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“Analyzer for the determination of Hydrocarbons and Hydrogen” Dedicated Instruction Manual

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“Analyzer for the determination of the Hydrocarbons and Hydrogen” TRACE™ GC Ultra Dedicated Instruction Manual May 2004 Edition © 2003 Thermo Electron Italia S.p.A. All rights reserved. Printed in Italy Published by Thermo Electron Italia S.p.A., Strada Rivoltana, 20090 Rodano - Milan – Italy Tel: +39 02 95059373 Fax: +39 02 95059388 Disclaimer Technical Information contained in this publication is for reference purposes only and is subject to change without notice. Every effort has been made to supply complete and accurate information; however, Thermo Electron assumes no responsibility and will not be liable for any errors, omissions, damage, or loss that might result from any use of this manual or the information contained therein (even if this information is properly followed and problems still arise). This publication is not part of the Agreement of Sale between Thermo Electron and the purchaser of a TRACE™ GC Ultra system. In the event of any conflict between the provisions of this document and those contained in Thermo Electron’s Terms and Conditions, the provisions of the Terms and Conditions shall govern. Reference to System Configurations and Specifications supercede all previous information and are subject to change without notice. Trademarks TRACE™ is a trademark of Thermo Electron Italia S.p.A. Other brand and product names may be trademarks or registered trademarks of their respective companies.

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Declaration

Manufacturer: Thermo Electron Italia S.p.A. Thermo ElectronItalia S.p.A. is the manufacturer of the instrument described in this manual and, as such, is responsible for the instrument safety, reliability and performance only if:

•installation

•re-calibration

•changes and repairs

have been carried out by authorized personnel and if:

•the local installation complies with local law regulations

•the instrument is used according to the instructions provided and if its operation is only entrusted to qualified trained personnel

Thermo Electron Italia S.p.A. is not liable for any damages derived from the non-compliance with the aforementioned recommendations.

Thermo Electron Italia S.p.A. Strada Rivoltana 20090 RODANO (MI)

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Index

Analyzer for the determination of the Hydrocarbons and Hydrogen……………………………

General Description 08

Description of the Analyzer 08 Analytical Unit 09

General Description 09 Valve Oven 09

Valve Functions 10 Set-up of Analyzer 11

Packed Column Conditioning 11 Nuts Tightening 11 Leak Check Hydrogen Channel 11 Leak Check Hydrocarbons Channel 12

Analytical Tuning 13 Analytical Separation Hydrogen Channel 14 Analytical Separation Hydrocarbons Channel 14 Analytical Parameters 15

Analytical Result 16 Troubleshooting 18

Loss of chromatographic solution 18 Increase of the Height of interfering Peaks 18

Consumables 18

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Analyzer for the determination of the Hydrocarbons and Hydrogen

This manual describes detailed operation of a dedicated GC configuration based on the TRACE GC Ultra gas chromatograph and manufactured by Thermo Milan, equipped with one TCD (Thermal Conductivity Detector) and one FID (Flame Ionization Detector) able to perform the analysis of Hydrocarbons and Hydrogen.

Index… General description 08 Analytical Unit 09 Set-up of analyzer 11 Analytical tuning 13 Analytical result 16 Troubleshooting 18 Consumables 18

For typographical conventions, symbols and customer communication please refer to Operating Manual of the TRACE GC Ultra.

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General Description

Description of the Analyzer The Trace GC Ultra 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 are installed two valves and packed columns. The capillary column is installed inside the GC Oven. Valve #2, gas sampling valve, also permits to backflush the packed columns for a quicker elution to vent of remaining components. Valve #3, gas sampling valve, make the injection on the Hydrocarbons Channel. The complete configuration of the system is shown in the figure1-1.

Figure 1-1 Configuration of the system

Legend Description

Carrier 1 Left Carrier Gas (Helium) Hydrocarbons Channel CG1 Manual Carrier Gas (Nitrogen) Hydrogen Channel CG2 Manual Carrier Gas (Nitrogen) Hydrogen Channel NV1 Needle Valve which can be used to adjust the carrier flow for TCD.

Regulation of this valve can be accomplished from the front part of the valve oven.

NV2 Needle Valve which can be used to set a back pressure on the sample loop for Hydrogen channel. Regulation of this valve can be accomplished from the front part of the valve oven.

NV3 Needle Valve which can be used to set a back pressure on the sample loop for Hydrocarbons channel. Regulation of this valve can be accomplished from the front part of the valve oven.

In/Out Hydrogen Sample In – Sample Out in the front of Valve Oven for Hydrogen Channel

In/Out Hydrocarbons Sample In – Sample Out in the front of Valve Oven for Hydrocarbons Channel

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

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Analytical Unit

General Description The system includes the following analytical channels: Hydrocarbons Channel

This channel includes one capillary column: - 50 m, 0.53 ID RT-Alumina, 6 µm film thickness. The sample is injected by Valve # 3, with 250 µl sample loop.

Hydrogen Channel

The system include the following packed columns: - Column 1: 1 m, 1/8” Molecular Sieve 13X, 60 - 80 mesh. - Column 2: 1 m, 1/8” Haysep Q, 60 - 80mesh. The sample is introduced by valve # 2, with 1 ml sample loop.

The analysis of Hydrocarbons and hydrogen are described following in detail.

Valve Oven 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.

The switching of all valves has been factory set-up in the RUN TABLE menu. 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):

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- 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 Sampling valve #1 and press ENTER

The following screen appears:

o Inject at parameter is the time into the run that the sample is to be injected. o 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.

Valve Functions

Valve# Setting Function Valve# 2 Load Fill 1 ml sample loop and backflush the packed columns Valve# 2 Inject for Inject on analytical channel Valve# 3 Load Fill 250 µl sample loop for Hydrocarbons columns Valve# 3 Inject for Inject on analytical channel

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Set-up of Analyzer

The analyzer is supplied fully tested for the specific analysis and it is equipped with dedicated columns. However, during the transportation, vibrations and thermal fluctuations could loose some nuts. Additionally some air can diffuse and be adsorbed on to the column. The following procedure must be therefore applied in order to get smooth installation of the instrument in the lab.

Packed Columns Conditioning All columns must be conditioned before operating. Because of the different nature of their stationary phases these have to be conditioned at different temperatures and therefore in different steps.

o Haysep column must NOT exceed 180°C during conditioning o Molecular Sieve column must NOT exceed 300°C during conditioning o Capillary column must NOT exceed 200°C during conditioning

We strongly recommend to condition all these columns in an external Oven at a temperature 10°C lower than the maximum indicated above at a carrier gas flow rate of (suggested He) 20 ml/min for packed columns and 5 ml/min for capillary column. Columns conditioning should be performed for at least four hours.

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.

Leak check on Hydrogen Gas channel To perform a leak check, operate as follows:

1. Connect the columns and all the gases to the back of the Valve Oven. 2. Place the Valve #2 in the Inject position. 3. Cap the Right TCD detector outlet at the top of the GC by using a stopper and Cap the vent outlet 4. Set the pressure of the GC1 and GC2 at value of 100 kPa. Maintain the system in this condition for at least two minutes. 5. Close the manual regulators. Observe for any pressure decrease in the pressure gauge in the next two minutes. If the pressure does not decrease this means that the system is leak free. 6. In case of leak try to identify the leak point repeating the above operations and checking all connections starting from the valve. If the system is leak free, place the Valve #2 in the Load position and repeat steps 4 and 5. 7. Remove the cap.

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Leak check on Hydrocarbons channel To perform a leak check, operate as follows:

1.Connect the column and all the gases to the back of the GC. 2.Place the Valve #3 in the Inject position. 3. Cap the Fid base body using the blind jet p/n 40401901 provided in the standard outfit. Turn off the split and septum purge vents of the split/splitless injector 4.Set the pressure of the Left DPFC at a value of 100 kPa. Maintain the system in this condition for at least two minutes. 5. Set the 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. 6. 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. If the system is leak free place the Valve #3 in the Load position and repeat steps 4 and 6. 7. Remove the cap.

For the search of the leaks we recommend the use of electronic device. We dissuade the use of water and soap or other liquids

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Analytical Tuning

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

Test Mix 1 Component Concentration %

H2 1.10 Methane Matrix

Test Mix 2 Component Concentration %

Methane 1.10 Ethane 1.10 Ethylene 1.10 Propane 1.10 Propylene 1.10 n - Butane 1.10 1 - Butene 1.10 n - Pentane 1.10 1,3 - Butadiene 1.10 Pentene 1.10 Cis 2 - Pentene 1.10 n-Hexane 1.10 Helium Matrix

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Analytical Separation A schematic of the separation performed by the analyzer are the following: Hydrogen channel Step 1

The hydrogen channel comprises a gas sample valve injecting directly onto a combination of molecular sieve and porous polymer column in series. The sample is injected onto the columns where the separation of the hydrogen is made from the remaining components.

Step 1

Step 2

Once Hydrogen is eluted, the columns are placed in reverse flow and the remaining components are send to vent.

Step 2

Hydrocarbons channel Step 1

This channel comprises a gas sampling valve injecting into a split/splitless injector. The operator can therefore choose the ideal split ratio for the sample to be analyzed or to use the recommended split ratio. The sample is then passed onto a capillary column. The detector used on this channel is a Flame Ionization Detector (FID).

Step 1

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Analytical Parameters

Parameter Value Injector

Temperature 200° C DPFC Mode Constant Flow Carrier Gas Flow 2.5 ml/min Mode Split

Left SSL

Split flow 120 ml/min GC1 (A) Pressure 100 kPa GC2 (B) Pressure 40 kPa Detector

Base temperature 200°C Air Flow 350 ml/min Hydrogen Flow 35 ml/min

Left FID

Make up Flow 30 ml/min Block Temperature 200°C Transfer Temperature 190°C Filament Voltage 10 V Max Filament Temperature 400°C Make-Up Flow 10 ml/min

Right TCD

Reference Flow 30 ml/min Oven

Initial Temperature 80°C Initial Time 1 min Rate 10°C/min Final Temperature 160°C Final Time 10 min

Valve Oven Temperature 50°C Run Table Hydrogen Channel Time Valve# Position 00.01 Valve# 2 Sampling Inject for 0.70 Run Table Hydrocarbons Channel Time Valve# Position 00.01 Valve# 3 Sampling Inject for 0.30

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Analytical Result

Typical chromatograms produced in previous condition are reported in figure 1-2

Figure 1-2 Typical chromatogram of Test Mix1 on Hydrogen Channel Red Chromatogram: Analysis without backflush Blue chromatogram: Analysis with backflush

Test Mix 1 Retention Time Component Name 0.540 H2

1.653 Methane

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Typical chromatograms produced in previous condition are reported in figure 1-3

Figure 1-3 Typical chromatogram of Test Mix2 on Hydrocarbons channel

Retention Time Component Name 4.750 Methane 4.930 Ethane 5.103 Ethylene 5.442 Propane 6.175 Propylene 6.775 n - Butane 8.083 1 - Butene 9.160 n - Pentane 9.475 1,3 - Butadiene 10.855 Pentene 11.130 Cis 2 - Pentene 12.610 n - Hexane

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Troubleshooting

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

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.

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.

Consumables Part Number Description PKBA00000006000 Column: 1 m, 1/8” Haysep Q, 60-80 mesh PKBA00000010000 Column: 1 m, 1/8” Molecular Sieve 13X, 60-80 mesh RT-19701 Column: 50 m, 0.53 ID Alumina, 6 µm film thickness 27207026 1 ml sampling loop 27207029 0.25 ml sampling loop