
40
60
80
100
10
30
50
Seconds
70
90
Seconds
Methyl iso-Butyl
Carbinol (MIBC)
110
130
150
For More Information
www.agilent.com/chem
These data represent typical results. For more information on
our products and services, visit our Web site at
www.agilent.com/chem.
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2011
Printed in the USA
June 8, 2011
5990-8361EN
Analysis of BTEX in Air using the
Agilent 490 Micro GC
Application Note
Micro Gas Chromatography, Environmental Analysis
Authors
Pascal Vattaire,
Agilent Technologies, Inc.
Les Ulis
France
Remko van Loon,
Agilent Technologies, Inc.
Middelburg
The Netherlands
Introduction
Monocyclic aromatic hydrocarbons are a class of chemicals with a six membered ring
structure and alternating double and single bonds between the carbon atoms. These
compounds are considered to be toxic and therefore of interest for analysis.
This application note shows the analysis of benzene, toluene, ethylbenzene, and the
xylenes in an air matrix using the Agilent 490 Micro GC. To separate all xylenes, including meta- and para-xylene, a special channel equipped with a 10-meter CP-Wax 52 CB
column is used. The standard 4-meter CP-Wax 52 CB column channel can be used for
the analysis of BTEX as well, however p- and m-xylene will co elute and reported as a
single result.
The advantage of the 490 Micro GC, in combination with the CP-WAX 52 CB column
channel, is the ease-of-use and the speed of analysis. The analysis of the BTEX compounds is performed in less than 150 seconds. The Agilent 490 Micro GC delivers labquality separations in an ultra-compact, portable instrument. You get the results you
need in seconds - for faster, better decision making and confident process control.
Instrumentation
Sample information
Instrument
Agilent 490 Micro GC (G3581A)
Matrix
Column channel
CP-Wax 52 CB, 10 m (special channel)
Benzene
low ppm range
Column temperature
50 °C
Toluene
low ppm range
Carrier gas
Helium, 150 kPa
Ethylbenzene
low ppm range
Injection time
50 msec
Xylenes
low ppm range
Air
Benzene
Toluene
p-Xylene
Ethylbenzene
m-Xylene
o-Xylene
5x Zoom
5x Zoom
0
30
60
90
120
150
Sec
For More Information
These data represent typical results. For more information on
our products and services, visit our Web site at
www.agilent.com/chem.
www.agilent.com/chem/microgc
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2011
Printed in the USA
December 1, 2011
5990-9527EN
Analysis of Volatile Solvents on
CP-Sil 5 CB using the
Agilent 490 Micro GC
Application Note
Micro Gas Chromatography, Environmental Analysis, Solvent Analysis
Author
Remko van Loon
Agilent Technologies, Inc.
Middelburg
The Netherlands
Introduction
This application note shows the analysis of Ethyl acetate, n-Hexane, Cyclohexane, isoOctane, Aniline, and Toluene in an Air matrix using the Agilent 490 Micro GC. These
volatile solvents, harmful to the environment, are analyzed on a CP-Sil 5 CB column
channel in less than 2 minutes.
When you need to analyze on a location where no carrier gas or power is available,
the portable field case option provides you measurements in the field. The 490 Micro
GC can easily be transported in this fully self-contained field case, built-in gas
cylinders, and rechargeable battery provide up to eight hours productive measuring
time.
The Agilent 490 Micro GC delivers lab-quality separations in an ultra-compact,
portable instrument. You get the results you need in seconds, for faster, better
decision making, and confident process control.
Instrumentation
Instrument
Column channel
Injector
Column temperature
Carrier gas
Injection time
Agilent 490 Micro GC (G3581A) with portable
field case
4 m CP-Sil 5 CB
Unheated
70 °C
Helium, 100 kPa
200 msec
Air matrix
Ethyl acetate
n-Hexane
Cyclohexane
Toluene
iso-Octane
Aniline
0
30
60
Seconds
90
120
For More Information
For more information on our products and services, visit our
Web site at www.agilent.com/chem.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2011
Printed in the USA
July 25, 2011
5990-8699EN
Analysis of Acetone, Methanol, and
Ethanol in Air using the
Agilent 490 Micro GC
Application Note
Micro Gas Chromatography, Environmental Analysis
Authors
Mohamed Bajja and Remko van Loon,
Agilent Technologies, Inc.
Middelburg
The Netherlands
Introduction
This application note shows the analysis of acetone, methanol, and ethanol in an air
matrix using the Agilent 490 Micro GC equipped with a CP-Wax 52 CB column channel.
The advantage of the Agilent 490 Micro GC, in combination with the CP-Wax 52 CB
column channel, is the ease-of-use and the speed of analysis. The analysis is
performed in less than 30 seconds.
The Agilent 490 Micro GC can optionally be equipped with a portable field case.
This self-contained field case can be used to measure at a location where no carrier
gas or power is available. Build-in gas cylinders and rechargeable batteries provide
up to eight hours productive field time.
The Agilent 490 Micro GC delivers lab-quality separations in an ultra-compact,
portable instrument. You get the results you need in seconds – for faster, better
decision making, and confident process control.
Instrumentation
Sample information
Instrument
Agilent 490 Micro GC (G3581A)
Air
Matrix
Column channel
CP-Wax 52 CB, 4 m
Acetone
0.07 %
Column temperature
60 °C
Methanol
0.31 %
Carrier gas
Helium, 150 kPa
Ethanol
0.16 %
Injector temperature
110 °C
Injection time
40 msec
Composite air peak
Methanol
Ethanol
Acetone
0
10
Seconds
20
30
For More Information
These data represent typical results. For more information on
our products and services, visit our Web site at
www.agilent.com/chem.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2011
Printed in the USA
October 13, 2011
5990-9105EN
Analysis of Dichloromethane from
Waste Water Using the 490 Micro GC
Application Note
Authors
Martin Pijl
Agilent Technologies, Inc.
Introduction
Dichloromethane (DCM) is a colorless, oily, organic liquid with a sweet, chloroformlike odor. It is mainly used to produce vinyl chloride monomer, the major precursor
for PVC production. It is also used as a solvent for resins and fats, and in
photography, photocopying, cosmetics, drugs and as a soil fumigant. DCM can be
harmful to wildlife and human health, and so it is regulated in Europe under EC
Directive 76/464 ‘Pollution of the aquatic environment by dangerous substances’
(plus daughter directives).
Fast, on-line analysis of DCM is accomplished using the Agilent 490 Micro GC.
Instrumentation
Instrument:
490 Micro GC
Module:
Fused silica, non-
polar phase
1
Peak Identification
1.
Air
2.
Dichloromethane
1
25,000
Conditions
Sample Conc:
Carrier Gas:
Injector Temp:
Detector:
7400 mg/m3 and 4 mg/m3
Helium, ca. 45 kPa
Unheated
µ-TCD
Materials and Reagents
Dichloromethane was extracted from
waste water via purge and trap. The
water was stripped and the stream
directly analyzed via the 490 Micro GC.
2
15,000
2
20,000
10,000
Results and Discussion
Figures 1 and 2 show the effect
of different dichloromethane
concentrations on its separation.
5,000
0
Sec
Figure 1. Dichloromethane in air at 7400 mg/m3
2
20 [sec]
20
Conclusion
11
-25
The 490 Micro GC successfully
analyzed waste water samples
containing dichloromethane, even at
very low levels. The 490 Micro GC
is a rugged, compact, “lab-quality”
gas analysis platform that delivers
high efficiency analyses. When
the composition of gas mixtures is
critical, this fifth generation microgas chromatograph generates more
data in less time for faster and better
performance.
uV
-50
-75
-100
2
2
-125
0
Figure 2. Dichloromethane in air at 4 mg/m3
Sec
20
20 [sec]
www.agilent.com/chem
This information is subject to change without notice.
© Agilent Technologies, Inc. 2010
Published in UK, August 20, 2010
SI-02642
Permanent Gas Analysis –
Separation of Helium, Neon and
Hydrogen a MolSieve 5A column using
the Agilent 490 Micro GC
Application Note
Micro Gas Chromatography, Permanent Gas Analysis
Author
Remko van Loon
Agilent Technologies, Inc.
Middelburg
The Netherlands
Introduction
This application note shows an example of the permanent gas analysis in a sample
with high % level of Oxygen and Nitrogen (Air) on an Agilent 490 Micro GC, including
the separation of Helium, Neon, and Hydrogen (ppm level). The separation of these
compounds is done on a 10 m MolSieve 5A column and requires the use of Argon as
carrier gas to detect all potential other carrier gases like Helium, Hydrogen, and
Nitrogen.
The advantage of the Agilent 490 Micro GC, is the ease-of-use and the speed of
analysis, resulting in a total analysis time of less than 40 seconds.
The Agilent 490 Micro GC is a rugged, compact, and portable lab-quality gas analysis
platform. When the composition of gas mixtures is critical, count on this fifth generation
micro gas chromatography.
Instrumentation
Instrument
Sample information
Agilent 490 Micro GC (G3581A)
Helium
ppm level
Column channel
MolSieve 5A, 10 m
Neon
ppm level
Column temperature
80 °C
Hydrogen
ppm level
Carrier gas
Argon, 240 kPa
Oxygen
high % level
Injector temperature
60 °C
Nitrogen
high % level
Injection time
60 msec
For More Information
These data represent typical results. For more information on
our products and services, visit our Web site at
www.agilent.com/chem.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2011
Printed in the USA
July 5, 2011
5990-8527EN
Permanent Gas Analysis – Separation
of Argon and Oxygen on a
MolSieve 5A Column using the
Agilent 490 Micro GC
Application Note
Micro Gas Chromatography, Permanent Gas Analysis
Authors
Mohamed Bajja and Remko van Loon
Agilent Technologies, Inc.
Middelburg
The Netherlands
Introduction
This application note shows an example of the analysis of permanent gases, including
the separation of Argon and Oxygen, using the Agilent 490 Micro GC. For the
separation of Argon and Oxygen, a High Resolution 20 m MolSieve 5A column is used.
The advantage of the Agilent 490 Micro GC is speed of analysis. Even with the
20 m HR MolSieve 5A column, you get the results fast. Total analysis time for the permanent gases until Nitrogen is approximately 3 minutes. The Agilent 490 Micro GC
delivers lab-quality separations in an ultra-compact, portable instrument.
Instrumentation
Sample information
Instrument
Column channel
Column temperature
Carrier gas
Injection time
Agilent 490 Micro GC (G3581A)
20 m MolSieve 5A
40 °C
Helium, 200 kPa
40 msec
Neon
Hydrogen
Argon
Oxygen
Nitrogen
Helium
18 ppm
1.0 %
0.2 %
0.2 %
0.2 %
matrix
Argon
Hydrogen
Oxygen
Neon
Nitrogen
15 × Zoom
Neon
30
Hydrogen
60
90
120
150
180
Seconds
For More Information
For more information on our products and services, visit our
Web site at www.agilent.com/chem.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2011
Printed in the USA
July 27, 2011
5990-8700EN
Fast Separation of Oxygen and Nitrogen
on a MolSieve 5A Channel Using the
Agilent 490 Micro GC
Application Note
Micro Gas Chromatography, Permanent Gas Analysis
Authors
Mohamed Bajja and Remko van Loon
Agilent Technologies, Inc.
Middelburg
The Netherlands
Introduction
When a really fast separation of Oxygen and Nitrogen is required, the Agilent
490 Micro GC, equipped with a short MolSieve 5A column channel, delivers the
speed you need.
This application note shows the fast separation of Oxygen and Nitrogen using a
4 m MolSieve 5A column channel instead of using the standard 10 m MolSieve 5A
column channel. The advantage of the Agilent 490 Micro GC, in combination with
this 4 m MolSieve 5A column channel, is the ease-of-use and the speed of analysis.
Nitrogen will elute in less than 20 s.
Argon and Oxygen will not be separated on the 4 m MolSieve 5A column. These
compounds will coelute. The separation of Argon and Oxygen requires the use of a
20 m MolSieve 5A column channel on a low temperature.
The Agilent 490 Micro GC is a rugged, compact and portable lab-quality gas
analysis platform. When the composition of gas mixtures is critical, count on this
fifth generation micro gas chromatography.
Instrumentation
Sample information
Instrument
Agilent 490 Micro GC (G3581A)
Hydrogen
1.0%
Column channel
MolSieve 5A, 4 m
Oxygen
0.4%
Column temperature
100 °C
Nitrogen
0.2%
Carrier gas
Helium, 100 kPa
Injection time
40 msec
For More Information
These data represent typical results. For more information on
our products and services, visit our Web site at
www.agilent.com/chem.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this publication are subject to change
without notice.
© Agilent Technologies, Inc., 2011
Printed in the USA
June 28, 2011
5990-8529EN
C1 – C3 Hydrocarbon Analysis Using
the Agilent 490 Micro GC – Separation
Characteristics for PoraPLOT U and
PoraPLOT Q Column Channels
Application Note
Micro Gas Chromatography, Hydrocarbon analysis
Author
Remko van Loon
Agilent Technologies, Inc.
Middelburg
The Netherlands
Introduction
This application note shows the possibilities and limitations in fast analysis of
saturated and unsaturated C1 to C3 hydrocarbons using an Agilent 490 Micro GC.
The chromatograms and results outline the similarities and differences when using
a CP-PoraPLOT U and a CP-PoraPLOT Q columns channels. Both the PoraPLOT U
and the PoraPLOT Q are capable of resolving methane from the composite air peak
and separate CO2 from methane and the C2 hydrocarbons.
The PoraPLOT U column channel will have the following separation characteristics:
• Baseline separation for ethane, ethylene and acetylene
• Coelution of propane and propylene
The separation characteristics for the PoraPLOT Q column channel are:
• Coelution of ethylene and acetylene
• Baseline separation for propane and propylene
If you want to the ability to measure anywhere and get the
results you need in seconds, the Agilent 490 Micro GC is the
ideal solution. With its rugged, compact, laboratory quality
gas analysis platform, the 490 Micro GC generates more data
in less time for faster, and better, business decisions.
Instrumentation
For this application an Agilent 490 Micro GC (G3581A)
equipped with a PoraPLOT U and a PoraPLOT Q was used.
The setup parameters for the column is found in the table
below.
PoraPLOT U, 10 m
PoraPLOT Q, 10 m
Column temperature
80 °C
80 °C
Carrier gas
Helium, 200 kpa
Helium, 200 kpa
Injector temperature
110 °C
110 °C
Injection time
20 ms
20 ms
Composite air peak
Propane/propylene
PoraPLOT U
Methane
Carbon dioxide
Ethylene
Sample information
Nitrogen
Methane
Carbon dioxide
Etylene
Ethane
Acetylene
Propylene
Propane
1,2-Propadiene
Propyne
Balance
5.0 %
3.0 %
2.0 %
4.0 %
1.0 %
1.0 %
2.0 %
0.97 %
0.99 %
Propadiene
Propyne
Ethane
5 × zoom
Acetylene
0
PoraPLOT Q
20
40
60
80
100
Seconds
For More Information
These data represent typical results. For more information
on our products and services, visit our Web site at
www.agilent.com/chem.
Composite air peak
Propane
Methane
Carbon dioxide
Propylene
Propadiene
Ethylene/acetylene
Propyne
Ethane
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or for incidental or consequential
damages in connection with the furnishing, performance, or use of this material.
5 × zoom
Information, descriptions, and specifications in this publication are subject to change
without notice.
0
20
40
Seconds
60
80
© Agilent Technologies, Inc., 2011
Printed in the USA
October 4, 2011
5990-9165EN
MICRO GC APPLICATION TABLE
The following is a list of gases that we have prently analyzed with the Varian Chrompack MicroGC.
We will continue to add gases as we develop new application directly or via our customer.
For all new compound not present in this list contact you nearest Varian office.
MicroGC Column modules choice list for applications (Max. two per system).
NOTICE: This document contains references to Varian.
Please note that Varian, Inc. is now part of Agilent
Technologies. For more information, go to
www.agilent.com/chem.
Molsieve 5A :
Hayesep A :
CP-sil 5,8 CB :
CP-sil 19 CB :
CP-WAX 52 CB :
PLOT Al2O3/KCl :
Poraplot Q,U :
CP-COX :
CP SIL 19 Special :
CP SIL 13 Special :
CP Poraplot Special :
CP Sulphur Special :
permanent gases, methane, CO, NO ,etc.(H.R. for O2-Ar baseline separation)
hydrocarbons C1-C3, N2, CO2, air, volatile solvents ,etc.
hydrocarbons C3-C10, aromatics, organic solvents, etc.
hydrocarbons C4-C10, high boiling solvents, BTX, etc.
polar higher boiling solvents, etc.
light hydrocarbons C1-C5 saturated and un-saturated , etc.
hydrocarbons C1-C6, freons, Anaestetics,H2S, CO2, SO2, volatile solvents,..
CO, CO2, H2, air, CH4, etc.
THT and C3-C6 + in Natural Gas Matrix, etc.
TBM and C3-C6+ in Natural Gas Matrix, etc.
PPQ, specially tested for H2S in natural gas (10 to 50 ppm)
Unique column specially tested for MES (Spotleak 2323) in natural gas (1 ppm)
Varian Chrompack MicroGC Column module choice list for single compound.
The limit of quantification L.O.Q. (two times the noise) is just as reference level, matrix, carrier gas and other parameters should influence the sensitivity.
The (x) indicates witch column(s) will do the separation..
COMPOUND
L.O.Q.
ABLUTON T30
ACETENE
ACETIC ACID BUTYL ESTER
ACETIC ACID ETHYL ESTER
ACETIC ETHER
ACETIDIN
ACETONE
ACETONE, METHYL
ACETOXYTHANE
ACETYLEN
ACETYLENE
ACETYLENE
DICHLORIDE
ACETYLENE
TRICHLORIDE
ACRALDEHYDE
ACROLEIN
ACRYLALDHYDE
ACRYLIC ALDEHYDE
AEROTHENE
AEROTHENE MM
AEROTHENE TT
AETHER
AETHYLIS
AETHYLIS CHLORIDUM
Molsieve
10ppm
Haysep
10 ppm
CPCOX
10 ppm
CPSil 5 8/13/1CPWax
1 ppm
1 ppm
X
X
X
X
X
X
X
X
X
X
X
CPAl2O3
1 ppm
Poraplot
1 ppm
X
X
X
X
X
X
X
X
X
X
X
X
AIR
ALCOHOL
ALCOHOL DENATURED
ALCOHOL
METHANOL
ALCOHOL PROPYL ISO REGAL
ALCOHOL DEHYDRATED
ALCOHOL DENATURATED
ALCOHOL ISOPROPYL
ALCOHOL METHYL
ALCOHOLS
ALCOWIPE
ALGOFRENE TYPE2
ALGOFRENE
TYPE6
ALGRAIN
ALLENE
ALLYLENE
ALTENE DG
ANESTHESIA ETHER
ANESTHESIC
ETHER
ANHYDROL
ANKILOSTIN
ANODYNON
ANTISOL 1
ANYDROUS DIETHYL ETHER
AQUALIN
AQUALINE
ARCTON 4
ARCTON 6
ARCTON O
ARGON
ARKLONE
AVANTINE
BALTANE CF
BALTANE D
BENZENE
BENZENE METHYL
BENZENE PROPYL
BENZENE CHLORO
BENZENE ETHYL
BENZENE CHLORIDE
BENZOLENE
BFV
BICARBURRETED HYDROGEN
BICHLOETHANE 1,2BIETHYLENE
BIMETHYL
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
BIOCIDE
BIOGAS
BIVINYL
BLAZER BUTANE FUEL
BLAZER BUTANE GAS
BORER SOL
BROCIDE
BU-GAS
BUTA-1,3-DIENE
BUTADIENE
BUTADIENE 1,3
BUTANE
BUTANE NBUTANE FUEL
BUTANE.2-METHYL
BUTANOL
BUTANOL 1BUTANOL NBUTANONE 2BUTANONE
(MEK) 2
BUTANONE , 2BUTENE 1BUTENE CIS-2
BUTENE TRANS-2BUTENE (E)-2BUTENE (Z)-2BUTENE -(E)-2BUTENE , (E)-2BUTENE ,(Z)-2BUTENE-CIS -2
BUTYL ACETATE
BUTYL ACETATE 1BUTYL ACETATE NBUTYL ALCOHOL 1BUTYL ALCOHOL NBUTYL ALCOHOL
BUTYL ALCOHOL ACETATE
BUTYL ALCOHOL, ACETATE
BUTYHL ETHANOATE
BUTYLENE ABUTYLENE RC10 NCARBINOL
CARBON BICHLORIDE
CARBON CHLORIDE
CARBON DIOXID
CARBON DIOXIDE
CARBON DIOXIDE
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CALIBRATION SALT
CARBON DIOXIDE FILLING SOLUTION
CARBON FLUORIDE
CARBON MONOXIDE GAS
CARBON MONOXIDE IN AIR
CARBON OXIDE (CO)
CARBON TETRACHLORIDE
CARBON TETRAFLUORIDE
CARBONA
CARBONIC ACID GAS
CARBONIC ANHYDRIDE
CARBON OXIDE
CARBONICE
CARDICE
CATION HYDROGEN FORM
CFC 10
CFC 11
CFC 113
CFC 123
CFC 134A
CFC 14
CFC 20
CFC 22
CFC 30
CFC -11
CFC 12
CH4
CH4 IN N2
CHELEN
CHEVRON ACETONE
CHLORBENZEN
CHLORDIFUORO-METHANE
CHLORDIFUORO-METHANE AIR DUST REMOVER
CHLORDIFUORO-METHANE DUST REMOVER
CHLORDIFUORO-METHANE IN AIR DUST REMOVER
CHLORETHYL
CHLORFORM
CHLORIDUM
CHLORINATED FLUOROCARBON
CHLOROBENZENE
CHLOROBENZOL
CHLORODIFLUO-ROMETHANCE
CHLORODIFLUO-ROMETHANE
CHLOROETHANE
CHLOROETHENE
CHLOROETHYLE-NE
CHLOROFLUORO-CARBON
CHLOROFORM
METHYL
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CHLOROFORM
CHLOROTHANE NU
CHLOROTHENE
CHLOROTHENE VG
CHLORTEN
CHLORYL
CHLORYL
ANESTHETIC
CIS-2-BUTYLENE
CLEAN D MCO2
COLOGNE SPIRIT
COLONIAL SPIRIT
COLUMBIAN SPIRIT
CYCLOHEXATRIENE
DABCO CS90
DCM
DECANE
DECANE NDELF FABRIC PROTECTOR
DENATURED ALCOHOL
DENATURE ETHYL ALCOHOL
DENATURED SPIRIT
DESTRUXOL BORER-SOL
DICARBURRETED HYDROGEN
DICHLOREMUL-SION
DICHLORETANE
1,2DICHLORETHYLENE 1,2DI-CHLOR-MULSION
DICHLOROMETHANE
DICHLORO-1,1,1TRIFLUOROETHANE 2,2DICHLORODIFLUORO METHANE
DICHLORODIFLUOROMETHANE
DICHLOROETHA-NE 1,2DICHLOROETHA -NE 1,3DICHLOROETHA-NE (ETHYLENE CHLORIDE) 1,2DICHLOROETHA-NE (PHOTREX) 1,2DICHLOROETHA-NE D4 1,2DICHLOROETHE-NE 1,2DICHLOROETHE-NE S (TOTAL), 1,2DICHLOROETHY-LENE 1,2DICHLOROETHY-LENES 1,2DICHLOROMETHANE
DICHLOROMETHANE (METHYLENE CHLORIDE)
DICHLOROTRI-FLUOROETHANE
DIDAKENE
DIETHYL
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
DIETHYL ETHER
DIETHYL OXIDE
DIFF-QUICK FIXATIVE
DIFLON S-3
DIFLUOROCHLO-ROMETHANE
DIFLUORODICHLOMONOMETHANE
DIHYDROGEN
OXIDE
DIMETHYL
DIMETHYL KETONE
DIMETHYLBENZENE 1,2DIMETHYLBENZENE 1,3DIMETHYLBENZENE 1,4DIMETHYLCARBINOL
DIMETHYLETHY-LENE 1,1
DINITROGEN OXIDE
DIOFORM
DIPROPAL METHANE
DIPROPYL METHANE
DISPARIT B
DISTILLEX DS1
DISTILLEX DS2
DISTILLEX DS4
DISTILLEX DS5
DISTILLEX DS6
DIVINYL
DRICOLD
DRIKOLD
DRIVERIT
DRY ICE
DRY ICE6
DUTCH LIQUID
E 290
E 938
E 939
E 941
E 942
EB
EDC
ELAYL
ELECTRO-CF 12
ELECTRO-CF 22
ERYTHRENE
ESKIMON 12
ESKIMON 22
ETHANA
ETHANE
ETHANE 1,1,1,TRICHLORO-
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ETHANE 1,1,2,TRICHLORO-1,2,2-TRIFLUOROETHANE 1,1’-OXYBIS
ETHANE, 1,2-DICHLORIDE
ETHANE ,1,1,2,TRICHLORO-1,2,2-TRIFLUOROETHANE ,1,1’-OXYBIS
ETHANE ,1,2,DICHLOROETHANE ,2,2,DICHLORO-1,1,1-TRIFLUOROETHANE, CHLOROETHANE, PHENYLETHANOL
ETHENE CHLOROETHENE TETRA-CHLOROETHENE TETRACHLOROETHENE
ETHENE, TRICHLORO
ETHER
ETHER CHLORATUS
ETHER HYDROCHLORIC
ETHER MURIATIC
ETHER, ETHYL
ETHINE
ETHOL ALCOHOL
ETHOXYETHANE
ETHY ETHER
ETHYL ACETATE
ETHYL ACETIC ESTER
ETHYL ALCHOHOL
ETHYL ALCOHOL
ETHYL CHLORIDE
ETHYL CHLORIDE BP
ETHYL ETHANOATE
ETHYL ETHER
ETHYL ETHER A.C.S.
ETHYL HYDRATE
ETHYL HYDRITE
ETHYL HYDROXIDE
ETHYL METHYL
KETONE
ETHYL OXIDE
ETHYLACETATE
ETHYLALACOHOL ZOO PROOF
ETHYLBENZENE
ETHYLBENZOL
ETHYLCHLORIDE
ETHYLCYCLOEXAN
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ETHYLDIMETHYL-METHANE
ETHYLENE
ETHYLENE TETRACHLOROETHYLENE TRICHLOROETHYLENE CHLORIDE
ETHYLENE DICHLORIDE 1,2ETHYLENE DICHLORIDE
ETHYLENE MONOCHLORIDE
ETHYLENE TRICHLORIDE
ETHYLETHYLENE
ETHYLIDENE DICHLORIDE 1,2ETHYLOL
ETHYNE
ETOH
EVERCLEAR
EXHAUST GAS
EXXSOL HEPTANE
EXXSOL HEXANE
EXXSOL ISOPENTANE
F12
F14
F22
FA
FANNOFORM
FASCIOLIN
FC12
FC14
FEDAL-UN
FERMANTATION
ALCOHOL
FIRE DAMP
FLUE GAS
FLUKOIDS
FLUOROCARBON 11
FLUOROCARBON 12
FLUOROCARBON 22
FLUOROCARBON -12
FLUOROCARBON-22
FLUOROTRICHLOROMETHANE
FORMALDEHYDE
FORMALDEHYDE
GERMACIDE
FORMALIN
FORMALIN 40
FORMALITH
FORMIC ALDEHYDE
FORMOL
FORMYL TRICHLORIDE
FREON
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
FREON 11
FREON 12
FREON 14
FREON 20
FREON 22
FREON 30
FREON F-12
FREON MF
FREON R-11
FREON R-12
FREON R-22
FREON TF
FRIGEN
FRIGEN 12
FURAR TETRAHYDROFYDE
GENESOLV A SOLVENT
GENESOLV D SOLVENT
GENETRON 11
GENETRON 12
GENETRON 22
GLYCOL DICHLORIDE
GRAIN ALCOHOL
H20
HALOCARBON 22
HALON 14
HCFC 22
HELIUM
HELIUM, HP
HEPTANE
HEPTANE NHEPTANE, NHEPTYL HYDRIDE
HERCULES 37M6-8
HEXAN
HEXANE
HEXANE NHEXONE
HEXYL HYDRIDE
HFC 22
HIGH PRURITY METHANOL
HOCH
HYDROCARBONS C6
HYDROCARBONS C7
HYDROCARBONS C8
HYDROCARBONS C9
HYDROCHLORIC ETHER
HYDROGEN
HYDROGEN (H2)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
HYDROGEN MIN.
HYDROGEN OXIDE
INHIBISOL
IPA
ISANOL
ISCEON 22
ISOBUTANE
ISO-BUTANE
ISOBUTENE
ISO-BUTENE
ISOBUTYLENE
ISO-BUTYLENE
ISOCOUMENE
ISOPENTANE
ISOPROPANOL
ISOPROPYL ALCOHOL
ISOPROPYLACETONE
ISOTRON 12
ISOTRON 22
IVALON
JAYSOL S
KARSAN
KATHARIN
KELENE
KETONE PROPANE
KETONE, DIMETHYL
KETONE, METHYL ETHYL
KETOPROPANE BLAUGHING GAS
LEDON
LUTOSOL
LYSOFORM
MARSH GAS
MASTER APPLIANCE BUTANE FUEL
MCB
MEETCO
MEK
MEOH
MES
METHANAL
METHANE
METHANE TETRACHLOROMETHANE TRICHLOROMETHANE DICHLORIDE
METHANE, CHLORODIFLUO
ROMETHANE,
DICHLOROMETHANE,
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
XSPEC
X
X
X
X
X
X
X
X
X
X
X
DICHLORODI
FLUORO
METHANE TETRAFLUOROMETHANE,
TRICHLOROFLUORO
METHANOL
METHOKLONE
METHYALCOHOL
METHYL ACETONE
METHYL ALCOHOL
METHYL ALCOHOL
(ANHYDROUS)
METHYL ALCOHOL
(METHANOL)
METHYL ALDEHYDE
METHYL ETHYL KETONE
METHYL HYDRATE
METHYL HYDRIDE
METHYL HYDROXIDE
METHYL ISOBUTYL KETONE
METHYL KETONE
METHYL PROPENE
METHYL-1-PROPENE 2METHYL-2-PENTANONE 4METHYL-2-PENTANONE, 4METHYL-2-PROPANETHIOL 2METHYLACETYLENE
METHYLALCO HOL
METHYLBENZENE
METHYLBUTANE 2METHYLCARBI NOL
METHYLCHLORO
FORM
METHYLCYCLOEXANE
METHYLENE BICHLORIDE
METHYLENE CHLORIDE
METHYLENE DICHLORIDE
METHYLENE GLYCOL
METHYLENE OXIDE
METHYLETHENE
METHYLETHYLE NE
METHYLETHYL METHANE
METHYLFORMATE
METHYLMETHA NE
METHYLOL
METHYLPROPANE 2METHYLPROPANE (ISOBUTANE) 2METHYLPROPANE ,99% (ISOBUTANE) 2METHYLPROPENE 2-
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
MIBK
MOLASSES ALCOHOL
MOLECULAR HYDROGEN
MONOCHLORE THANE
MONOCHLOR
BENZENE
MONOCHLORE
THANE
MONOCHLORO
BENZENE
MONOCHLORODI
FLUOROMETHA
NE
MONOCHLORO
ETHANE
MONOCHLORO
ETHENE
MONOFLUORO
TRICHLORO
METHANE
MONOHYDROXYMETHANE
MORBICID
MURIATIC ETHER
M-XYLENE
N2
N20
NARCOTILE
NARCYLEN
NARKOTIL
NECATORINA
NEMA
NEON
NEVOLIN
NITRAL
NITROGEN
NITROUS OXIDE
NONANE
NONAE NNORFLURANE
NORMAL HEPTANE
NORMAL HEXANE
O2
OXOMETHANE
OXYBISETHANE
OXYGEN
O-XYLENE
OXYMETHYLENE
PENTANE
PENTANONE, 4-METHYL- 2-
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
PER
PERAWIN
PERCHLOR
PERCHLOROETHY
LENE
PERCHLOMETHA
NE
PERCLENE
PERCOSOLVE
PERFLUOROME
THANE
PERK
PERKLONE
PERSEC
PETRHOL
PHENE
PHENYL CHLORIDE
PHENYL HYDRIDE
PHENYLCHLORI DE
PHENYLETHANE
PHENYLMETHANE
POLYOXYMETHY
LENE GLYCOLS
POLYRINYL ALCOHOL
POTATO ALCOHOL
PROP-2-EN-1-AL
PROPADIENE
PROPADIENE 1,2PROPANE
PROPANE, 2-METHYL- 2PROPANOL 2PROPANONE 2PROPANONE
PROPELLANT 12
PROPELLANT 22
PROPEN-1-ONE 2PROPENAL 2PROPENAL
PROPENE
PROPENE, 2-METHYL-1PROPENE,2,
METHYLPROPYL CARBINOL
PROPYLBENZENE
PROPYL
CARBINOL
PROPYLENE
PROPYNE
PUNCTILIOUS ETHYL ALCOHOL
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
PURE ETHYL ALCOHOL
P-XYLENE
PYRO
PYROACETIC ETHER
PYROBENZOL
PYROXYLIC SPIRIT
PYRROLYENE
PYRROLYLENE
R 10
R14
R30
R-22
REAGENT ALCOHOL
REFRIGERANT 11
REFRIGERANT 12
REFRIGERANT 12
DICHLORODIFLUO
TOMETHANE
REFRIGERANT 22
REFRIGERANT 30
REGEATTE
RONSON BUTANE FUEL
RONSON MULTI-FILL BUTANE FUEL
SASETONE
SHELL ACETONE
SLIMICIDE
SOLAESTHIN
SOLMETHINE
SOLVETHANE
SPIRIT
SPIRIT OF WINE
STERETHOX
STYRENE
SULFURIC ETHER
SUPERLYSOFORM
SYM-DICHLOROETHY
LENE
SYNASOL
SYN-DICHLORO
ETHANE
SYS -DICHLOROETHY
LENE
TCE
TCM
TEBOL 88
TEBOL 99
TECSOL
TERT-BUTANETHIOL
TERT-BUTYL MERCAPTAN
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
TESCOL
TETLEN
TETRACAP
TETRACHLORE
THYLENE
TETRACHLORO
ETHENE
TETRACHLORO
ETHYLENE
TETRACHLOME
THANE
TETRAFINOL
TETRAFLUORO
ETHANE 1,1,1,2TETRAFLUORO
ETHANE
TETRAFORM
TETRAHYDRO
FURAN
TETRAHYDRO
THIOPHENE
TETRALENO
TETRALEX
TETRAOXY
METHYLENE
TETRASOL
TETRAVEC
TETROGUER
TETROPIL
THAWPIT
THF
THIOPHENE
TETRAHYDROTOGA
TISSUE FIXATIVE
TOLUENE
TRIAZINEN,N’,N”-TRICHLORO-2,4,6,-TRIAMINO -1,3,5TRICHLORO-1,2,2TRIFLUOROETHANE
TRICHLORO-1,2,2TRIFLUOROETHANE 1,1,2TRICHLORO ETHANE 1,1,1TRICHLORO ETHANE
TRICHLORO ETHENE
TRICHLORO ETHYLENE
TRICHLORO ETHYLENE 1,1,2TRICHLORO ETHYLENE , 1,1,2TRICHLORO ETHYLENE -14C
TRICHLORO ETHYLYENE
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TRICHLORO
FLUORO METHANE
TRICHLORO
FLUOROMETHANE
TRICHLOROFORM
TRICHLORO
METHANE
TRICHLOROME THANE 1,1,1,TRICHLOROMONO
FLUOROMETHANE
TRICHLOROSTHONE 1,1,1TRICHLOROTRI
FLUOROETHANE
1,1,2TRICHLOROTRI
FLUOROETHANE
1,2,2TRICHLOROTRI
FLUOROETHANE
TRICLENE
TRI-ETHANE
TRIFLUORO-1,2,2,
TRICHLOROETHA
NE 1,1,2TRIFLUOROTRICHLOROETHA
NE 1,1,2TRIKLONE
TRILENE
TRIMETHYLME
THANE
UCON 12
UCON 22
UHP HELIUM
UHP METHANE
ULTRATANE BUTANE FUEL
UNIVERM
UNS.DIMETHYL
ETHYLENE
USI IN OVAL
VC
VCM
VERMOESTRICID
VINEGAR NAPHTHA
VINYL CHLORIDE
VINYL CHLORIDE
MONOMER
VINYLETHYLENE
WATER
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WESTROSOL
WOOD ALCOHOL
WOOD NAPHTHA
WOOD SPIRIT
XENON
XYLENE 1,2XYLENE 1,3XYLENE 1,4XYLENE MXYLENE OXYLENE PXYLENE-D10 OXYLENE -D10 PHv
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