Dedicated Instruction Manual

Determination of traces of CO and CO2 in gas streams

1. Introduction
This manual describes detailed operation of a dedicated GC configuration based on the
TRACE Ultra gas chromatograph and manufactured by Thermo Electron, equipped with FID
(Flame Ionization Detector) and methanizer able to perform the analysis at low level of
concentration of CO and CO2 in high purity hydrogen and other gas-phase samples.
The lower limit of detection for either CO and CO2 in hydrogen is 0.1 ppm.
Higher concentrations of methane (above 5%) will interfere with the determination of carbon
dioxide.

The system includes the following column:

- Packed column 1/8”, 2 m long, HaySep Q 80-100 mesh (p/n PKDA00000007000)

A methanizer placed before the FID is used to convert CO and CO2 in methane.
Sample is injected by Valve #1 which is also responsible for placing the packed column in
backflush mode. The system is equipped with hydrogen sensor to allow safety use of
Hydrogen in the equipment.

2. Description of the Analyzer

The Trace GC is equipped with a Valve Oven housing, which includes two zones, a heated
and a cold one. In the heated area of the Valve Oven is installed the sampling valve.
The complete configuration of the system is shown in the diagram reported below.

NV: is a needle valve which can be used to adjust the carrier gas flow rate. Regulation of
these valves can be accomplished from the front part of the valve oven.

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Valve #1 is responsible for sample injection and back flush of the Haysep column.
Carrier gas used is Helium. In case a different carrier gas (hydrogen) must be used, it is
enough to change the carrier gas configuration as follows:

- On the TRACE GC keypad press CONFIG button and scroll to “Right carrier”
- Press MODE/TYPE to display a submenu of carrier gases

- Scroll to the gas to be used and press ENTER to confirm the selection. An asterisk
appears on the left of the gas selected

NOTE: Never close completely the needle valve otherwise the valve needle could be
irreversible damage.

The Valve Oven temperature can be programmed between 40°C up to 175°C in the aux page
of the TRACE GC. In order to heat the valve oven use the following steps:
- On the TRACE GC keypad press AUX button
- Scroll to Temperature Zones and press ENTER button
- Enter the target temperature and press ENTER button.

The Valve switching is controlled through the Valve interface page on the Trace GC keypad
and may be manually actuated by pressing ON/OFF buttons on the keypad or time
programmed through the RUN TIME menu on the Trace GC keyboard.
Manual switching of the valve is useful for set-up the analyzer step by step, or for
troubleshooting.

In order to switch the valve manually use the following steps (for instance for valve #1):
- Press VALVES button on the TRACE GC keypad
- Select gas sample valve #1
- Press ON to place the valve in the inject position or OFF to place the valve in the load
position.

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The switching of all valves has been factory set-up in the run table. You can change the
switching time of these valves by adding the desired value to the run table. The following
steps allow you to change these values (for instance for valve #1):
- On the TRACE GC keypad press the RUN TABLE button
- Scroll to Add Run Time Event and press ENTER button
- Select Valve and press ENTER
- Scroll to the sampling valve #1 and press ENTER
- The following screen appears:

- The “Inject at” parameter is the time into the run that the sample is to be injected. The
“Inject for” parameter is the time that the valve will be returned to the Load position.
If the Inject for time exceeds the GC run time, the GC will automatically reset the
valve to the Load position at the end of the run.

A schematic of the separation performed by the analyzer is the following:

The sample is injected directly onto the column where the separation of the CO, CO2 and
methane is made from the remaining components. After conversion of CO and CO2 in
methane all these components are detected by the FID.

HayeSep Methanizer FID

C2’s and CO, CO2, and CH4

high boiling
components

Once these components have been eluted, the Haysep column is placed in reverse flow and
the remaining components are backflushed to the vent.

HayeSep Methanizer FID

C2’s high boiling CO, CO2,

components and CH4

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 3.1 Packed Columns Conditioning
The column must be conditioned before operating.

• HayeSep column must NOT exceed 180°C during conditioning

We strongly recommend to condition this column at a temperature 10°C lower than

the maximum indicated above at a carrier gas flow rate of (suggested He) 20 ml/min.
Columns conditioning should be performed for at least two hours.

3.2 Nuts tightening

Control all the nuts present in the column oven and in the heated Valve Oven and
tighten them if needed, paying attention not to over-tighten them with an
excessive strength.

3.3 Leak check

To perform a leak check, operate as follows:

1. Place the Valve #1 in the “Inject” position

2. Cap the right base body using the blind jet p/n 40401901 provided in the standard
outfit

3. Set the Right DPFC pressure at 200 kPa and maintain the system in this condition
for two minutes.

4. Set the Right carrier OFF and observe for any pressure decrease in the display, in
the next two minutes. If the pressure does not decrease this means that the system is
leak free.

5. In case of leak try to identify the leak point repeating the above operations and
checking all connections starting from the valve. A leak tester will also help in this
operation.

6.Cap the vent outlet number 2. Then set the Left DPFC pressure at value of 100 kPa
and maintain the system in this condition for one minute

7. Set the Left carrier OFF and observe for any pressure decrease in the display, in the
next two minutes. If the pressure does not decrease this means that the system is leak
free.

If the system is leak free place the Valves #1 in the load positions and repeat steps 3
to 7.

Removes the caps

3.5 Analytical tuning

Instrument has been factory –tuned and tested using the following sample mixture:

Carbon monoxide 1 ppm, Carbon dioxide 1 ppm and Methane 1 ppm in Helium

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 Valve functions

Valve # Setting Function

Valve 1 Load Fill 1 ml sample loop/BackFlush HaySep Q column
to vent
Valve 1 Inject time Inject on FID channel

NOTE: The methanizer set-up, operation and parameters are described in the
relevant manual included with the TRACE GC Ultra set of documentation.
Pls verify accurately the activation of the methanizer catalyst before starting
injecting the sample

The other parameters should be set as follows:

Right DPFC mode Constant Pressure

Right Carrier Gas pressure 140 kPa
Right base temperature Off

Left DPFC mode Constant Pressure

Left Carrier Gas pressure 60 kPa
Left base temperature Off

FID base temperature 280°C

H2 flow 35 ml/min
Air flow 350 ml/min
Make up gas flow 30 ml/min

Initial oven temperature 40°C

Initial time 5.00 min

Valve oven temperature (Aux 0) 70°C

Methanizer temperature (Aux 1) 380°C

Time Item Setting Function

0.01 Valve#1 Inject for 2.81 min Inject on CO and CO2 channel

NOTE: The valve #1 switching time has been selected to permits complete
elution to the methanizer/FID of CO, CH4 and CO2 but to avoid heavier
hydrocarbons, if present, to be eluted to the methanizer.
With this setting all components eluted after CO2 are back flushed to the vent.

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 Typical chromatogram produced in this condition is the following:

Retention Time Component

0.827 Carbon Monoxide
1.222 Methane
2.360 Carbon Dioxide

4. Troubleshooting
The following solutions can fix the most common problems generated during the
operation of the analyzer.

4.1 Loss of chromatographic resolution

A loss of resolution is generally caused by dirty columns (water and other
components in the sample absorbed by the column). To short out this
problem, proceed with the conditioning of the column as described in the
related section.

4.2 Increase of the Height of Interfering Peaks and Switching Disturbs

After some time the instrument is in stand by mode, some air may diffuse through the
valves, contaminating the columns and compromising the analytical result. To
overcome this problem it is sufficient to run 3 or 4 blank analyses (without sampling)
with a different run time program which speeds up significantly the blank analysis.

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