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Fundamentals of Gas Chromatography

Class # 5170-1
John Renfrow
ABB Totalflow
7051 Industrial Blvd
Bartlesville, OK. 74006
John.s.renfrow@us.abb.com

INTRODUCTION
The objective of the analyzation of natural gas by gas chromatography is to obtain a sample from the system in
question and analyze the product without changing the composition or environment. There are 3 basic systems in
obtaining a natural gas analysis by gas chromatography:
1. Sampling Systems
2. Gas Chromatography
3. Calculation of data.
In this paper we will discuss each system.

SAMPLING SYSTEMS

All sampling systems have certain requirements Sample probes are always recommended to be used and inserted
into the middle 1/3 of the pipeline when taking a sample of any type. Sample probes should be 5 times the pipe
diameter downstream of any obstruction. The sample system temperature must be 20-50 degrees above the
sample hydrocarbon dew point.
The 3 types of sampling natural gas are:
1. Spot Sampling

2. Continuous Sampling

3. On-line Sampling with Chromatography

Spot Sampling

Spot sampling is the process of obtaining an instantaneous sample from the system. There are 2 types of spot
sampling:

1. Constant volume cylinder

2. Portable chromatography

Gas Processor’s Association Method 2166 explains in detail the 8 different procedures for taking spot samples
using a constant volume. It is important to consult with laboratory personnel and agree on the method of spot
sampling to be used. The cleaning of
spot sample cylinders is an important part of obtaining a good sample. G.P.A 2166(Appendix A) explains the
procedures for cleaning cylinders. When transporting sample containers D.O.T. regulations should be reviewed by
a company safety department to insure technicians comply with the shipping regulations.
Portable chromatographs are the second type of spot sampling. The chromatograph is either taken to the point of
sample or sample systems are taken to a vehicle where the instrument resides. Instead of sampling with cylinders,
insertion probes are used with tubing to remove the product from the sample point. Sample lines must be 20-50
degrees above the hydrocarbon dew point of the sample gas.

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Continuous Sampling
A mechanical sampling device is used in continuous sampling. There are 2 types of continuous sampling:

1. Time proportional sampling uses a timer to actuate the mechanical sampler.

2. Proportional to flow sampling requires a sampler actuated by a flow computer or other flow calculation
device.

Both proportional to flow and time proportional sampling requires an approximate estimation of the gas flow to
determine the sampling intervals. The continuous sampler uses 2 types of cylinders:

1. Constant volume cylinders

2. Constant pressure cylinders

Constant volume cylinders require a single port sample probe. Constant pressure cylinders require a dual port
sample probe. The continuous sampler usually produces an average sample over a predetermined flow or time
period.

On-line Chromatography

On-line chromatography is the use of a permanently installed gas chromatograph at the sample point of the
system. The chromatograph may be installed on the system piping, in an environmental enclosure or an analyzer
building. Probe regulators are recommended to be installed to transfer sample to the chromatograph. The pressure
of the probe regulator is usually 15 PSIG. The probe regulator and calibration standard regulator should be the
same outlet pressure. It is recommended to install the chromatograph as close to the sample point as possible.
Regulatory codes may restrict where the chromatograph is installed in regard to sample point. Carrier and
calibration gas cylinders and accessories are onsite at these installations. Real Time measurement is the use of
gas chromatography communicating analysis data to a flow computer. The communication of data between
chromatograph and flow computer enables measurement calculations to be performed in the field. Remote
communication is common at these installations. Common carriers of communication are radio, telephone,
Ethernet or satellite.

GAS CHROMATOGRAPHY SYSTEMS

Chromatography is the ability to separate components based upon their affinities for two separate phases.
Stationary and mobile are the two phases of gas chromatography. In gas chromatography the mobile phase is the
carrier gas (usually helium for a C6+ natural gas analysis). The stationary phase is the chromatograph column. A
chromatograph system is comprised of the following:

1. Sampling system(s)

2. Valves

3. Column Sets

4. Detectors

Sampling systems are designed to introduce the sample to the chromatograph without altering the composition of
the gas. All components of the sampling system should be made of 316 stainless steel. It is required that the
temperature of the system be 20-50 degrees above the hydrocarbon dew point of the sample gas. The system
must be conditioned between samples to remove the previous sample. Conditioning of the sample system may
consist of evacuation, helium purge, next sample purge or a combination of purges.
Chromatograph valves are designed to inject and/or transfer the flow of the sample. The sample valve has a
sample loop to inject the sample onto the column system. The column valves are designed to separate the different
components in natural gas and transfer them to the detector in the desired elution order.
Packed and capillary column sets are used in natural gas chromatography. Packed columns are the most
common type and are usually 1/16” stainless steel tubing and approximately .5mm in diameter. There is a variety of

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packed column material used for natural gas depending on the application. Capillary columns are usually for
extended analysis and are approximately .1 mm in diameter.
The two types of detectors most commonly used in natural gas analysis are Thermal Conductivity (TCD) and
Flame Ionization (FID) detectors. TCD detectors are the most frequently used for C6+ natural gas applications. FID
detectors are usually in laboratories for extended analysis applications. The trace generated by the detector signal
is called the chromatogram (Figure 1). The flow rate of the carrier gas and the temperature of the column must be
carefully controlled to yield repeatable chromatograms.

13500

11500

9500

7500

Series1
5500

3500

1500

-500 6 11 16 21 26 31 36 41 46 51

-2500

Figure 1- Detector Trace or Chromatogram

It is necessary to control these parameters because components are identified by their retention time. The retention time
is the amount of time from the beginning of the analysis until the component exits the column. If flow and temperature
are held constant, the retention time is very repeatable. Retention time is the primary means of identification.
The concentration of the component is determined by comparing the peak area of the unknown to the peak area of a
known standard. To calculate the amount of a given component, follow the equation:
Cunk = PAunk/PAstd * Cstd
Where
Cunk = Concentration of unknown
Cstd = Concentration of standard
PAunk = Peak Area of unknown
PAstd = Peak Area of standard
Various combinations of columns, valves and detectors are used in natural gas applications. The most important
part of the chromatograph system is producing repeatable results from a quality standard.
Purchase a calibration standard with all the components in the sample gas. The calibration standard blend is the
reference that all sample gas is compared. It is extremely important that all standards be gravimetrically blended
and has certified molecular percentages and dew-point. Below is an example of a natural gas standard
concentration.
Component Mol. %
N2 = 2.5%
CO2 = 1.00%
C1 = 89.564%
C2 = 4.99%
C3 = 0.999%
iC4 = 0.305%
nC4 = 0.309%
NeoC5 = 0.101%
iC5 = 0.100%
nC5 = 0.102%
C6+ = 0.030%
Total = 100.000%

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GPA Method 2261 (Analysis for Natural gas and Similar Gaseous Mixtures by Gas Chromatography) is the
standard for analyzing natural gas. GPA 2261 explains in detail the chromatography and procedures for natural gas
using gas chromatography.

CALCULATION OF DATA
After the gas chromatograph has been properly calibrated and the molecular percentages of the natural gas
sample determined, several calculations may be computed. The most common calculations in gas measurement
are, B.T.U. (British Thermal Unit), Relative Density, and Compressibility. G.P.A Method 2172 (Calculation of Gross
Heating Value, Relative Density, and Compressibility Factor for Natural Gas Mixtures from Compositional Analysis)
describes in detail the calculation of data to be used for natural gas measurement data. The method for obtaining
natural gas factors needed for calculation is 2145. G.P.A Method 2261 gives an average factor to use for C6+. The
contract between two companies may predefine the C6+ factors. An extended analysis may be required in certain
applications to determine C6+ factors.

CONCLUSION
The fundamentals of chromatography require quality procedures in sampling, chromatography, and calculation of
data. There are several techniques to sample natural gas. It is advisable to work with the laboratory and
measurement department to agree on the method most suitable for the system. Laboratories should be audited on
a regular basis for repeatability. Calculations should also be audited and updated on a regular basis. Any deviation
from industry standards may produce undesirable results.

References
1. GPA Standard 2145-03, Table of Physical Constants for Hydrocarbons and Other Compounds of Interest to the
Natural Gas Industry
2. GPA Reference Bulletin 181-06, Heating Value As A Basis For Custody Transfer of Natural Gas (1984 Draft)
3. GPA Standard 2261-00 Analysis for Natural Gas and Similar Mixtures by Gas Chromatography
4. "Btu Measurement in Natural Gas Using Process Gas Chromatography", Kizer and Sund, Proc. of Gulf Coast
Meas. Soc. #24, 1989, p. 72
5. Kizer, "Natural Gas Energy Determination Review", ISA Proceedings, 1991, p. 777
6. “Energy Measurement Using On-Line Chromatography”, Kizer, Proc. Of the71st International school of
Hydrocarbon Measurement, 1996, p. 544 ff.
7. AGA Report No. 8

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