Proven On-Site Analysis of Gaseous Fuels With Analytical Laboratory Precision Increases

Productivity and Allows You to Meet Important Schedule Milestones

Mr. Mitchell Martin, Texas OilTech Laboratories, Inc. and
Mr. Jeffrey C. Mocsari, Siemens Westinghouse Power Corporation
High quality on-site analysis of gaseous fuels is now available. Technological advances in the
field of gas analysis have created the opportunity to perform precision tests never before possible
outside of a controlled laboratory setting. Portable, high speed, ultra-sensitive, micro-gas
chromatographs (micro-GCs) allow for the simultaneous analysis of complex gas streams, such
as the natural gas used in gas turbines at the power plant construction site. On-site testing of fuel
will change the way you operate and can save your company time and money.
Fuel gas is almost universally analyzed in accordance with the procedures developed by the
American Society for Testing Materials, specifically Method ASTM D 1945-03, Standard Test
Method for Analysis of Natural Gas by Gas Chromatography. This complex set of instructions
for the analysis of natural gas also details and establishes precision standards for data
repeatability and reproducibility. Most gas turbine manufacturers mandate this test method and
it meets the American Society of Mechanical Engineers, ASME Performance Test Code
requirements for gaseous fuel analysis. Appendix A of this report provides a very basic
overview of the formulae involved in ASME PTC 22-1997: Performance Test Code on Gas
Turbines and ASME PTC 46-1996: Performance Code on Overall Plant Performance. Both
of these codes establish the three basic performance measurements required for the calculation of
thermal efficiency of the engine and the overall plant cycle, i.e., 1) the power output, 2) the rate
of fuel consumption (volumetric or mass basis) (Figure 1) and 3) the heating value of the fuel.
Perhaps the most critical information in determining the efficiency of an engine is the heating
value of the fuel gas. The calculation of fuel heating value (Btu/ft3 or Btu/lbm) requires
knowledge of its molecular composition. In order to achieve this, gas samples are taken in small
high-pressure gas cylinders from the fuel supply-line (Figure 2), or other relevant location, and
shipped to an off-site laboratory for analysis.

Figure 1: This is a typical fuel orifice for measuring the flow of gaseous fuels to a combustion turbine (CT).

Figure 2: This is a typical fuel sampling port. To ensure quality, the cylinder requires pressurization and venting at
least three times before taking the final sample.

Historically, high-quality gas analyses required sophisticated equipment available only in

specially equipped laboratories. The typical instrument setup consists of a large, non-portable
device called the gas chromatograph (GC). The instrument performs a function similar to a
distillation, with separation, detection and measurement of the individual gas components. The
GC is a combination of precision temperature-controlled, insulated ovens (Figure 3). Each oven
contains one or more long, thin tubes, called columns. It is common to have four or more
columns in a typical GC setup. The columns are made from coated fused silica, stainless steel or
special alloys. Since the columns are long, varying from 6 to 30 meters in length, they are coiled

Figure 3. This is a schematic of a typical bench gas chromatograph. It consists of several ovens (in this case four are
depicted) with columns. Two detectors are shown, the TCD and the FID, which are used in conjunction with the
multiple columns and switching valves to acquire the data.

inside the ovens. Each of the columns contains specially designed materials and coatings called
the stationary phase. This provides a suitable surface for the separation of the various
components of the complex natural gas mixture.
A small portion of the plant-site collected gas sample is bled from the cylinder into a specially
designed, rotating sample port. At a given instant, the valve is rotated and a fixed volume of gas
is allowed to enter the instrument. The proper distribution of the sample through the instrument
requires the GC to be equipped with several computer controlled switching and back-flushing
valves. The instrument also contains chemical detectors. Typically, there are two types of
detectors used in gas analysis. The first is a thermal conductivity detector (TCD), normally
called a universal detector, generally used for the non-combustible gases. The second is a flame
ionization detector (FID), which is very sensitive for combustible gases, i.e., hydrocarbons. The
ovens, columns, valves and detectors all work to separate and acquire the data which can then be
quantified and processed with a computer and proprietary software. The process continues with
the determination of the normalized mole percent of each gas component, the heating value and
the specific gravity of the gaseous fuel. The analytical process concludes with the submission of
a final laboratory report to the appropriate plant engineer. Under good circumstances, this
process usually takes one to two days. Often, the logistics of shipping cause delays adding
several days to the process. However, high quality gas analysis no longer requires shipping, and
is no longer limited to the traditional controlled laboratory.
Recent improvements in technology and equipment miniaturization have made high-quality, fast,
on-site analysis of complex gas samples possible through the creation of micro-sized, portable,
solid-state GCs. The micro-GC is capable of performing the same analyses as the large
laboratory instruments. The micro-GC can analyze the fixed gases: oxygen, nitrogen, carbon
dioxide and argon. It can also analyze the fuel gases: hydrogen, carbon monoxide, methane,
ethane, propane, butane, pentane and hydrocarbons greater than hexane (C6+) and their various
isomers.
From this information, the calculated heating values, compressibility factors and
specific gravity of the fuel are computed in accordance with Method ASTM D 3588, Standard
Practice for Calculating Heat Value, Compressibility Factor, and Relative Density of Gaseous
Fuels, just as is done at the main laboratory.
A typical gas fuel analysis on a micro-GC takes 1.5 to 2.5 minutes, depending on the instrument
and conditions. Normally, an on-site analysis is performed two or three times to ensure
repeatability. It is possible to run three or more runs in 10 minutes. Compare this analytical time
to that of the high-quality, laboratory instrumentation, which can take approximately 30 minutes
for a single test.
Numerous comparative evaluations have demonstrated the reliability,
repeatability and reproducibility of the micro-GC and on-site testing techniques. When properly
calibrated using high quality certified reference gases, the micro-GC results are analytically
equivalent to the results obtained in the laboratory. Table 1 presents a comparison of typical onsite test results to those from subsequent analyses performed at the main laboratory. In most
cases, the on-site micro-GC instrument met the same operator, same instrument repeatability
specifications set forth in Method ASTM D 1945 and shown in Table 2. The calculated Gross
Btus per cubic foot were within one Btu. The relative percent differences between the on-site
and main laboratory, as displayed in Table 3, were typically less than 0.05% or less than 1 part
in 2000. When used to determine engine efficiency, there are no significant or practical
differences in these results.

Table 1 - Comparison of On-Site Results with Results from Main Laboratory

1st Day

2nd Day

14th Day

18th Day

Mole %

Mole %

Mole %

Mole %

Hydrogen
Oxygen
Nitrogen
Methane
Carbon Dioxide
Ethane
Propane
Iso-butane
n-Butane
Iso-pentane
n-Pentane
Hexane plus
TOTAL%

0.006
0.000
0.598
94.637
1.701
2.496
0.410
0.052
0.055
0.019
0.007
0.019
100.000

0.002
0.000
0.435
94.617
1.954
2.430
0.415
0.059
0.050
0.018
0.006
0.014
100.000

0.001
0.000
0.443
94.682
1.730
2.532
0.443
0.060
0.058
0.023
0.009
0.019
100.000

0.001
0.000
0.471
94.595
1.706
2.612
0.451
0.058
0.058
0.020
0.007
0.021
100.000

Calculated Btu/ft 3

1015.76

1014.28

1018.29

1018.80

1st Day

2nd Day

14th Day

18th Day

Mole %

Mole %

Mole %

Mole %

Hydrogen
Oxygen
Nitrogen
Methane
Carbon Dioxide
Ethane
Propane
Iso-butane
n-Butane
Iso-pentane
n-Pentane
Hexane plus
TOTAL%

0.006
0.005
0.563
94.553
1.788
2.485
0.415
0.055
0.058
0.020
0.009
0.043
100.000

0.008
0.005
0.398
94.648
1.979
2.390
0.408
0.055
0.052
0.019
0.007
0.031
100.000

0.006
0.005
0.445
94.564
1.776
2.573
0.436
0.065
0.061
0.024
0.010
0.035
100.000

0.003
0.005
0.482
94.458
1.768
2.653
0.443
0.062
0.061
0.022
0.009
0.034
100.000

Calculated Btu/ft 3

1016.31

1014.53

1018.74

1018.97

ON-SITE
RESULTS
PARAMETER

FIXED
LABORATORY
RESULTS
PARAMETER

Table 2 ASTM D 1945: Repeatability and Reproducibility

The difference between two successive results obtained by the same operator with the same
apparatus under constant operating conditions on identical test materials should be considered
suspect if they differ by more than the following amounts:
Repeatability, same operator, same instrument:
Concentration (mol %)
0 to 0.1
0.1 to 1.0
1.0 to 5.0
5.0 to 10
Over 10

Repeatability
0.01
0.04
0.07
0.08
0.10

The difference between two results obtained by different operators in different laboratories on
identical test materials should be considered suspect if they differ by more than the following
amounts:
Reproducibility, different operator, different instrument:
Concentration (mol %)
0 to 0.1
0.1 to 1.0
1.0 to 5.0
5.0 to 10
Over 10

Reproducibility
0.02
0.07
0.10
0.12
0.15

Table 3 - Comparative On-Site versus Fixed Laboratory Reproducibility

Sample
Acquired

On-Site
Results

Main
Laboratory
Results

Btu/ft 3

Absolute
Net Difference
Btu/ft 3

Relative Percent
Difference

Btu/ft 3

A 1st Day

1015.76

1016.31

0.55

0.054

B 2nd Day

1014.28

1014.53

0.24

0.024

C 14th Day

1018.29

1018.74

0.45

0.044

D 18th Day

1018.80

1018.97

0.18

0.017

Average Absolute Net Difference, Btu/ft 3

0.36

Average Relative % Difference

0.035

This accuracy is possible because there are four individual GC modules in one micro-GC
package (Figure 4). The modules contain a silicon micro-injector, a temperature controlled
capillary column and a micro-TCD. Selected stationary phases in each of the individual columns
provide the necessary flexibility to analyze a wide variety of refinery and natural gas samples.
The columns typically are a molecular sieve column (MS5A) for the atmospheric gases and
methane, a PoraPLOT U column (PPU), an Alumina column (Al) and an OV-1 column to
differentiate the lighter and heavier hydrocarbons. The individual systems also contain precolumns with back-flush valves that are capable of venting to the atmosphere, to ensure long-life
and column performance. The back-flush valves also function to reduce the analytical cycle time
on several of the columns, to keep the analytical times short.

Figure 4. This is a schematic of a micro-gas chromatograph. It consists of four individual modules. Each module
contains silicon injectors, pre-columns, columns, valves and micro thermal conductivity detectors.

The micro-GCs analytical precision is improved compared to conventional systems by virtue of

its solid-state construction and by using the same style of injector and detector for each of the
GC modules. The micro-TCD detector system exhibits high analytical repeatability and low
standard deviations. This allows for consistently repeatable results. The micro-GC also has a
phenomenally linear detector response over five orders of magnitude. This allows the micro-GC
to have an extremely accurate linear dynamic range response from 10 ppm to 100 percent for
most analytes. This gives the micro-GC excellent quantitative precision. Table 4 details the
quantitative precision and repeatability of the micro-GC over 50 replicates of a prepared gas
sample. The instrument results are impressive and typically vary by less than 0.5% relative
standard deviation (RSD). Analytically, this means the micro-GC is capable of providing
excellent quality, accurate and timely analyses at the plant site.
Table 4 - Quantitative Precision Over 50 Analyses of Gas*

Component

Column

Mol%

Deviation

Methane
Carbon Monoxide
Ethane
n-Propane
iso-Butane
iso-Pentane
n-Hexane

MS5A
MS5A
PPU
Alumina
OV-1
Alumina
OV-1

4.980
0.997
4.005
2.034
0.300
0.100
0.048

0.0150
0.0020
0.0200
0.0007
0.0007
0.0004
0.0003

*Excerpted from Agilent Technologies, Inc. 5988-6700EN, June 7, 2002

%Relative
Standard
Deviation
0.305
0.238
0.505
0.363
0.246
0.423
0.565

At the plant site, timely and accurate fuel analysis allows key commercial and engineering
decisions to be made before initiating a critical plant start-up test. If an engine or plant is
meeting contractual requirements, then the parties can agree to run an official test. During a
performance test or commissioning trial the on-site micro-GC allows real-time measurement of
the fuel composition, synchronized with the real-time power and fuel flow measurements. This
allows for the immediate calculation of efficiency. Additionally, the fuel composition can be
monitored to detect variations that could adversely affect the out come of the test.
Historically, the normal practice for a typical performance test has been to monitor the power
output and raw fuel flow measurements (line pressure, line temperature, differential pressure,
pulses per time, etc.) in real time. Those values could be reviewed at any time during the test
run. In order to determine the fuel composition, periodic gas samples were taken from the fuel
supply line and they were shipped to an off-site laboratory for analysis. This created a delay in
obtaining the actual fuel composition, and the final calculation of plant efficiency. In many
cases, problems were discovered that invalidated the test, necessitating the scheduling of a retest.
Today, this approach is no longer acceptable.
In some cases, the plant or the gas supplier may have an inline gas chromatograph, which may or
may not be certified or calibrated at the time of a test. If available, the inline-GC data may be
useful for preliminary calculations, but referee analyses of fuel samples are still required.
Equally, during engine tuning, preliminary testing and before an actual test period, data from an
earlier fuel analysis may be used for calculating an estimated performance. However, since fuel
supplies can vary over short periods, particularly for sites with multiple fuel sources, this can
result in a delta greater than 1% between a preliminary fuel analysis and the actual fuel
composition.
Due caution must be exercised when making commercial and engineering
decisions based on old fuel data.
The overall cost for a performance test, or re-test, can exceed $40,000 for instrumentation,
worker support, fuel cost, engine operating hours and plant personnel. Real-time heat rate
calculations obtained from on-site analytical data can prevent parties from entering into an
official test with an error in instrumentation or engine settings that can invalidate the
performance test and force a costly re-test. Many times, on-site testing has permitted personnel
to uncover problems with contract fuel composition; incorrect valve settings; incorrect
thermocouples; incorrect emissions; and even hidden computer/spreadsheet calculation errors.
For example, if the engine or plant is not meeting contractual requirements based on the realtime fuel composition, the test instrumentation and engine operation can be scrutinized for
errors. Adjustments can be made to the engine or plant to improve the performance shortfalls
before initiating an official test. The official test can then be run with a high degree of
confidence and minimal potential for re-tests.
It is apparent that the fuel composition used for performance test calculations is critical to the
accuracy of the final test result. In addition to the actual cost of the test, contract performance
tests determine the transaction of millions of dollars between the equipment supplier and the
customer in the form of final acceptance payments and liquidated damages for performance
shortfalls. Clearly, the value of on-site fuel analysis can far outweigh the increased initial cost
over the historically typical process of off-site lab analysis.

Additionally, in todays political climate, on-site fuel analysis is also recommended, and in some
cases necessitated by the inability to transport gas cylinders. Many international sites experience
difficulties and significant delays when shipping hazardous materials such as compressed gas
fuel samples back to the United States. In some cases where transport to a lab in the USA is not
possible, and the use of domestic laboratories is questionable or unreliable, on-site fuel analysis
is the only viable method for obtaining valid fuel composition analysis.
Companies that have used on-site testing and the engineers responsible for the outcomes of those
tests have been very pleased with the benefits they obtained. Typical benefits include:

determination of real time fuel composition

flexible and increased sampling frequency
greater confidence in test results
discovery of hidden critical problems
timely data reporting
test results to the buyers on the same day
final sign-off with the buyer
minimized necessity for retesting
reduced personnel time at the plant site
flexible reporting format

On-site testing has proven to be a logical approach for providing time-critical and cost-critical
analytical results to the engineers responsible for startups, performance tests and commissioning
trials. The advantages of on-site micro-GC gas analysis are its: speed, accuracy, precision and
reliability.

APPENDIX A
On Site Fuel Gas Analysis: Plant Performance Testing
The composition of fuel consumed during the thermal performance test for a gas turbine engine
(GT) and for a combined cycle plant (CC) is one of the three basic performance measurements
required to determine the thermal efficiency of the engine and overall plant cycle. In North
America, GT thermal performance tests are typically run in accordance with the ASME Test
Code PTC-22-1997 (1). CC thermal performance tests are run per ASME PTC-46-1996 (2). In
both codes thermal efficiency is defined as:
=

Power Output
Heat Input

In North America, Heat Rate (HR) is the working standard for depicting engine and plant
efficiency. Heat rate is the reciprocal of efficiency
HR =

Heat Input
Power Output

For tests run on gaseous fuel, the heat input is determined by

&(HV p ) + SH p
Heat Input = m

where
m&

fuel mass flow rate, typically in lbm/hr

HVp = heating value of fuel at constant pressure, typically in Btu/lbm. Heating value must be
identified as high heat value (HHV) or low heat value (LHV).
SHp = sensible heat at constant pressure in Btu/hr referenced to 60F and 14.696 psia.
The composition of the fuel gas at the time of the test is required to determine the three
parameters used to calculate the Heat Input:

Fuel mass flow rate is measured by a flow meter, typically an orifice meter or a turbine flow
meter. In all cases gas density at the meter is required to determine mass flow rate. The gas
composition is required to determine the molecular weight of the gas and the compressibility
factor, which are required to calculate gas density. (1), (2)

For constant pressure heating value, the composition is required to calculate the heating value
of the gas per ASTM D 3588.

For sensible heat, the composition is required to determine the enthalpy of the fuel gas
mixture.

The micro-GC technology at a site allows real time measurement of the fuel composition, which
directly corresponds to the real time power and fuel flow measurements. This allows for real
time analysis of the heat rate with a high degree of confidence and minimal risk of results
shifting due to incorrect preliminary fuel composition.
Fuel composition can be monitored during the test to detect any variations in fuel composition
and since the micro GC technology meets the ASME Performance Test Code requirements for
gaseous fuel analysis, final performance results can be generated at site shortly after the
completion of the test.
The fuel sampling and analysis process with an onsite analyzer is very similar to the process used
for off-site lab analysis. Fuel samples are taken from the gas supply line in high-pressure sample
cylinders typically used for off site lab analysis. The sample cylinders are processed on site by
the micro-GC and analysis reports are printed upon completion of the analysis. Since the microGC uses a small fraction of the gas sample, the remainder of gas in the cylinders can then be
saved for confirmation of the on-site fuel analyses. Samples may be taken and analyzed every
15 minutes.
References:
(1) ASME PTC 22-1997: Performance Test Code on Gas Turbines, American Society of
Mechanical Engineers, 1997.
(2) ASME PTC 46-1996: Performance Test Code on Overall Plant Performance, American
Society of Mechanical Engineers, 1997.
(3) ASTM D 1945-03: Standard Test Method for Analysis of Natural Gas by Gas
Chromatography, American Society for Testing Materials.
(4) ASTM D 3588-98: Standard Practice for Calculating Heat Value, Compressibility Factor,
and Relative Density of Gaseous Fuels, American Society for Testing Materials.