APPLICATION NOTE

GPA2286: Extended Analysis for Natural Gas and Similar Gaseous Mixtures by Temperature programmed Gas Chromatography
Analysis time under 30 minutes High sensitivity, linearity, accuracy and precision GasXLNC software for flexible and easy reporting Keywords: GPA 2286, Extended NGA, Micropacked , Natural Gas Analyzer
The value of an individual natural gas is related primarily to the amount of thermal energy it contains, British Thermal Units (BTU) or Calorific Value (CV), and certain other physical properties, such as liquid content, burning characteristics, dew point, density, and compressibility. The composition of an individual natural gas varies depending on its source and, therefore, its value will vary. 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
Natural gas is a part of a continuum of hydrocarbons, ranging from methane to the heaviest end of oil, that are found in geological accumulations. By far, the largest use of natural gas is as a fuel; other uses are as a chemical feed stock or as a source of pure single hydrocarbon gases. Gas separated from a natural gas field will burn in that form but is usually treated to remove or to control traces of particular components for regulatory compliance or for quality control. Hydrogen sulfide is a toxic and corrosive gas; therefore, natural gas is subject to very low specification limits of hydrogen sulfide.

SOLUTION
The AC NGA GPA 2286 system consists of an Agilent 7890A Series GC optimized for GPA 2286 natural gas analysis. The AC NGA GPA 2286 system determines hydrocarbons from C1 up to C14+, carbon dioxide, nitrogen, oxygen, and hydrogen sulfide. The AC NGA GPA 2286 system complies with the GPA standard 2286-02 for natural gas analysis and incorporates a high level of automation. Calibration, reporting and specific calculations are all performed with the GasXLNC 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
The AC NGA GPA 2286 system consists of two channels. One channel contains a gas sampling valve and four columns: a stripper Pre-Column and three analysis columns. Detection is done by a TCD. The second channel utilizes a gas sampling valve, a split/ splitless injector, a capillary column, and an FID. This channel analyzes the individual components of the C6+ fraction. The sample is injected on both channels at the same time.

TCD Channel
3950 3450 2950 Siganl (pA) 2450
Carbondioxide Nitrogen Ethane Methane n-Butane neo-Pentane

1950 1450
Propane
i-Pentane

i-Butane

950
C6+

n-Pentane

450
-50 0

10

15 Time (min)

20

Oxygen

25

30

Figure 3: Micropacked column separation on TCD channel

FID Channel
5000 4500 4000
Methane

3000 2500 2000 1500 1000 500 0 3

Ethane Propane i-Butane neo-Pentane n-Butane

3500 Siganl (pA)

i-Pentane n-Pentane

The stripper Pre-column separates the C6+ fraction from the other components. The C6+ fraction is back flushed to the detector. By using multiple valves and columns, the other components are divided into different fractions, further separated and detected by the TCD. The second channel splits the sample utilizing the split inlet and the gas sampling valve. The capillary column separates the C5C14+ components. The GasXLNC software integrates the analyses results of both channels utilizing i-pentane and n-pentane as bridge components. The micropacked columns are located in a separate isothermal column box. This allows running both channels simultaneous, resulting in total analysis runtime of less than 30 minutes. 5
Hexane

3.5

4 Time (min)

4.5

Figure 4: Capillary Column Separation on FID Channel

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

REPEATABILITY
Area and retention time are the two primary measurements in Gas Chromatography. The precision (repeatability) in which they are measured ultimately determines the validity of the generated quantitative data.

Component FID i-Pentane FID n-Pentane TCD Propane

Ret. time Average 4.88 4.97 5.36

Ret. time Stdev (n=20) 0.0001 0.0001 0.0074

Component FID i-Pentane FID n-Pentane

Average Concentration Concentration Stdev (n=20) 0.201% 0.397% 0.001 0.002

RSD 0.447% 0.447%

TCD Propane
FID n-Hexane TCD i-Butane TCD n-Butane TCD Neopentane TCD Carbondioxide TCD Ethane

1.000%
0.050% 0.400% 1.000% 0.099% 3.040% 3.010%

0.002
0.000 0.001 0.002 0.001 0.009 0.007

0.245%
0.456% 0.239% 0.233% 0.731% 0.281% 0.233%

FID n-Hexane
TCD i-Butane TCD n-Butane TCD Neopentane TCD Carbondioxide TCD Ethane

5.50
6.63 7.64 8.15 16.15 19.24

0.0001
0.0153 0.0227 0.0263 0.0096 0.0353

TCD Oxygen
TCD Nitrogen TCD Methane

20.92
21.81 23.54

0.0064
0.0121 0.0222

TCD Oxygen
TCD Nitrogen TCD Methane

0.201%
9.000% 81.600% 100.00%

0.002
0.029 0.171

0.930%
0.324% 0.210%

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 dilutions of a representative NGA calibration gas with helium. 7 levels of the diluted NGA gas are used to perform an injection by the GSV. For each component the concentrations in the dilutions are calculated, and linearity plots are created (see examples below). All calibration lines have a linearity correlation > 0.999.
T C D M ethane, T C D 2 B Area = 1275.5887*Am t +500.98275 Area 100000 80000 60000 40000 20000 0 0
7 65 4 3 2

Dilution Level Cal Gas (ml/min) Helium (ml/min) Dilution factor

2 19.50 19.90

3 10.10 20.00 2.98

4 7.10 20.10 3.83

5 4.00 20.20 6.05

6 3.00 20.40 7.80

7 1.80 20.40 12.33

neat

2.02

Table 3: Dilution table

T C D N itrogen, T C D 2 B Area = 1703.05191*Am t +12.780395 Area 15000 12500 10000 7500 5000 2500
7 4 65 3 2

R el. R es% (3): 7.8402e-1

1

R el. R es% (4): 9.0893e-1

1

C orrelation: 0.99996 50 T C D O xygen, T C D 2 B Area = 1510.25687*Am t -0.360469 Amount[%]

0 0 5

C orrelation: 0.99998 Amount[%]

T C D n-Pentane, T C D 2 B Area = 3586.39408*Am t +2.5398637 Area 1400 1200 1000 800 600 400 200 0 0 R el. R es% (4): 5.3125e-1
1

Area 300 250 200 150 100 50 0 0

R el. R es% (5): -5.9927e-1

1

2 4 7 65 3

2 4 7 65 3

C orrelation: 0.99983 0.1 Amount[%]

C orrelation: 0.99999 0.2 Amount[%]

FID n-Pentane, FID 1 A Area = 2505.67456*Am t -0.1470738 Area 1000 800 600 400 200 0 0 0.2
7 65 4 3 2

FID n-H exane, FID 1 A Area = 2983.40688*Am t -0.2739378 Area

1

R el. R es% (5): 3.1504e-1

R el. R es% (2): -1.563

1

C orrelation: 0.99998 Amount[%]

140 120 100 80 60 40 20 0 0

2 4 7 65 3

C orrelation: 0.99994 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 l of a hydrocarbon test mix is injected on the front channel, using the correct split ratio and temperature program settings (see figure 6 for the chromatogram). The peak retention times and peak areas are recorded by the FID. Response factors are calculated using the exact concentrations of the components. Finally the measured response factors are compared with the theoretical response factors (table 4). It can be concluded that all determined Response Factors are comparable with the theoretical response factors (maximum deviation 0,02).

1200 1000
Benzene C5 C6 C7

Siganl (pA)

800
600 400 200 0 0 5

Toluene C8

C11

C10

C12

10

15 Time (min)

20

C13

C9

C14

25

30

Figure 6: Chromatogram discrimination check reference sample

Component Percentage Weight (gram) 0.32 0.32 0.62 26.11 0.62 0.31 0.31 0.31 0.32 0.31 0.31 0.32 Peak Area pA*s 709.25 712.15 1,541.53 58,389.14 1,518.70 709.39 703.18 705.61 726.57 708.19 692.39 722.30 Area % Response factor 1.50E-05 1.49E-05 1.34E-05 1.48E-05 1.35E-05 1.46E-05 1.46E-05 1.45E-05 1.46E-05 1.45E-05 1.46E-05 1.45E-05 Resp. factor relative to C5 1.00 1.00 0.89 0.99 0.90 0.97 0.97 0.97 0.97 0.97 0.98 0.97 Theoretical Resp. Factor (rel. to C5) 1.00 1.00 0.90 0.99 0.91 0.99 0.99 0.99 0.99 0.98 0.98 0.98

Pentane Hexane Benzene Heptane Toluene Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane

1.06% 1.06% 2.06% 86.54% 2.05% 1.03% 1.02% 1.02% 1.06% 1.03% 1.01% 1.05%

1.046 1.050 2.272 86.071 2.239 1.046 1.037 1.040 1.071 1.044 1.021 1.065

Table 4: Results discrimination test mix

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APPLICATION NOTE
DETECTION AND QUANTIFICATION LIMIT
Detection and quantification limit of each component is calculated using the chromatogram of level 7 ( 12 x diluted) NGA gas. LOD is defined as 3 * standard deviation of the noise, LOQ is defined as 10 * standard deviation of the noise. = 3
Component FID i-Pentane FID n-Pentane FID n-Hexane TCD Propane TCD i-Butane TCD n-Butane TCD Neopentane TCD Carbondioxide TCD Ethane LOD (3x N) < 0.001% < 0.001% < 0.001% < 0.001% < 0.001% < 0.001% < 0.001% < 0.001% < 0.001% < 0.001% < 0.001% < 0.001% Range/Scope covered GPA 2286 0.001-100 % 0.001-100 % 0.001-100 % 0.001-100 % 0.001-100 % 0.001-100 % 0.001-100 % 0.005-100 % 0.001-100 % 0.005-100 % 0.005-100 % 0.001-100 %

10 = Where: N = Noise of signal (pA) C = Concentration of component (ppm) W = Peak width (s) A = Area (pA*s)

TCD Oxygen TCD Nitrogen TCD Methane

Table 5: LOD and LOQ for major Natural gas components

Separation H2S / Propane

550 450 Siganl (pA)
3.871 H2S 4.346 Propane

SEPARATION H2S/PROPANE
H2S elutes just before Propane. The resolution is calculated between the two peaks, based on the retention times en peak width at half height reported by ChemStation. Specification 1.5 (baseline separation).
= 2 1 1 + 2

350 250 150 50

Where: Rt1 = Retention time H2S (min.) Rt2 = Retention time Propane (min.) W1 = Peak width at half height of H2S (min.) W2 = Peak width at half height of Propane (min.) =

-50
2.7 3.7 Time (min) 4.7

4.346 3.871 0.1136 + 0.1069

= 2.15

Figure 7: Overlay of H2S and Propane in Natural gas

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APPLICATION NOTE
CALCULATIONS
The AC NGA GPA 2286 system defines many calculations for the analyst, including calculations established in ASTM D 2421, D 2598, D 3588, ISO 6976 and GPA 2172. Table 6 lists a subset of standard calculations that can be performed using GasXLNC software. To reduce operator involvement, the software contains a standard database of component constants and formulas. A user-friendly edit mode allows authorized users to edit the database. The GasXLNC software includes several standard report formats. In addition, a user can easily create customized reports.
Methane Ethane Propane i-Butane n-Butane i-Pentane n-Pentane

Parameter Liquid volume Liquid vapor pressure Relative density of liquefied petroleum gas (LPG) Compressibility of mixture Real specific gravity at 15.55C (60 F) Real BTU GPM Ideal calorific value on molar basis (inferior and superior) Ideal calorific value on mass basis (inferior and superior) Ideal calorific value on volume basis (inferior and superior) Real calorific value on volume basis (inferior and superior) Ideal & Real wobbe index (superior) Density Table 6: Some of the standard gas calculations available in GasXLNC software

FID Channel

490

390

methyl cyclopentante

n-Hexane

Siganl (pA)

290

Benzene iso-Octane methyl cyclohexane

Cyclohexane

n-Heptane

Toluene

ethyl benzene

90

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

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

n-Octane

190

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meta-xylene

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ortho-xylene n-nonane

para-xylene