APPLICATION NOTE

GPA2286: Extended Analysis for Natural Gas and

Similar Gaseous Mixtures by Temperature
programmed Gas Chromatography
• Analysis time under 30 minutes The value of an individual natural gas is related
• High sensitivity, linearity, accuracy primarily to the amount of thermal energy it
and precision contains, British Thermal Units (BTU) or Calorific
• GasXLNC software for flexible and Value (CV), and certain other physical properties,
such as liquid content, burning characteristics, dew
easy reporting
point, density, and compressibility. The composition
Keywords: of an individual natural gas varies depending on its
GPA 2286, Extended NGA, Micropacked , source and, therefore, its value will vary.
Natural Gas Analyzer
This application note describes GPA 2286-02
Extended using the AC Natural Gas Analyzer with
micropacked columns. This method is an extension
of GPA 2261-00.
INTRODUCTION
SOLUTION
Natural gas is a part of a continuum of hydro-
carbons, ranging from methane to the heaviest end The AC NGA GPA 2286 system consists of an
of oil, that are found in geological accumulations. By Agilent 7890A Series GC optimized for GPA 2286
far, the largest use of natural gas is as a fuel; other natural gas analysis. The AC NGA GPA 2286
uses are as a chemical feed stock or as a source of system determines hydrocarbons from C1 up to
pure single hydrocarbon gases. Gas separated from C14+, carbon dioxide, nitrogen, oxygen, and
a natural gas field will burn in that form but is hydrogen sulfide. The AC NGA GPA 2286 system
usually treated to remove or to control traces of complies with the GPA standard 2286-02 for natural
particular components for regulatory compliance or gas analysis and incorporates a high level of
for quality control. Hydrogen sulfide is a toxic and automation. Calibration, reporting and specific
corrosive gas; therefore, natural gas is subject to calculations are all performed with the GasXLNC
very low specification limits of hydrogen sulfide. software.

Figure 1: The largest use of natural gas is as a fuel

Figure 2: Flow diagram NGA system

Carbon dioxide is a less acidic gas but is still

potentially corrosive at pressures used for gas
transmission, and its concentration is also
controlled to very low percentage levels.
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APPLICATION NOTE
ANALYSIS
TCD. The second channel utilizes a gas sampling
The AC NGA GPA 2286 system consists of two valve, a split/ splitless injector, a capillary column,
channels. One channel contains a gas sampling and an FID. This channel analyzes the individual
valve and four columns: a stripper Pre-Column and components of the C6+ fraction. The sample is
three analysis columns. Detection is done by a injected on both channels at the same time.

TCD Channel

Methane
3950
3450
2950
Siganl (pA)

2450
1950

Nitrogen
Carbondioxide
1450
neo-Pentane
Propane

n-Butane

n-Pentane

950
i-Pentane

Ethane
i-Butane

Oxygen
450
C6+

-50
0 5 10 15 20 25 30
Time (min)

Figure 3: Micropacked column separation on TCD channel

FID Channel The stripper Pre-column separates the C6+ fraction

from the other components. The C6+ fraction is
5000 back flushed to the detector. By using multiple
Methane

4500 valves and columns, the other components are

divided into different fractions, further separated
4000 and detected by the TCD. The second channel
3500 splits the sample utilizing the split inlet and the gas
Ethane

sampling valve. The capillary column separates the

Siganl (pA)

3000
C5–C14+ components. The GasXLNC software
neo-Pentane n-Butane

2500 integrates the analyses results of both channels

Propane

2000 utilizing i-pentane and n-pentane as bridge

n-Pentane

components.
i-Butane

1500
i-Pentane

1000 The micropacked columns are located in a separate

Hexane

isothermal column box. This allows running both

500
channels simultaneous, resulting in total analysis
0 runtime of less than 30 minutes.
3 3.5 4 4.5 5
Time (min)

Figure 4: Capillary Column Separation on FID Channel

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APPLICATION NOTE
VALIDATION
Retention time and area precision require that all
The system and methodology of the AC NGA GPA
parameters (temperatures, pressure, flow, injection)
2286 system are thoroughly tested to comply with
are controlled to exacting tolerances. For active
GPA 2286-02 Extended. Repeatability, Linearity,
compounds, the inertness of the flow path can
Discrimination, Detection levels and Critical
dramatically affect area precision, especially at low
Separation of H2S / Propane will be discussed
levels.
further.
Area and retention time repeatability for the AC
NGA GPA 2286 system are measured for 20 runs
REPEATABILITY (table 1 and 2). Very good repeatability values are
obtained, which is possible because of the excellent
Area and retention time are the two primary stability of the Agilent 7890 Series GC electronic
measurements in Gas Chromatography. The pneumatics control, the precise temperature control
precision (repeatability) in which they are measured of all heated zones, the stable control of the
ultimately determines the validity of the generated injection volume by the gas sampling valve and the
quantitative data. inertness of the entire flow path.

Ret. time Ret. time Average Concentration

Component Component RSD
Average Stdev (n=20) Concentration Stdev (n=20)
FID i-Pentane 4.88 ± 0.0001 FID i-Pentane 0.201% ± 0.001 0.447%
FID n-Pentane 4.97 ± 0.0001 FID n-Pentane 0.397% ± 0.002 0.447%
TCD Propane 5.36 ± 0.0074 TCD Propane 1.000% ± 0.002 0.245%
FID n-Hexane 5.50 ± 0.0001 FID n-Hexane 0.050% ± 0.000 0.456%

TCD i-Butane 6.63 ± 0.0153 TCD i-Butane 0.400% ± 0.001 0.239%

TCD n-Butane 7.64 ± 0.0227 TCD n-Butane 1.000% ± 0.002 0.233%

TCD Neopentane 8.15 ± 0.0263 TCD Neopentane 0.099% ± 0.001 0.731%

TCD Carbondioxide 16.15 ± 0.0096 TCD Carbondioxide 3.040% ± 0.009 0.281%

TCD Ethane 19.24 ± 0.0353 TCD Ethane 3.010% ± 0.007 0.233%

TCD Oxygen 20.92 ± 0.0064 TCD Oxygen 0.201% ± 0.002 0.930%

TCD Nitrogen 21.81 ± 0.0121 TCD Nitrogen 9.000% ± 0.029 0.324%

TCD Methane 23.54 ± 0.0222 TCD Methane 81.600% ± 0.171 0.210%

100.00%
Table 1: Retention time repeatability using NGA
calibration gas Table 2: Area repeatability using NGA calibration
gas

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APPLICATION NOTE
LINEARITY

The linearity of the system is checked using dynamic Dilution Level 1 2 3 4 5 6 7

dilutions of a representative NGA calibration gas with Cal Gas (ml/min) 19.50 10.10 7.10 4.00 3.00 1.80
helium. 7 levels of the diluted NGA gas are used to
Helium (ml/min) 19.90 20.00 20.10 20.20 20.40 20.40
perform an injection by the GSV. For each
component the concentrations in the dilutions are Dilution factor neat 2.02 2.98 3.83 6.05 7.80 12.33
calculated, and linearity plots are created (see Table 3: Dilution table
examples below). All calibration lines have a linearity
correlation > 0.999.

T C D M ethane, T C D 2 B T C D N itrogen, T C D 2 B
Area = 1275.5887*Am t +500.98275 Area = 1703.05191*Am t +12.780395
Area R el. R es% (3): 7.8402e-1 Area R el. R es% (4): 9.0893e-1
100000 15000
1 1
12500
80000
10000
60000 2 2
7500
3 3
40000 4 4
5000
20000 65 65
7 2500 7
0 C orrelation: 0.99996 0 C orrelation: 0.99998
0 50 Amount[%] 0 5 Amount[%]

T C D O xygen, T C D 2 B T C D n-Pentane, T C D 2 B
Area = 1510.25687*Am t -0.360469 Area = 3586.39408*Am t +2.5398637
Area R el. R es% (5): -5.9927e-1 Area R el. R es% (4): 5.3125e-1
300 1400
1 1
250 1200
200 1000
2 800 2
150
3 600 3
100 4 4
400
65 65
50 7 200 7
0 C orrelation: 0.99983 0 C orrelation: 0.99999
0 0.1 Amount[%] 0 0.2 Amount[%]

FID n-Pentane, FID 1 A FID n-H exane, FID 1 A

Area = 2505.67456*Am t -0.1470738 Area = 2983.40688*Am t -0.2739378
Area R el. R es% (5): 3.1504e-1 Area R el. R es% (2): -1.563
1000
1 140 1
800 120
100
600 2 2
80
400 3 60 3
4 4
40
200 65 65
7 20 7
0 C orrelation: 0.99998 0 C orrelation: 0.99994
0 0.2 Amount[%] 0 0.02 0.04 Amount[%]

Figure 5: Examples of linearity plots on both FID and TCD channel

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APPLICATION NOTE
DISCRIMINATION CHECK

Using a microliter syringe, 0,5 µl of a hydrocarbon Finally the measured response factors are
test mix is injected on the front channel, using the compared with the theoretical response factors
correct split ratio and temperature program settings (table 4). It can be concluded that all determined
(see figure 6 for the chromatogram). The peak Response Factors are comparable with the
retention times and peak areas are recorded by the theoretical response factors (maximum deviation
FID. Response factors are calculated using the 0,02).
exact concentrations of the components.

1200
C7
Benzene

1000
Toluene

800
Siganl (pA)

600
C5
C6

400
C8

C11

C14
C10

C12

C13
C9

200

0
0 5 10 15 20 25 30
Time (min)

Figure 6: Chromatogram discrimination check reference sample

Component Percentage Weight Peak Area Area % Response Resp. factor Theoretical
(gram) pA*s factor relative to C5 Resp. Factor
(rel. to C5)
Pentane 1.06% 0.32 709.25 1.046 1.50E-05 1.00 1.00
Hexane 1.06% 0.32 712.15 1.050 1.49E-05 1.00 1.00
Benzene 2.06% 0.62 1,541.53 2.272 1.34E-05 0.89 0.90
Heptane 86.54% 26.11 58,389.14 86.071 1.48E-05 0.99 0.99
Toluene 2.05% 0.62 1,518.70 2.239 1.35E-05 0.90 0.91
Octane 1.03% 0.31 709.39 1.046 1.46E-05 0.97 0.99
Nonane 1.02% 0.31 703.18 1.037 1.46E-05 0.97 0.99
Decane 1.02% 0.31 705.61 1.040 1.45E-05 0.97 0.99
Undecane 1.06% 0.32 726.57 1.071 1.46E-05 0.97 0.99
Dodecane 1.03% 0.31 708.19 1.044 1.45E-05 0.97 0.98
Tridecane 1.01% 0.31 692.39 1.021 1.46E-05 0.98 0.98
Tetradecane 1.05% 0.32 722.30 1.065 1.45E-05 0.97 0.98
Table 4: Results discrimination test mix

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APPLICATION NOTE
DETECTION AND QUANTIFICATION
LIMIT
LOD Range/Scope covered
Component (3x N) GPA 2286
Detection and quantification limit of each
FID i-Pentane < 0.001% 0.001-100 %
component is calculated using the chromatogram of
level 7 (≈ 12 x diluted) NGA gas. LOD is defined as FID n-Pentane < 0.001% 0.001-100 %
3 * standard deviation of the noise, LOQ is defined FID n-Hexane < 0.001% 0.001-100 %
as 10 * standard deviation of the noise. TCD Propane < 0.001% 0.001-100 %

3∗𝑁∗𝐶 ∗𝑊 TCD i-Butane < 0.001% 0.001-100 %

𝐿𝑂𝐷 =
𝐴 TCD n-Butane < 0.001% 0.001-100 %
TCD Neopentane < 0.001% 0.001-100 %
10 ∗ 𝑁 ∗ 𝐶 ∗ 𝑊
𝐿𝑂𝑄 = TCD Carbondioxide < 0.001% 0.005-100 %
𝐴
TCD Ethane < 0.001% 0.001-100 %
Where: TCD Oxygen < 0.001% 0.005-100 %
N = Noise of signal (pA)
TCD Nitrogen < 0.001% 0.005-100 %
C = Concentration of component (ppm)
W = Peak width (s) TCD Methane < 0.001% 0.001-100 %
A = Area (pA*s)
Table 5: LOD and LOQ for major Natural gas
components

Separation SEPARATION H2S/PROPANE

H2S / Propane H2S elutes just before Propane. The resolution is
calculated between the two peaks, based on the
4.346 Propane

retention time’s en peak width at half height

550
reported by ChemStation. Specification ≥ 1.5
(baseline separation).
450
𝑅𝑡2 − 𝑅𝑡1
𝑅𝑠 =
𝑊1 + 𝑊2
Siganl (pA)

350
3.871 H2S

Where:
250
Rt1 = Retention time H2S (min.)
Rt2 = Retention time Propane (min.)
150 W1 = Peak width at half height of H2S (min.)
W2 = Peak width at half height of Propane (min.)
50
4.346 − 3.871
𝑅𝑠 =
-50 0.1136 + 0.1069
2.7 3.7 4.7
𝑅𝑠 = 2.15
Time (min)

Figure 7: Overlay of H2S and Propane in Natural gas

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APPLICATION NOTE
CALCULATIONS
Parameter
The AC NGA GPA 2286 system defines many Liquid volume
calculations for the analyst, including calculations Liquid vapor pressure
Relative density of liquefied petroleum gas (LPG)
established in ASTM D 2421, D 2598, D 3588,
Compressibility of mixture
ISO 6976 and GPA 2172. Table 6 lists a subset
Real specific gravity at 15.55°C (60° F)
of standard calculations that can be performed Real BTU
using GasXLNC software. GPM
Ideal calorific value on molar basis (inferior and superior)
To reduce operator involvement, the software Ideal calorific value on mass basis (inferior and superior)
contains a standard database of component Ideal calorific value on volume basis (inferior and superior)
constants and formulas. A user-friendly edit Real calorific value on volume basis (inferior and superior)
mode allows authorized users to edit the Ideal & Real wobbe index (superior)
database. The GasXLNC software includes Density
several standard report formats. In addition, a Table 6: Some of the standard gas calculations available
user can easily create customized reports. in GasXLNC software
Ethane

FID Channel
n-Butane
Methane

n-Pentane

methyl cyclopentante

490
Propane
i-Butane
i-Pentane

390
n-Hexane

methyl cyclohexane
Cyclohexane

290
Siganl (pA)

iso-Octane

n-Heptane

Toluene

ethyl benzene

ortho-xylene
meta-xylene
para-xylene
190
n-Octane

n-nonane
Benzene

90

-10
3 4 5 6 7 8 9 10
Time (min)

Figure 8: Unknown Natural Gas, FID Channel

CONCLUSION

The AC NGA GPA 2286 system is a specialized solution for Natural Gas stream composition analysis.
Its performance exceeds GPA 2286-02 Extended, which allows for very accurate value determination.
The dedicated GAS XLNC software automates analysis and calibration functions and facilitates simple
reporting of individual component concentrations and a variety of physical properties, reducing errors and
increasing laboratory productivity.

AC Analytical Controls® has been the recognized leader in chromatography analyzers for gas, naphtha and gasoline streams in crude
oil refining since 1981. AC also provides technology for residuals analysis for the hydrocarbon processing industry. Applications cover
the entire spectrum of petroleum, petrochemical and refinery, gas and natural gas analysis; ACs Turn-Key Application solutions
include the AC Reformulyzer ® , DHA, SimDis, NGA, Hi-Speed RGA and Customized instruments.

00.00.191 2012/1 - © Copyright 2012 PAC L.P. All rights reserved

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