The Science Behind Natural Gas Sample Conditioning

The Science Behind Natural Gas Sample Conditioning for On-Line BTU Analysis .
The Importance of the Sample Conditioning System
Figure 1: Typical sample system schematic for “on-line” analyzer
1. The sample conditioning system consists of all the components used to extract a sample
from a source (probe), condition it for compatibility with the analyzer (regulators,
filters, flow meters, etc.), and then transport it from the extraction point to the analyzer
(sample tubing). See Figure 1
2. The objectives of the sample conditioning system are:

a. Deliver a REPRESENTATIVE sample of the actual components being measured in the
gas stream to the analyzer
b. Protect the analyzer
3. A properly designed sample system is the key to analyzer performance and accurate
analysis. If the sample conditioning system is designed incorrectly, it will result in the
largest source of error for the analyzer. Approximately 80% of analytical error can be
attributed to the sample conditioning system.
4. There are several factors that must be considered in the design of the sample
conditioning system:
a. The type of analysis to be performed (BTU, H2S, H20, etc.) & type of analyzer
b. The gas composition (rich vs. lean)
c. The normal amount of contaminant present and types of contaminants
(condensates, amines, glycol, etc.)
d. The pressure and temperature of the source gas
e. The required flow rate to the analyzer
f. Ambient temperature conditions
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Basic Chemistry & Physics

1. The liquid that exists in the pipeline is dynamic and constantly changing forms (aerosols,
droplets, pipe wall film, liquid pool at pipe bottom). The reason that you cannot extract
a representative sample of the gas and the liquid is that only the suspended droplets
would be sampled AND the relationship between the droplets and the total liquid load is
unknown. (See Figure 2)
Figure 2
2. Liquids must be separated because there is no technology available for extracting a gas
sample containing a representative amount of the total liquid load in the line.
3. Vapor/Liquid Equilibrium of a pure substance- When a gas and a liquid consisting of a
single component are in intimate contact at a given pressure and temperature for a
period of time, equilibrium is attained (See Figure 3). When that occurs, the gas phase
is saturated with the liquid vapor. The gas phase is also at its dew point temperature.
An increase in temperature or a decrease in pressure will result in additional liquid
vaporizing thereby increasing its concentration in the gas phase. If the temperature is
decreased or the pressure is increased, some of the vapor will condense and return to the
liquid phase causing a decrease in its concentration in the gas phase.
Figure 3
4. Vapor Liquid Equilibrium of multiple components- A second example is when a gas and
a liquid consisting of multiple components are in intimate contact and equilibrated at a
given pressure and temperature. Each component of the liquid mixture will vaporize to
some degree into the gas phase (See Figure 4). The amount of vapor contributed by
each liquid at that condition depends upon its concentration in the liquid phase and its
volatility.
Figure 4
5. If the gas and liquid mixture temperature is increased and/or its pressure is decreased,
some of the liquid mixture will vaporize thereby increasing the concentration of each
liquid component in the gas phase (See Figure 5). Since the volatility of each
component varies, their concentrations in the gas phase will not increase in direct
proportion to their concentration in the liquid phase. The net result is that the vapor
concentrations of all liquid components will increase in the gas phase. The more volatile
components will increase in greater proportion then the less volatile components.
Therefore, not only will there be an increase of all liquid component concentrations in
the gas phase, but their ratios will also shift.
Figure 5
6. If the gas and liquid temperature is decreased and/or the pressure is increased, the
opposite occurs. Some of the liquid vapor components of the gas phase will condense
thereby decreasing their concentration in the gas phase (See Figure 6). Components will
not condense in equal proportions; therefore their ratio in the gas phase will also shift.
Figure 6
7. It can therefore be stated that when liquid is present in a natural gas sample, a change
in either the temperature and/or the pressure will result in a change of the gas phase
composition. For this reason, it is imperative that liquid is removed at the prevailing
pressure and temperature condition of the source gas.
Natural Gas Industry Standards

1. Natural gas sampling has been performed for years with techniques handed down from
one generation of technicians to another; however, a lot of these sampling techniques
are not sufficient to meet today’s requirements of accuracy and repeatability. Industry
standards have been developed to provide guidelines and bring uniformity to sampling
techniques. Technicians and other personnel who are responsible for overseeing
sampling should be familiar with the techniques described in these standards.
2. There are 2 industry standards pertaining to natural gas sampling:
a. American Petroleum Institute (API): 14.1-- Natural Gas Fluids Measurement
(Collecting & Handling Natural Gas Samples for Custody Transfer)
b. Gas Processors Association (GPA): 2166-05—Obtaining Natural Gas Samples for
Analysis by Gas Chromatography
Both of these standards address sampling of single phase streams, above the hydrocarbon
dew point. They DO NOT address sampling 2 phase streams or supercritical fluids.
3. Some of the guidelines provided in the standards are:
a. Spot , composite, and on-line BTU analysis for single phase streams
b. Exclusion of liquid compounds or contaminants (must be performed under flowing
gas temperature and pressure..can use a phase separation membrane)
c. Heating requirements- Importance of measuring the hydrocarbon dew point and
maintaining the sample above the hydrocarbon dew point
d. Recommended types of sample conditioning components and guidelines on
material of construction (probes, regulators, filters, etc.)
4. Since the standards say that liquid from the source cannot be included in the sample, a
representative natural gas sample is defined as the vapor phase only at source pressure
and source temperature conditions at the point of sampling.
5. When liquids are present in the source, the gas is saturated and at its dew point.
Heating the sample, allowing ambient temperature conditions to warm the sample, or
dropping the pressure (even with an insertion regulator) will vaporize the liquid and
change the gas composition. Allowing the sample to cool will cause condensation and
change the gas composition.
6. In accordance with the standards, the entrained liquid should be separated from the gas
phase under flowing line temperature & pressure conditions with the use of a membrane
tipped probe inserted directly in the source. Sampling in that manner will provide a
sample representing the gas phase composition of the source at its prevailing pressure
and temperature.
7. The membrane on the probe tip is a phase separation membrane, separating liquids from
gases based on the property of surface tension.
8. Once the liquid has been separated, steps to de-saturate the sample can be taken
(pressure reduction & heating). If steps to de-saturate (pressure reduction and heating)
the sample were taken BEFORE liquid was separated at line conditions, the following are
likely to occur:
a. Liquids ( an arbitrary amount) would become vaporized
b. Vapor composition is altered (i.e.-richer)
c. BTU value is increased
d. Physical constants calculated from the composition are incorrect
e. Flow (volume) calculations are incorrect
f. Monetary value assigned to Natural Gas is incorrect
Natural Gas Phase Diagrams

1. Natural gas phase diagrams (P/T diagrams) show the gas/liquid phase relationships at
various pressures and temperatures (See Figure 7). They are a visual tool that is useful
for making decisions in the design, operation, and troubleshooting of the sample
conditioning system.
Figure 7
Adsorption/Desorption Effects
1. Adsorption is the attraction (“sticking”) of gases or liquids to solid surfaces, either
through chemical or physical processes. Desorption is the reverse process.
2. Decreasing the pressure and increasing the temperature will tend to increase the rate of
adsorption, while increasing the temperature and decreasing the pressure tend to reduce
adsorption. (See Figure 8)
Figure 8
3. The fact that the rate of adsorption changes when pressure or temperature changes
means that the composition entering the analyzer could differ from the composition
entering the sample system whenever the adsorption is not in equilibrium.
a. When ambient temperature is stable and the pressure, temperature and
composition of the sample source are all stable, then adsorption in the sample
system will reach an equilibrium and the sample composition that enters the
analyzer will match the composition that enters the sample system.
b. If ambient temperature drops, then adsorption will increase. Some of what enters
the sample system is then adsorbed before it reaches the analyzer; therefore, the
composition that enters the sample system is not the same as the composition
reaching the analyzer until a new adsorption equilibrium is established. Likewise
if the ambient temperature increases, the sample composition that enters the
analyzer will contain molecules that desorb from the interior surfaces of the
sample system and will be different than the composition entering the sample
system, until the adsorption equilibrium is re-established at the new temperature.
c. Even if only the composition changes, the adsorption equilibrium must re-establish
throughout the entire sample system before the composition entering the analyzer
exactly matches the composition entering the sample system. Hence, there is
always a time delay to re-establish sample system equilibrium after a change in
pressure or temperature
4. Adsorption can be pronounced when trying to measure in the ppm range. Heavier
hydrocarbons will be more affected by adsorption than lighter hydrocarbon molecules.
Water is also greatly affected by adsorption.
5. It is best to minimize adsorption effects in order to minimize temp/press sensitivity &
longer equilibrium time after composition changes. Note that when you desaturate the
sample by reducing the pressure and heating, you also reduce adsorption.
6. The cal gas cylinder can experience the same adsorption/desorption affects as the
sample system (as the cylinder heats during the day, molecules will desorb….as the
cylinder cools during the night, molecules will adsorb).
7. If calibration gas is removed when the adsorption/desorption rate is not equilibrated, the
gas phase composition of the cylinder will be changed and the cylinder will no longer be
valid.
8. It is recommended that the a heated cylinder blanket be placed on the cylinder at the
time the cylinder is put in service (before gas is extracted) and that it be allowed to heat
30F above its HCDP for a couple of hours before any gas is pulled out of the cylinder.
a. Adding heat to the cylinder after some of the gas has been extracted could cause
distortion of its gas phase composition. For example, If heavy molecules were
either adsorbed and/or condensed and gas is removed during this time, then
heating the cylinder after gas has been removed could cause the heavy molecules
to desorb and/or vaporize enriching the remaining gas
Joule-Thomson Cooling vs. Latent Heat of Vaporization

1. Joule Thomson Effect- the cooling that occurs when a highly compressed gas is allowed to
expand in such a way that no external work is done
a. It is usually not the cause of condensation because lowering the pressure also
lowers the dew point temperature; however, condensation can occur when a
mixture is at a pressure above the cricondentherm and near the retrograde
portion of the phase envelope.
2. Latent heat of vaporization- the heat required to change a liquid to a gas or vapor,
without a change of temperature.
a. Latent heat of vaporization is the most frequent cause of regulator freeze ups.
Vaporizing liquids requires a lot of energy.
Detecting Liquid
1. The origin of liquid found in any natural gas sample system, sample container, or
analyzer may be either the result of liquid which was entrained in the source gas or
condensation that occurred during the sampling process. Determining the origin of this
liquid is of utmost importance as it determines the proper treatment for the liquid.
2. Detecting liquid is sometimes difficult because we cannot always see it. Some
indications that liquid may be present when we cannot see it are:
a. Erratic gas analysis
b. Disagreement between spot/composite and on-line analysis
c. Valves or pressure regulators freezing up
d. The hydrocarbon dew point temperature of the source gas is above the pipeline
temperature indicates liquid in the source (entrained liquid)
e. The hydrocarbon dew point temperature of the sample gas is above the ambient
temperature indicates liquid condensation is likely occur in the sample system.
References
American Petroleum Institute. Manual of Petroleum Measurement Standards, Chapter 14.1-
Collecting and Handling Natural Gas Samples for Custody Transfer. Washington, D.C.:
American Petroleum Institute, 2006.
Gas Processors Association. GPA Standard 2166-05, Obtaining Natural Gas Samples for
Analysis by Gas Chromatography. Tulsa, OK: Gas Processors Association, 2005.
George, Darin L. The Chemistry and Physics of Natural Gas Sampling and Conditioning.
Proceedings of the Natural Gas Sampling Technology Conference, 2007.
Kelner, Eric and Darin L. George. Lessons Learned from the API 14.1 Gas Sampling Project:
An Overview of Common Causes of Gas Sample Distortion and Information Needed for
Proper Gas Sampling. Proceedings of the American School of Gas Measurement
Technology, 2008.
Mayeaux, Donald P. Fundamentals of Sampling Natural Gas for BTU Determination.
Proceedings of the 84th International School of Hydrocarbon Measurement, 2009.

The Science Behind Natural Gas Sample Conditioning

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The Science Behind Natural Gas Sample Conditioning for On-Line BTU Analysis .

The Importance of the Sample Conditioning System

Figure 1: Typical sample system schematic for “on-line” analyzer

2. The objectives of the sample conditioning system are:

Basic Chemistry & Physics

Natural Gas Industry Standards

Natural Gas Phase Diagrams

Joule-Thomson Cooling vs. Latent Heat of Vaporization

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