Trace CO and CO2 in Hydrogen and Light Gaseous Hydrocarbons

by GC
UOP Method 603-12
Scope
This method is for determining low concentrations (0.2 to 500 mol-ppm) of carbon monoxide (CO)
and carbon dioxide (CO2) in high purity hydrogen, methane and other gas-phase samples. The lower
limit of quantitation for CO and CO2 in samples containing high concentrations of hydrogen, nitrogen,
and other gases, is 0.2 mol-ppm. For samples containing high methane concentrations, an analysis
under a different valve configuration is necessary to resolve carbon dioxide from interfering methane.

References
Analyzer manufacturer’s operating manual
UOP Method 999, “Precision Statements in UOP Methods,” www.astm.org

Outline of Method
A repeatable volume of sample is introduced through the gas sampling/backflush valve into a
two-column system. After the elution of CO2 from the first column into the second column, the valve is
switched to back flush the components remaining in the first column to the vent. For samples
containing high methane, the 4-port switching valve is used as a heart cut valve to vent the bulk of
methane eluting from the first column. CO, CO2 and methane are separated on the second column and
converted in the methanizer into methane. A flame ionization detector is used to detect the methane
produced. Concentrations of CO and CO2 are calculated using the external standard method of
quantitation.

Apparatus
References to catalog numbers and suppliers are included as a convenience to the method user. Other
suppliers may be used.
Analyzer, gas analyzers are available pre-configured, including a data system, from several suppliers.
A typical flow diagram of such an analyzer is shown in Figure 1. Confirm with the supplier that the
analyzer is appropriate for the stream to be analyzed and the analysis required. A partial list of
suppliers include: Agilent Technologies, Analytical Controls (PAC), PerkinElmer, and Separation
Systems.
Instrument gas supply regulators; not all instruments will require all regulators listed below.
IT IS THE USER'S RESPONSIBILITY TO ESTABLISH APPROPRIATE PRECAUTIONARY PRACTICES AND TO
DETERMINE THE APPLICABILITY OF REGULATORY LIMITATIONS PRIOR TO USE. EFFECTIVE HEALTH AND SAFETY
PRACTICES ARE TO BE FOLLOWED WHEN UTILIZING THIS PROCEDURE. FAILURE TO UTILIZE THIS PROCEDURE IN
THE MANNER PRESCRIBED HEREIN CAN BE HAZARDOUS. MATERIAL SAFETY DATA SHEETS (MSDS) OR
EXPERIMENTAL MATERIAL SAFETY DATA SHEETS (EMSDS) FOR ALL OF THE MATERIALS USED IN THIS
PROCEDURE SHOULD BE REVIEWED FOR SELECTION OF THE APPROPRIATE PERSONAL PROTECTION
EQUIPMENT (PPE).

© COPYRIGHT 1971, 1988, 2012 UOP LLC. All rights reserved.

Nonconfidential UOP Methods are available from ASTM International, 100 Barr Harbor Drive, PO Box C700, West
Conshohocken, PA 19428-2959, United States. The UOP Methods may be obtained through the ASTM website, www.astm.org,
or by contacting Customer Service at [email protected], 610.832.9555 FAX, or 610.832.9585 PHONE.

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Regulator, air, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi), Matheson
Tri-Gas, Model 3122-590
Regulator, helium, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi),
Matheson Tri-Gas, Model 3122-580
Regulator, hydrogen, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi),
Matheson Tri-Gas, Model 3122-550
Regulator, nitrogen, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi),
Matheson Tri-Gas, Model 3122-580
Leak detector, gas, Grace Davison, Cat. No. 60229

Reagents and Materials

References to catalog numbers and suppliers are included as a convenience to the method user. Other
suppliers may be used.
Columns, replacement, 2 m of 1/16-inch OD x 0.050-inch ID stainless steel tubing, micropacked
“Hayesep Q”, two required. These are typical columns used for the analysis. Contact the analyzer
manufacturer for specific columns and part numbers.
Instrument gases; not all instruments will require all gases listed below.
Air, zero gas, total hydrocarbons less than 2.0 ppm as methane
Helium, zero gas, total hydrocarbons less than 0.5 ppm as methane
Hydrogen, zero gas, total hydrocarbons less than 0.5 ppm as methane
Nitrogen, zero gas, total hydrocarbons less than 0.5 ppm as methane
Gas calibration blends; purchase only those required for the sample compositions to be analyzed
Blend 1, 5 mol-ppm CO, 5 mol-ppm CO2 and 25 mol-ppm methane in hydrogen, Matheson
Tri-Gas or local supply
Blend 2, 200 mol-ppm CO, 200 mol-ppm CO2 and 200 mol-ppm methane in hydrogen, Matheson
Tri-Gas or local supply
Blend 3, 5 mol-ppm CO, 5 mol-ppm CO2 in methane, Matheson Tri-Gas or local supply
Gas purifiers, for carrier gases, to remove oxygen and moisture, VICI Mat/Sen, Cat. Nos. P100-1
(helium), P200-1 (hydrogen), P300-1 (nitrogen), and (optional) indicating oxygen traps, Restek,
Cat. No. 22010, as needed for the specific instrument used
Methanizer, replacement, nickel catalyst tube. Contact the analyzer manufacturer for specific
configuration and part number.

Procedure
The analyst is expected to be familiar with general laboratory practices, the technique of gas
chromatography, and the equipment being used. Dispose of used reagents, materials, and samples in an
environmentally safe manner according to local regulations.
Preparation of Apparatus
1. Install the gas purifier in the supply line between the carrier gas source and the carrier gas inlets
on the gas chromatograph.

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• Column life is significantly reduced if gas purifiers are not used. Replace the gas purifiers at intervals
determined by good laboratory practice. Indicating oxygen traps may be placed downstream of the
gas purifiers. When the indicator shows one-half used, replace both the gas purifier and the
indicating trap.
2. Follow the instrument set-up procedure provided by the manufacturer but do not initially apply
heat to the column oven; see Column Conditioning, below.
• CAUTION: Hydrogen leakage into the confined volume of the column oven can cause a violent
explosion. Therefore, it is mandatory to check for leaks each time a connection is made and
periodically thereafter.

Column Conditioning
The columns must be conditioned to remove any traces of solvent or volatile components in the liquid
phase and allow the phase to distribute itself evenly over the surface of the solid support. For porous
polymers, conditioning is necessary to remove residual solvents used during polymerization and any
compounds adsorbed during storage and handling. This column conditioning is required when the
instrument is first installed, and whenever columns are replaced.
Pre-condition the chromatographic columns individually in the chromatograph column oven using
the following procedures:
1. Connect the column to the inlet and flush the column with carrier gas to remove air. Do not
connect the column to the detector while conditioning: any volatile material released from the
column may form deposits on the detector. If the carrier gas is hydrogen, connect a piece of
tubing to the outlet end of the column and route it outside the column oven to prevent the
accumulation of flammable gas within the column oven.
2. Using analytical flow rates, heat the column to 100°C, or 50°C below the maximum operating
temperature, whichever is lower, and maintain for 30 minutes.
3. Heat the column to the final conditioning temperature at a rate of 4°C/min or less. Maintain this
temperature for at least 4 hours with normal carrier gas flow rates. The final conditioning
temperature should ideally be at least 20°C above the analysis temperature, but not higher than
10-15°C below the maximum operating temperature for the column.
• It may be more convenient to condition the columns in a separate GC, if available.
4. When the columns are conditioned, reconnect them to the valves in the column oven and check
for leaks.
• CAUTION: Hydrogen leakage into the confined volume of the column oven can cause a violent
explosion. Therefore, it is mandatory to check for leaks each time a connection is made and
periodically thereafter.

Chromatographic Technique
1. Connect the sample or calibration blend cylinder to the sample inlet and purge the system with
the gas to be analyzed.
2. Flush the inlet tubing and sample loop with the gas for one minute with a flow of approximately
50 mL/min. Stop the sample flow for a few seconds, allowing the contents of the sample loop to
equilibrate to atmospheric pressure.
• Some instruments are programmed to stop the flow of sample and allow the contents of the sample
loop to equilibrate to atmospheric pressure before the sample is injected. In this case, the analysis
may be started without stopping the sample flow.
3. Start the analysis on the GC. A typical chromatogram is shown in Figure 2.

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• For samples containing high methane, the 4-port switching valve is used as a heart cut valve to vent
the bulk of methane eluting from the first column. Follow the instructions for high methane containing
samples in the instrument operating manual.

Calibration
Response factors are required to relate the peak areas of the converted CO and CO2 to mol-ppm. A
standard blend containing 5 mol-ppm CO, 5 mol-ppm CO2 and 25 mol-ppm methane in hydrogen is
used for calibration of samples containing low concentrations of CO and/or CO2, while a blend
containing 200 mol-ppm CO, 200 mol-ppm CO2 and 200 mol-ppm methane is used for samples
containing high concentrations of CO and/or CO2. The methane is included in the blends to monitor
separation efficiency of the chromatographic columns and the hydrogenation efficiency of the
methanizer. A standard blend containing 5 mol-ppm CO and 5 mol-ppm CO2 in methane is used for
samples containing high concentrations of methane.
Analyze the appropriate blend as described under Chromatographic Technique for CO, CO2 and
methane. Determine the peak areas of the methane and the converted CO and CO2. Calculate the
response factor relating to the mol-ppm/unit of peak area for each component using Equation 1:
P
K= (1)
A
where:
A = peak area for converted CO, CO2 or methane
K = response factor for converted CO, CO2 or methane
P = mol-ppm of CO, CO2 or methane
If baseline resolution is obtained between all three components, the separation efficiency of the
chromatographic columns is satisfactory. If the response factors for CO and CO2 are within 5% of the
methane factor, the hydrogenation reactor efficiency is satisfactory.
Determine response factors as directed above daily when samples are analyzed.

Calculations
Calculate the mol-ppm of either component of interest in the sample to the nearest 1 mol-ppm using
Equation 2:
Component, mol-ppm = KS (2)
where:
K = response factor for the converted component, previously defined
S = peak area for the converted component

Notes
1. It is necessary to prevent heavier hydrocarbons from passing over the methanizer in order to avoid
any buildup of carbon on the surface of the catalyst. This is accomplished by the backflushing of
the first column.
2. Samples with high methane concentrations can cause carbon buildup on the catalyst of the
methanizer. To remove this carbon buildup, inject nitrogen multiple times or until the observed CO
is less than 0.2 mol-ppm.
Precision
Precision statements were determined using UOP Method 999, “Precision Statements in UOP
Methods.”

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Repeatability and Site Precision

A nested design was carried out for determining impurities in two samples containing primarily
hydrogen and two samples containing primarily methane. The four samples were analyzed by two
analysts, with each analyst performing analyses on two separate days, performing four analyses each
day for a total of 64 analyses. Using a stepwise analysis of variance procedure, the within-day and
within-lab estimated standard deviations (esd) were calculated at the concentration means listed in
Table 3. Two analyses performed in one laboratory by the same analyst on the same day should not
differ by more than the repeatability allowable differences shown in Table 3 with 95% confidence.
Two analyses performed in one laboratory by different analysts on different days should not differ by
more than the site precision allowable differences shown in Table 3 with 95% confidence.
Table 3
Repeatability and Site Precision, mol-ppm
Repeatability Site Precision
Within- Allowable Within- Allowable
Sample Mean Day esd Difference Lab esd Difference
CO in hydrogen 4.9 0.04 0.1 0.06 0.2
CO in hydrogen 200.6 0.17 0.3 0.27 1.0
CO2 in hydrogen 5.1 0.02 0.1 0.03 0.1
CO2 in hydrogen 203.4 0.16 0.5 0.46 2.8
CO in methane 5.0 0.02 0.1 0.02 0.1
CO in methane 200.7 0.23 0.2 0.27 0.7
CO2 in methane 5.1 0.04 0.1 0.04 0.1
CO2 in methane 203.4 0.93 1.2 1.16 4.0
The data in Table 3 represent short-term estimates of the repeatability of the method. When the test is
run routinely, use of a control standard and a control chart is recommended to generate an estimate of
long-term repeatability.
Reproducibility
There is insufficient data to calculate the reproducibility of the test at this time.

Time for Analysis

The elapsed time and labor requirements for one analysis are identical, 0.25 hour.

Suggested Suppliers
Agilent Technologies, 2850 Centerville Rd., Wilmington, DE 19808-1610, USA (302-633-8000)
www.agilent.com
Analytical Controls (PAC), 8824 Fallbrook Dr., Houston, TX 77064, USA (203-925-4602)
www.paclp.com
Grace Davison Discovery Sciences, 2051 Waukegan Rd., Deerfield, IL 60015, USA (847-948-8600)
www.discoverysciences.com
Matheson Tri-Gas, 166 Keystone Dr., Montgomeryville, PA 18936, USA (215-641-2700)
www.mathesontrigas.com
PerkinElmer, 940 Winter St., Waltham, MA 02451, USA (203-925-4602) www.perkinelmer.com
Restek, 110 Benner Circle, Bellefonte, PA 16823, USA (814-353-1300) www.restek.com

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Separation Systems, 100 Nightingale Ln., Gulf Breeze, FL 32561, USA (850-932-1433)
www.separationsystems.com
VICI Mat/Sen, 7806 Bobbitt, Houston, TX 77055 USA (713-688-9345) www.vicimatsen.com

603-12

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