

Extended Natural
Gas Analyzer

Specials and Solutions Group

For use with G3445 Option 541 or G3440 SP1 7890-0171
Rev B
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General information
This GC is configured to do an extended natural gas analysis up to C14. The analyzer is a
three valved system using 1/8 inch packed columns and a PONA capillary column for the
detailed hydrocarbon analysis. A plumbing diagram is shown below.


FLOW
Valve System
INJECTION VALVE COMPARTMENT
Date :
Order No :
S/N :

Item :
DETECTOR
OVEN LEFT SIDE
SOURCE PORT BLOCK 2 BLOCK 1

1/800/502/504

Out
Sample
In
Back Aux 7 6 5
8 4 1 ml
Ch 2 250 ul 9 3
Side

PCM C 0101-0303
10
1 2 0101-0299
Ch 1
Back Inl
Back

TCD
(220)
Front Inl Front
Front

860 CAP Col 1

EPC (112) FID
Col 3 (210)
Vent 4
4
3
Front Aux 5
3 5
6 2
6 2
1
1

Col 2
3/705 2/702

Options SP1 options Remarks

112,210,220,309,502,504,702,705,753,800,860, 7890-0171

Fig.1

The columns used in this analyzer are as follows.

Column 1 3 Foot HayeSep Q 80/100 mesh

Column 2 6 Foot HayeSep Q 80/100 mesh
Column 3 10 Foot Molecular Sieve 13X 45/60 mesh
Column 4 50m x 200um x 0.5um PONA column

The plumbing diagram shows a pneumatics control module (PCM) as the flow source for the
valves. The packed inlet can also be used as a flow source. Valve 1 is a 10 port valve
configured as a dual gas sampling valve injecting into the capillary injection port and column
1. Valve 2 is a column isolation valve. Valve 3 is a 6 port valve configured as backflush of
the pre-column to vent that will prevent heavier components from entering the column.

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There are two ways to set up this analyzer, depending on how the GC will be calibrated.
Software is supplied which will allow the user to either calibrate ALL of the peaks or to
calibrate only the early peaks on the TCD and use a bridging compound(s) with the FID and
then use response factors to calculate the amounts present on the FID.

Set up when all peaks are calibrated.

Analysis Sequence
The system consists of two independent channels. The channel using the FID for the
detailed hydrocarbon analysis is a simple Gas Sampling Valve injecting onto the PONA
capillary column.

The second channel using the packed columns is a little more complex.

1. Injection of sample.

3Ft HayeSepQ 6Ft HayeSepQ Mol Sieve 13X TCD

Aux
Vent
flow

2. Isolation of N2, O2 and CH4 in the Molecular Sieve column. Soon after the isolation the
CO2 will elute

3Ft HayeSepQ 6Ft HayeSepQ Mol Sieve 13X

CO2
C2 O2, N2 CH4

Aux
Vent
flow

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3. The precolumn is backflushed to vent and the Ethane will elute from the Hayesep Q
column.

3Ft HayeSepQ 6Ft HayeSepQ Mol Sieve 13X

C2

HC's O2, N2 CH4

Vent
Aux
flow

4. When the Ethane has eluted, the Molecular Sieve is switched back into the stream and
the oxygen, nitrogen and methane will elute from the column.

3Ft HayeSepQ 6Ft HayeSepQ Mol Sieve 13X

O2,N2,CH4
HC's

Vent
Aux
flow

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Installation.
Connect the Helium as carrier and the other gases to the GC and power up the GC.

Understand the application requirements for carrier and support gases before connecting
them. Connect the carrier(s) and the other gases to the GC and power up the GC. If the
system contains air actuated rotary valves, supply them with clean air which is oil, water and
particulates free at about 40 psi constant.
Start by setting the correct communication parameters in the GC found by pressing the keys
[OPTIONS] and then scrolling to "Communications" and pressing [ENTER]. Once done,
reboot the GC.
If this is the only factory tested method, then the checkout method set up for the instrument
will be stored in “Method # 9” GC memory position”. Load the GC method pressing [LOAD]
[METHOD] [9] in the GC keyboard or manually enter the parameters found in the method
text file found in the analyzer CD using the GC keyboard. Allow the system to stabilize.
If an Agilent Open Lab ChemStation rev. C.01.05 (or higher) is installed in the work station
(PC) – start the "Open Lab Control Panel" by clicking in the corresponding icon. Once open,
left click the "Configure Instrument" icon (round purple button with tools) and wait for the
next screen opens. Once opened, check that the selection for "Method Load on Startup"
condition is set to "Always ask user to choose an option". Then proceed to move one "7890
GC" icon from the "Configurable Modules" selection in the left field of the screen to the
"Selected Modules" field visible at the right of the screen. Double click on the 7890 GC icon
just moved in the previous operation and type the required information in "Connect Info".
Most important is the IP address and other communication parameters previously set in the
GC. Once this is done, immediately click the "Get GC Configuration" button and allow a few
seconds for the communication to establish. If a positive communication success message
displays, then the Open Lab ChemStation has received and stored the specific configuration
of that GC (Inlets, detectors, valves, etc.). Review the "Configuration" tab and verify that
matches the actual instrument. Exit this screen by pressing "OK". Once back in the
"Configure Instrument" screen, exit from there too by pressing "OK" button again.
Now start the instrument just configured pressing the round purple icon named "Launch".
After a few seconds, a screen labeled "Choose Method Load Option" will come up if this is
the first time the control software is used. In this case choose the option "New Method from
Instrument" which will take you to the ChemStation control screen under a default method
(def_gc.m) which has the same GC control parameters loaded as the method shipped in the
memory of the GC (provided that it was loaded as instructed before), but won't contain any
data analysis parameters like the calibration table for the checkout standard. This is when
the factory tested method needs to be loaded from the Specials CD (found in the Specials
ship kit) into the computer and from it to the ChemStation.
For this analyzer the method to be loaded is 7890-0171.M

Allow the GC to equilibrate for a length of time adequate for the application (detectors
baseline, column purge time, etc.).
NOTE: Some conditions might not appear exactly as described here, specially the valve
timing due to column variability between the original design and your current instrument.
Check the “Procedure for a New Setup” section in case of doubt.

Verify the following conditions:

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=====================================================================
Agilent 7890B
=====================================================================

Oven
Equilibration Time 3 min
Max Temperature 225 degrees C
Slow Fan Disabled
Oven Program On
60 °C for 11 min
then 36 °C/min to 200 °C for 5.111 min
Run Time 20 min

Front Injector
Syringe Size 5 μL
Injection Volume 0.5 μL
Solvent A Washes (PreInj) 0
Solvent A Washes (PostInj) 0
Solvent A Volume 4 μL
Solvent B Washes (PreInj) 0
Solvent B Washes (PostInj) 0
Solvent B Volume 4 μL
Sample Washes 0
Sample Wash Volume 4 μL
Sample Pumps 6
Dwell Time (PreInj) 0 min
Dwell Time (PostInj) 0 min
Solvent Wash Draw Speed 150 μL/min
Solvent Wash Dispense Speed 3000 μL/min
Sample Wash Draw Speed 150 μL/min
Sample Wash Dispense Speed 3000 μL/min
Injection Dispense Speed 3000 μL/min
Viscosity Delay 0 sec
Sample Depth Disabled
Injection Type Standard
L1 Airgap 0.1 μL

Front SS Inlet He
Mode Split
Heater On 250 °C
Pressure On 21.338 psi
Total Flow On 53.5 mL/min
Septum Purge Flow On 3 mL/min
Gas Saver Off
Split Ratio 100 :1
Split Flow 50 mL/min

Column #1
Agilent NGA column set
225 °C: Packed
In: PCM C-1 He
Out: Back Detector TCD

Flow Program On
28 mL/min for 0 min
Run Time 20 min

Column #2
Agilent 19091S-001HP-PONA
325 °C: 50 m x 200 μm x 0.5 μm
In: Front SS Inlet He
Out: Front Detector FID

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(Initial) 60 °C
Pressure 21.338 psi
Flow 0.5 mL/min
Average Velocity 16.38 cm/sec
Holdup Time 5.0876 min
Pressure Program On
21.338 psi for 9.5 min
then 50 psi/min to 42.6 psi for 0 min
Run Time 20 min

Front Detector FID

Heater On 250 °C
H2 Flow On 35 mL/min
Air Flow On 350 mL/min
Makeup Flow On 30 mL/min
Const Col + Makeup Off
Flame On
Electrometer On

Back Detector TCD

Heater On 150 °C
Reference Flow On 45 mL/min
Makeup Flow On 2 mL/min
Const Col + Makeup Off
Negative Polarity Off
Filament On

Valve 1
Other Off

Valve 2
Other Off

Valve 3
Other On

Valve 4
Other Off

PCM C-1 He: Supplies Column 1

PCM C-2 He
***Excluded from Affecting GC's Readiness State***
Pressure Program On
14.4 psi for 0 min
Run Time 20 min

Valve Box
Heater On 150 °C
Signals
Signal #1: Front Signal Save On
10 Hz
Signal #2: Back Signal Save On
10 Hz
Run Time Events

Time (min) Event Position Setpoint

0.01 Valve Valve 3 Off
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 0.05 Valve Valve 1 On
0.5 Valve Valve 1 Off
2.25 Valve Valve 2 On
2.8 Valve Valve 3 On
7.3 Valve Valve 2 Off

NOTE:

If the instrument has additional hardware installed, the previous parameters may not reflect
the additional values for other controlled zones. Always refer to the specific documentation
supplied for each particular instrument like valve diagrams and test methods.

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Procedure for a New Setup
This procedure will have to be carried out on a new GC or if new columns are installed or
the present columns are re-conditioned. If new columns are being installed, or present
columns need to be conditioned, condition columns as indicated in the Appendix A.

Set up of needle valve.

1. Ensure that you have the following conditions set up.

Oven Temp 60 C

Column 1 flow 28 ml/min
Valve 1 OFF
Valve 2 OFF
Valve 3 OFF

2. Monitor the head pressure of the columns by looking at the ‘Actual’ pressure for the PCM
C-1 (PCM primary or first channel). When this is steady, note the value.

3. Turn Valve 2 ON.

4. Adjust the needle valve associated with Valve 2 to give the same head-pressure noted in
step 2.

5. Turn Valve 2 OFF and Valve 3 ON

6. Connect a suitable flow meter and measure the flow for the backflush column at the line
marked V3 vent.

7. Adjust the PCM C-2 (PCM auxiliary or second channel) pressure to obtain a flow of 28
ml/min. This was achieved at about 14 psi in the instrument used to develop this
application.

Setting the backflush time.

Start with Valve 3 ON.

The object is to set the backflush time of Valve 3 so that any hydrocarbons other than
methane and ethane are backflushed out to vent. A suitable sample is either P/N G3440-
85017 (preferred) or 5080-8756 from Agilent Technologies.

1. Clear the run table of any entries and then enter the following into the run table.

Valve 3 OFF Time 0.01

Valve 1 ON Time 0.05
Valve 1 OFF Time 0.50
Valve 2 ON Time 0.05
Valve 3 ON Time 2.70

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2. Check that you have the following set up

Oven temp 60C

Oven time 11 min
Oven rate 0C/min.

3. Flush the sample loop with the sample, and press START on the GC. Allow to run for the
full 11 minutes. You should get a chromatogram similar to that shown below.

Fig 2.

It is important to check that the ethane peak is present and that there is no propane coming
out later in the run. If the backflush time (Valve 3 ON) is set too early you will see that the
ethane peak is missing or not all of the ethane is present. This situation is shown in Fig 3,
where a backflush time of 2.10 minutes was used.
If the backflush time is set too late, you will see C3 compounds come out later in the run.

Fig 3. Backflush too early

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The ideal time is found by increasing the backflush time of Valve 3 in 0.10 increments until
the ethane peak starts to appear. Note the area of the ethane peak and repeat the
injections with the Valve 3 incremented by 0.1 minutes until the area of the ethane peak is
constant. When you have found this time, save the method. You can now set up the timing
for the V2 column isolation valve.

Fig 4.

Note the times A and B from this chromatogram as follows:

Time A = Retention of Carbon Dioxide – 0.5 minutes
Time B = End of the Ethane peak + 1.0 minutes

Enter the following into the Run Table

Valve 2 ON Time A
Valve 2 OFF Time B

The addition of these commands to the run table will allow the air and methane to be
transferred into the Molecular Sieve column and after the carbon dioxide and ethane have
eluted from the Hayesep Q column, allow these compounds to elute from the Molecular
Sieve column.

The following two chromatograms in Fig. 5 show the results of running the Agilent natural
gas sample, P/N 5080-8756.

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 Fig 5.

However, since this analyzer is designed to go into the extended hydrocarbon range for the
less than typical natural gas sample, and since gas standards with compositions containing
hydrocarbons beyond n-hexane are expensive and not very stable, a different approach
was taken to determine the retention times of the homologous series of straight chain
hydrocarbon starting with n-hexane (n-C6) and ending in n-dodecane (n-C12) for the present
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analyzer under the conditions contained in the method, which include an oven heating ramp
and flow programming the capillary column after 11 minutes into the run for a total run time
of 20 minutes that allows the elution of n-dodecane (n-C12). Longer final time or higher final
temperature will be required into the method if heavier hydrocarbons are expected. Is not
recommended to increase the final oven temperature for extended periods of time unless
deemed necessary (i.e. column conditioning) as that can speed up the degradation of
polymeric stationary phases. Always check the maximum temperature limits for all the
columns inside the GC oven and don’t run it any hotter than the maximum temperature limit
of the lowest temperature-limited column in your system. (see Appendix A).

The extended analysis requires the injection of the natural gas standard Agilent P/N G3440-
85017 (preferred) or 5080-8756 through the gas sampling valve simultaneously with 0.5 µl
of a liquid standard Agilent P/N G3440-85013 containing equal amounts of the homologous
series of straight chain hydrocarbons (C6 to C12) through the capillary inlet either by means
of a 7693A Automatic Liquid Sampler or manually. The supplied method contains the
parameters for the ALS injection. Check that the Injection Source is configured to be the
ALS in the data acquisition method. Make sure the sample loop has been purged with the
gas standard for at least 30 sec. and the flow has been stopped after that interval by closing
the tank regulator valve before starting a single run from the instrument control software. If
an autosampler is not available proceed as follows:

1. Prepare a vial with the liquid standard P/N G3440-85013 suitable for syringe use and set
apart.

2. Connect the gas standard tank P/N G3440-85017 (preferred) or 5080-8756 to the
“Sample In” line (the one with the in-line filtering device) on the left side of the
instrument. You may use a small container with isopropanol or other suitable liquid to
submerge the tip of the “Sample Out” line to check for presence of sample flow through
the sampling loop.

3. Wait for the GC to show ready status displayed in its screen and open the cylinder valve.
Purge the sample lines and loop for 30 sec. and close the tank valve. Check the sample
bubbles stop in the liquid if the previously described technique was adopted. This allows
you to have the gas in the loop equilibrated with the ambient pressure.

4. Immediately after closing the gas valve, prepare yourself to inject 0.5 µL of the liquid
standard P/N G3440-85013. Inject and press the start button at the same time. Try to do so
within 30 – 45 sec after closing the gas valve on the sample tank. Do not “Idle” the syringe
needle into the capillary inlet before or after pressing the plunger to inject.

5. Repeat steps 3 and 4 for subsequent runs.

The use of G3440-85017 gas standard will yield one more hydrocarbon peak compared to
the 5080-8756 mix. The extra peak included is the neo-pentane (2,2, dimethyl propane)
visible right after the n-butane peak in the FID channel. An example of the combined
injection of both the gas and liquid standard is shown in Fig. 6 below.

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 Fig 6.

Care must be taken when calibrating the concentrations of the different compounds
contained in the gas and in the liquid samples, as both contain n-hexane and the peaks
elute (naturally) at the same RT. The combined injection is intended to set the expected RT
of the different components into the system, but the calibration should be accomplished by
means of a single, certified (and possible heated) gas mixture that resembles the real
sample to be analyzed in the instrument.

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The following chromatogram shows a more complex hydrocarbon mixture run on the
FID/PONA column channel

Fig 7.

Calibration
Connect up a calibration gas to the GC, purge the sample loop with the calibration gas and
allow the pressure in the loop to come down to atmospheric pressure before starting the
run. At the end of the run, calibrate the GC.

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 Appendix A
Conditioning the columns.

Molecular Sieve 13 X column.

This column should be removed from the GC and installed into a similar GC oven which does not
have valves installed on the top and does not have any other columns installed in the oven.
If a second GC oven is not available, remove all other columns from the oven, remove the valve box
top so that the valves are exposed to atmospheric temperature and turn off the heat to the zones
that heat the valves.
Condition at 350°C over night with a helium gas at 30-40ml/min.

Hayesep Q

You will also need to remove the other columns, but this can be conditioned in this GC. If the GC
has a packed inlet, connect one end of the column to the packed inlet and allow the other end to
hang free. If the GC does not have a packed inlet, remove the DC200 and UCW982 columns and
connect the Hayesep Q column to the line going to port 6 of Valve 1.
Condition at 225°C for 4 hours with helium gas at 30-40ml/min

PONA Capillary column

This column should be removed from the GC and installed into a similar GC oven which does not
have valves installed on the top and does not have any other columns installed in the oven.
If a second GC oven is not available, remove all other columns from the oven, remove the valve box
top so that the valves are exposed to atmospheric temperature and turn off the heat to the zones
that heat the valves.

Condition at 300°C for 4 hours with a helium gas at 2ml/min.

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 Appendix B

Configuring valves on the 7890.

Valves can be configured into the 7890 several ways, with some confusion. The choices are as
follows:
Gas Sampling
Switching
Other
Multiposition
Not Installed.

Multiposition.

Used to configure a valve as a stream selection valve. Only ONE valve on the GC may be
configured as a multiposition valve.

Not Installed

Used to uninstall a valve.

Other

Used to define something that is not actually a valve. For example the valve control could be used
to switch a relay which controls some other piece of equipment. This still acts as a valve control for
all intents and purposes.

Switching

Used to control a valve. Valve can be controlled from the run table or from the keyboard. Turning
the valve on has no effect on the GC status (see Gas Sampling). Valve will NOT turn to it’s original
position at the end of the run. To do this you will need a Run Table entry.
If you have a valve hardware configured as a gas sampling valve but configured in the 6890 as a
switching valve, you cannot start the run remotely from the GC ChemStation.

Gas Sampling

Now this is where the confusion starts. If a valve is configured as a Gas Sampling valve, the
following will happen.
 The GC can be started remotely from the GC ChemStation providing the injection source has
been set to “GC Valve”.
 An automatic sequence can be set up.
 The valve will return to the OFF position at the end of the run.
 If you press “START” on the GC, the GC program will start but the Gas Sampling valve will NOT
inject the sample.
 If Valve 1 is configured as a Gas Sampling valve and from the GC keyboard you enter Valve 1
ON, you will inject the sample AND start a GC run. This can be a nuisance if you are trouble
shooting, as all events in the Run Table will also execute.
 The switch on time of the Gas Sample Valve will NOT appear in the Run Time Table.
 You cannot stagger injection times if you have two or more valves injecting samples.

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 So what is the best way to set up?
The 6890 has eight valve control functions. It is rare that all are used up. Normally valves 1 to 4 are
used to actually control valves on the GC. This leaves valve controls 5 to 8 free. So configure all of
the valves in your valve system as switching valves and configure one of the unused positions as a
Gas Sampling Valve. This will give the following advantages.
 You can control the GC remotely from the GC ChemStation.
 You can set up a sequence.
 If you press “START” on the GC, the GC will start AND your sample will be injected.
 If you enter “Valve 1 ON”, valve 1 will switch on but the GC will NOT start a run.
 All switching times will appear in the Run Table.
 You can stagger injection times.

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